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Sample records for iron oxide cross-linked

  1. Block Copolymer Cross-linked Nanoassemblies Improve Particle Stability and Biocompatibility of Superparamagnetic Iron Oxide Nanoparticles

    PubMed Central

    Dan, Mo; Scott, Daniel F.; Hardy, Peter A.; Wydra, Robert J.; Hilt, J. Zach; Yokel, Robert A.; Bae, Younsoo

    2014-01-01

    Purpose To develop cross-linked nanoassemblies (CNAs) as carriers for superparamagnetic iron oxide nanoparticles (IONPs). Methods Ferric and ferrous ions were co-precipitated inside core-shell type nanoparticles prepared by cross-linking poly(ethylene glycol)-poly(aspartate) block copolymers to prepare CNAs entrapping Fe3O4 IONPs (CNA-IONPs). Particle stability and biocompatibility of CNA-IONPs were characterized in comparison to citrate-coated Fe3O4 IONPs (Citrate-IONPs). Results CNA-IONPs, approximately 30 nm in diameter, showed no precipitation in water, PBS, or a cell culture medium after 3 or 30 h, at 22, 37, and 43 °C, and 1, 2.5, and 5 mg/mL, whereas Citrate-IONPs agglomerated rapidly (> 400 nm) in all aqueous media tested. No cytotoxicity was observed in a mouse brain endothelial-derived cell line (bEnd.3) exposed to CNA-IONPs up to 10 mg/mL for 30 h. Citrate-IONPs (> 0.05 mg/mL) reduced cell viability after 3 h. CNA-IONPs retained the superparamagnetic properties of entrapped IONPs, enhancing T2-weighted magnetic resonance images (MRI) at 0.02 mg/mL, and generating heat at a mild hyperthermic level (40 ~ 42 °C) with an alternating magnetic field (AMF). Conclusion Compared to citric acid coating, CNAs with a cross-linked anionic core improved particle stability and biocompatibility of IONPs, which would be beneficial for future MRI and AMF-induced remote hyperthermia applications. PMID:23080062

  2. Enhancement of irradiation effects on cancer cells by cross-linked dextran-coated iron oxide (CLIO) nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Fu-Kuo; Chen, Wen-Chang; Lai, Sheng-Feng; Liu, Chi-Jen; Wang, Cheng-Liang; Wang, Chang-Hai; Chen, Hsiang-Hsin; Hua, Tzu-En; Cheng, Yi-Yun; Wu, M. K.; Hwu, Y.; Yang, Chung-Shi; Margaritondo, G.

    2010-01-01

    We investigated iron oxide nanoparticles with two different surface modifications, dextran coating and cross-linked dextran coating, showing that their different internalization affects their capability to enhance radiation damage to cancer cells. The internalization was monitored with an ultrahigh resolution transmission x-ray microscope (TXM), indicating that the differences in the particle surface charge play an essential role and dominate the particle-cell interaction. We found that dextran-coated iron oxide nanoparticles cannot be internalized by HeLa and EMT-6 cells without being functionalized with amino groups (the cross-linked dextran coating) that modify the surface potential from -18 mV to 13.4 mV. The amount of cross-linked dextran-coated iron oxide nanoparticles uptaken by cancer cells reached its maximum, 1.33 × 109 per HeLa cell, when the co-culture concentration was 40 µg Fe mL-1 or more. Standard tests indicated that these internalized nanoparticles increased the damaging effects of x-ray irradiation, whereas they are by themselves biocompatible. These results could lead to interesting therapy applications; furthermore, iron oxide also produces high contrast for magnetic resonance imaging (MRI) in the diagnosis and therapy stages.

  3. Enhancement of irradiation effects on cancer cells by cross-linked dextran-coated iron oxide (CLIO) nanoparticles.

    PubMed

    Huang, Fu-Kuo; Chen, Wen-Chang; Lai, Sheng-Feng; Liu, Chi-Jen; Wang, Cheng-Liang; Wang, Chang-Hai; Chen, Hsiang-Hsin; Hua, Tzu-En; Cheng, Yi-Yun; Wu, M K; Hwu, Y; Yang, Chung-Shi; Margaritondo, G

    2010-01-21

    We investigated iron oxide nanoparticles with two different surface modifications, dextran coating and cross-linked dextran coating, showing that their different internalization affects their capability to enhance radiation damage to cancer cells. The internalization was monitored with an ultrahigh resolution transmission x-ray microscope (TXM), indicating that the differences in the particle surface charge play an essential role and dominate the particle-cell interaction. We found that dextran-coated iron oxide nanoparticles cannot be internalized by HeLa and EMT-6 cells without being functionalized with amino groups (the cross-linked dextran coating) that modify the surface potential from -18 mV to 13.4 mV. The amount of cross-linked dextran-coated iron oxide nanoparticles uptaken by cancer cells reached its maximum, 1.33 x 10(9) per HeLa cell, when the co-culture concentration was 40 microg Fe mL(-1) or more. Standard tests indicated that these internalized nanoparticles increased the damaging effects of x-ray irradiation, whereas they are by themselves biocompatible. These results could lead to interesting therapy applications; furthermore, iron oxide also produces high contrast for magnetic resonance imaging (MRI) in the diagnosis and therapy stages. PMID:20023329

  4. Polyethylene Glycol Modified, Cross-Linked Starch Coated Iron Oxide Nanoparticles for Enhanced Magnetic Tumor Targeting

    PubMed Central

    Cole, Adam J.; David, Allan E.; Wang, Jianxin; Galbán, Craig J.; Hill, Hannah L.; Yang, Victor C.

    2010-01-01

    While successful magnetic tumor targeting of iron oxide nanoparticles has been achieved in a number of models, the rapid blood clearance of magnetically suitable particles by the reticuloendothelial system (RES) limits their availability for targeting. This work aimed to develop a long-circulating magnetic iron oxide nanoparticle (MNP) platform capable of sustained tumor exposure via the circulation and, thus, enhanced magnetic tumor targeting. Aminated, cross-linked starch (DN) and aminosilane (A) coated MNPs were successfully modified with 5 kDa (A5, D5) or 20 kDa (A20, D20) polyethylene glycol (PEG) chains using simple N-Hydroxysuccinimide (NHS) chemistry and characterized. Identical PEG-weight analogues between platforms (A5 & D5, A20 & D20) were similar in size (140–190 nm) and relative PEG labeling (1.5% of surface amines – A5/D5, 0.4% – A20/D20), with all PEG-MNPs possessing magnetization properties suitable for magnetic targeting. Candidate PEG-MNPs were studied in RES simulations in vitro to predict long-circulating character. D5 and D20 performed best showing sustained size stability in cell culture medium at 37°C and 7 (D20) to 10 (D5) fold less uptake in RAW264.7 macrophages when compared to previously targeted, unmodified starch MNPs (D). Observations in vitro were validated in vivo, with D5 (7.29 hr) and D20 (11.75 hr) showing much longer half-lives than D (0.12 hr). Improved plasma stability enhanced tumor MNP exposure 100 (D5) to 150 (D20) fold as measured by plasma AUC0-∞ Sustained tumor exposure over 24 hours was visually confirmed in a 9L-glioma rat model (12 mg Fe/kg) using magnetic resonance imaging (MRI). Findings indicate that both D5 and D20 are promising MNP platforms for enhanced magnetic tumor targeting, warranting further study in tumor models. PMID:21176955

  5. Thermally cross-linked superparamagnetic iron oxide nanoparticles: synthesis and application as a dual imaging probe for cancer in vivo.

    PubMed

    Lee, Haerim; Yu, Mi Kyung; Park, Sangjin; Moon, Sungmin; Min, Jung Jun; Jeong, Yong Yeon; Kang, Hae-Won; Jon, Sangyong

    2007-10-24

    We report the fabrication and characterization of thermally cross-linked superparamagnetic iron oxide nanoparticles (TCL-SPION) and their application to the dual imaging of cancer in vivo. Unlike dextran-coated cross-linked iron oxide nanoparticles, which are prepared by a chemical cross-linking method, TCL-SPION are prepared by a simple, thermal cross-linking method using a Si-OH-containing copolymer. The copolymer, poly(3-(trimethoxysilyl)propyl methacrylate-r-PEG methyl ether methacrylate-r-N-acryloxysuccinimide), was synthesized by radical polymerization and used as a coating material for as-synthesized magnetite (Fe3O4) SPION. The polymer-coated SPION was further heated at 80 degrees C to induce cross-linking between the -Si(OH)3 groups in the polymer chains, which finally generated TCL-SPION bearing a carboxyl group as a surface functional group. The particle size, surface charge, presence of polymer-coating layers, and the extent of thermal cross-linking were characterized and confirmed by various measurements, including dynamic light scattering, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The carboxyl TCL-SPION was converted to amine-modified TCL-SPION and then finally to Cy5.5 dye-conjugated TCL-SPION for use in dual (magnetic resonance/optical) in vivo cancer imaging. When the Cy5.5 TCL-SPION was administered to Lewis lung carcinoma tumor allograft mice by intravenous injection, the tumor was unambiguously detected in T2-weighted magnetic resonance images as a 68% signal drop as well as in optical fluorescence images within 4 h, indicating a high level of accumulation of the nanomagnets within the tumor site. In addition, ex vivo fluorescence images of the harvested tumor and other major organs further confirmed the highest accumulation of the Cy5.5 TCL-SPION within the tumor. It is noteworthy that, despite the fact that TCL-SPION does not bear any targeting ligands on its surface, it was highly effective for tumor

  6. Magnetic brain tumor targeting and biodistribution of long-circulating PEG-modified, cross-linked starch coated iron oxide nanoparticles

    PubMed Central

    Cole, Adam J.; David, Allan E.; Wang, Jianxin; Galbán, Craig J.; Yang, Victor C.

    2011-01-01

    Magnetic iron oxide nanoparticles (MNPs) have been studied to circumvent the limitations of status-quo brain tumor therapy and can be targeted by applying an external magnetic field to lesions. To address the pharmacokinetic challenges of MNPs that can limit targeting efficiency, we recently reported a long-circulating polyethylene glycol modified, cross-linked starch MNP (PEG-MNP) suitable for magnetic targeting. Using a rat model, this work explores the biodistribution patterns of PEG-MNPs in organs of elimination (liver, spleen, lung, and kidney) and shows proof-of-concept that enhanced magnetic brain tumor targeting can be achieved due to improvements in the circulation lifetime of MNPs. Reductions in liver (~12 fold) and spleen (~2.5 fold) concentrations at 1 hr compared to parent starch MNPs (D) confirm plasma pharmacokinetics observed previously. While liver concentrations of PEG-MNPs remained considerably lower than those observed for D at 1 hr throughout their plasma clearance, spleen values continue to increase through and are markedly higher at 12 and 60 hr – a trend also observed with histology. Limited to no uptake of PEG-MNPs was visualized in lung or kidney throughout the 60 hr course evaluated. Enhanced, selective magnetic brain tumor targeting (t = 1 hr, 12 mg Fe/kg) of PEG-MNPs was confirmed in 9L glioma tumors, with upto 1.0% injected dose/g tissue accumulation achieved – a 15-fold improvement over targeted D (0.07% injected dose/g tissue). MRI and histological analyses visually confirmed enhanced PEG-MNP delivery to tumors and also suggest limited passive contribution to tissue retention of nanoparticles. Nonetheless, our results are exciting and justify both further development of PEG-MNP as a drug delivery platform and concurrent optimization of the magnetic brain tumor targeting strategy utilized. PMID:21684593

  7. SIRB, sans iron oxide rhodamine B, a novel cross-linked dextran nanoparticle, labels human neuroprogenitor and SH-SY5Y neuroblastoma cells and serves as a USPIO cell labeling control.

    PubMed

    Shen, Wei-Bin; Vaccaro, Dennis E; Fishman, Paul S; Groman, Ernest V; Yarowsky, Paul

    2016-05-01

    This is the first report of the synthesis of a new nanoparticle, sans iron oxide rhodamine B (SIRB), an example of a new class of nanoparticles. SIRB is designed to provide all of the cell labeling properties of the ultrasmall superparamagnetic iron oxide (USPIO) nanoparticle Molday ION Rhodamine B (MIRB) without containing the iron oxide core. MIRB was developed to label cells and allow them to be tracked by MRI or to be manipulated by magnetic gradients. SIRB possesses a similar size, charge and cross-linked dextran coating as MIRB. Of great interest is understanding the biological and physiological changes in cells after they are labeled with a USPIO. Whether these effects are due to the iron oxide buried within the nanoparticle or to the surface coating surrounding the iron oxide core has not been considered previously. MIRB and SIRB represent an ideal pairing of nanoparticles to identify nanoparticle anatomy responsible for post-labeling cytotoxicity. Here we report the effects of SIRB labeling on the SH-SY5Y neuroblastoma cell line and primary human neuroprogenitor cells (hNPCs). These effects are contrasted with the effects of labeling SH-SY5Y cells and hNPCs with MIRB. We find that SIRB labeling, like MIRB labeling, (i) occurs without the use of transfection reagents, (ii) is packaged within lysosomes distributed within cell cytoplasm, (iii) is retained within cells with no loss of label after cell storage, and (iv) does not alter cellular viability or proliferation, and (v) SIRB labeled hNPCs differentiate normally into neurons or astrocytes. Copyright © 2016 John Wiley & Sons, Ltd.

  8. SIRB, sans iron oxide rhodamine B, a novel cross-linked dextran nanoparticle, labels human neuroprogenitor and SH-SY5Y neuroblastoma cells and serves as a USPIO cell labeling control.

    PubMed

    Shen, Wei-Bin; Vaccaro, Dennis E; Fishman, Paul S; Groman, Ernest V; Yarowsky, Paul

    2016-05-01

    This is the first report of the synthesis of a new nanoparticle, sans iron oxide rhodamine B (SIRB), an example of a new class of nanoparticles. SIRB is designed to provide all of the cell labeling properties of the ultrasmall superparamagnetic iron oxide (USPIO) nanoparticle Molday ION Rhodamine B (MIRB) without containing the iron oxide core. MIRB was developed to label cells and allow them to be tracked by MRI or to be manipulated by magnetic gradients. SIRB possesses a similar size, charge and cross-linked dextran coating as MIRB. Of great interest is understanding the biological and physiological changes in cells after they are labeled with a USPIO. Whether these effects are due to the iron oxide buried within the nanoparticle or to the surface coating surrounding the iron oxide core has not been considered previously. MIRB and SIRB represent an ideal pairing of nanoparticles to identify nanoparticle anatomy responsible for post-labeling cytotoxicity. Here we report the effects of SIRB labeling on the SH-SY5Y neuroblastoma cell line and primary human neuroprogenitor cells (hNPCs). These effects are contrasted with the effects of labeling SH-SY5Y cells and hNPCs with MIRB. We find that SIRB labeling, like MIRB labeling, (i) occurs without the use of transfection reagents, (ii) is packaged within lysosomes distributed within cell cytoplasm, (iii) is retained within cells with no loss of label after cell storage, and (iv) does not alter cellular viability or proliferation, and (v) SIRB labeled hNPCs differentiate normally into neurons or astrocytes. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26809657

  9. Nucleophilic cross-linked, dextran coated iron oxide nanoparticles as basis for molecular imaging: synthesis, characterization, visualization and comparison with previous product.

    PubMed

    Borny, Robert; Lechleitner, Thomas; Schmiedinger, Thomas; Hermann, Martin; Tessadri, Richard; Redhammer, Günther; Neumüller, Josef; Kerjaschki, Dontscho; Berzaczy, Gundula; Erman, Gürkan; Popovic, Martin; Lammer, Johannes; Funovics, Martin

    2015-01-01

    We present a new synthesis protocol for a multivalent, multimodality, nucleophilic nanoparticle ideal for in vivo imaging. Stability requirements necessitated covalent cross-linking of the carbohydrate cage, easy functionalization the introduction of sterically accessible amine groups. The new protocol aimed at more uniform particle size, less clustering and superior magnetic properties compared with commercial nanoparticles. Particles were precipitated from Fe(2+) and Fe(3+) in the presence of 10 kDa dextran monodispersed from the aerosol phase. Cross-linking was achieved with epichlorhydrin, nuclophilication with NH3, purification with ultrafiltration and dialysis. Particles and a commercial product (Rienso®, Takeda Pharma) underwent physicochemical characterizations. Biocompatibility was assessed by Resazurin on LLC-PK1 cells; the internalization rate was measured for three cell lines (HAEC, HASMC, HT29). Core size was 5.61 ± 1.25 nm; hydrodynamic size was 49.56 ± 11.73 nm. The number of sterically accessible amine groups averaged 9.9. The cores showed cubic magnetite structure. Values of r1 and r2 were 10.9 and 148.17 mM(-1) s(-1). Cellular viability was unchanged after incubation. Introduction of aerosol phase dextran resulted in a reduction of the overall hydrodynamic diameter and a narrower size distribution of the synthesized particles. Electron tomography visualized for the first time the postulated 'hairy layer' of the dextran coating and enabled the measurement of the overall diameter of 100.2 ± 7.92 nm. The resulting nanoparticle is biocompatible, functionalizable and detectable at nanomolar concentrations with MRI and optical imaging. It can potentially serve as a platform for multimodal molecular imaging and targeted therapy approaches.

  10. Oxidative protection of hemoglobin and hemerythrin by cross-linking with a nonheme iron peroxidase: potentially improved oxygen carriers for use in blood substitutes.

    PubMed

    Hathazi, Denisa; Mot, Augustin C; Vaida, Anetta; Scurtu, Florina; Lupan, Iulia; Fischer-Fodor, Eva; Damian, Grigore; Kurtz, Donald M; Silaghi-Dumitrescu, Radu

    2014-05-12

    The nonheme peroxidase, rubrerythrin, shows the ability to reduce hydrogen peroxide to water without involving strongly oxidizing and free-radical-creating powerful oxidants such as compounds I and II [formally Fe(IV)] formed in peroxidases and catalases. Rubrerythrin could, therefore, be a useful ingredient in protein-based artificial oxygen carriers. Here, we report that the oxygen-carrying proteins, hemoglobin (Hb) and hemerythrin (Hr), can each be copolymerized with rubrerythrin using glutaraldehyde yielding high molecular weight species. These copolymers show additional peroxidase activity compared to Hb-only and Hr-only polymers, respectively and also generate lower levels of free radicals in reactions that involve hydrogen peroxide. Tests on human umbilical vein endothelial cells (HUVEC) reveal slightly better performance of the Rbr copolymers compared to controls, as measured at 24 h, but not at later times.

  11. New iron pyridylamino-bis(phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates.

    PubMed

    Taherimehr, Masoumeh; Sertã, João Paulo Cardoso Costa; Kleij, Arjan W; Whiteoak, Christopher J; Pescarmona, Paolo P

    2015-03-01

    The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high epoxide conversions. The possibility of controlling the selectivity of the reaction towards either cyclic carbonate or polycarbonate was evaluated. An efficient switch in selectivity could be achieved when cyclic epoxides such as cyclohexene oxide and the seldom explored 1,2-epoxy-4-vinylcyclohexane were used as substrates. The obtained poly(vinylcyclohexene carbonate) presents pending vinyl groups, which allowed post-synthetic cross-linking by reaction with 1,3-propanedithiol. The cross-linked polycarbonate displayed a substantial increase in the glass transition temperature and chemical resistance, thus opening new opportunities for the application of these green polymers. PMID:25688870

  12. New iron pyridylamino-bis(phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates.

    PubMed

    Taherimehr, Masoumeh; Sertã, João Paulo Cardoso Costa; Kleij, Arjan W; Whiteoak, Christopher J; Pescarmona, Paolo P

    2015-03-01

    The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high epoxide conversions. The possibility of controlling the selectivity of the reaction towards either cyclic carbonate or polycarbonate was evaluated. An efficient switch in selectivity could be achieved when cyclic epoxides such as cyclohexene oxide and the seldom explored 1,2-epoxy-4-vinylcyclohexane were used as substrates. The obtained poly(vinylcyclohexene carbonate) presents pending vinyl groups, which allowed post-synthetic cross-linking by reaction with 1,3-propanedithiol. The cross-linked polycarbonate displayed a substantial increase in the glass transition temperature and chemical resistance, thus opening new opportunities for the application of these green polymers.

  13. In Vivo Oxidative Stability Changes of Highly Cross-Linked Polyethylene Bearings: An Ex Vivo Investigation.

    PubMed

    Rowell, Shannon L; Reyes, Christopher R; Malchau, Henrik; Muratoglu, Orhun K

    2015-10-01

    The development of highly cross-linked UHMWPEs focused on stabilizing radiation-induced free radicals as the sole precursor to oxidative degradation. However, secondary in vivo oxidation mechanisms have been discovered. After a preliminary post-operative analysis, we subjected highly cross-linked retrievals with 1-4 years in vivo durations and never-implanted controls to accelerated aging to predict the extent to which their oxidative stability was compromised in vivo. Lipid absorption, oxidation, and hydroperoxides were measured using infrared spectroscopy. Gravimetric swelling was used to measure cross-link density. After aging, all retrievals, except vitamin E-stabilized components, regardless of initial lipid levels or oxidation, showed significant oxidative degradation, demonstrated by subsurface oxidative peaks, increased hydroperoxides and decreased cross-link density, compared to their post-operative material properties and never-implanted counterparts, confirming oxidative stability changes.

  14. The relative contribution of calcium, zinc and oxidation-based cross-links to the stiffness of Arion subfuscus glue.

    PubMed

    Braun, M; Menges, M; Opoku, F; Smith, A M

    2013-04-15

    Metal ions are present in many different biological materials, and are capable of forming strong cross-links in aqueous environments. The relative contribution of different metal-based cross-links was measured in the defensive glue produced by the terrestrial slug Arion subfuscus. This glue contains calcium, magnesium, zinc, manganese, iron and copper. These metals are essential to the integrity of the glue and to gel stiffening. Removal of all metals caused at least a 15-fold decrease in the storage modulus of the glue. Selectively disrupting cross-links involving hard Lewis acids such as calcium reduced the stiffness of the glue, while disrupting cross-links involving borderline Lewis acids such as zinc did not. Calcium is the most common cation bound to the glue (40 mmol l(-1)), and its charge is balanced primarily by sulphate at 82-84 mmol l(-1). Thus these ions probably play a primary role in bringing polymers together directly. Imine bonds formed as a result of protein oxidation also contribute substantially to the stiffness of the glue. Disrupting these bonds with hydroxylamine caused a 33% decrease in storage modulus of the glue, while stabilizing them by reduction with sodium borohydride increased the storage modulus by 40%. Thus a combination of metal-based bonds operates in this glue. Most likely, cross-links directly involving calcium play a primary role in bringing together and stabilizing the polymer network, followed by imine bond formation and possible iron coordination.

  15. Electrospun gelatin nanofibers: a facile cross-linking approach using oxidized sucrose.

    PubMed

    Jalaja, K; James, Nirmala R

    2015-02-01

    Gelatin nanofibers were fabricated via electrospinning with minimal toxicity from solvents and cross-linking agents. Electrospinning was carried out using a solvent system based on water and acetic acid (8:2, v/v). Acetic acid concentration was kept as minimum as possible to reduce the toxic effects. Electrospun gelatin nanofibers were cross-linked with oxidized sucrose. Sucrose was oxidized by periodate oxidation to introduce aldehyde functionality. Cross-linking with oxidized sucrose could be achieved without compromising the nanofibrous architecture. Cross-linked gelatin nanofibers maintained the fibrous morphology even after keeping in contact with aqueous medium. The morphology of the cross-linked nanofibrous mats was examined by scanning electron microscopy (SEM). Oxidized sucrose cross-linked gelatin nanofibers exhibited improved thermal and mechanical properties. The nanofibrous mats were evaluated for cytotoxicity and cell viability using L-929 fibroblast cells. The results confirmed that oxidized sucrose cross-linked gelatin nanofibers were non-cytotoxic towards L-929 cells with good cell viability.

  16. Comparison of Wear and Oxidation in Retrieved Conventional and Highly Cross-Linked UHMWPE Tibial Inserts.

    PubMed

    Currier, Barbara H; Currier, John H; Franklin, Katherine J; Mayor, Michael B; Reinitz, Steven D; Van Citters, Douglas W

    2015-12-01

    Two groups of retrieved tibial inserts from one manufacturer's knee system were analyzed to evaluate the effect of a highly cross-linked bearing surface on wear and in vivo oxidation. The two groups ((1) conventional gamma-inert sterilized and (2) highly cross-linked, coupled with the same rough (Ra=0.25) Ti-6Al-4V tray) were matched with statistically similar in vivo duration and patient variables. The retrieved inserts were analyzed for ketone oxidation and wear in the form of dimensional change. The difference in oxidation rate between highly cross-linked and conventional gamma-inert sterilized inserts did not reach statistical significance. Observations suggest that the majority of wear can be accounted for by the backside interface with the rough Ti-6Al-4V tray; however, wear measured by thickness-change rate was statistically indistinguishable between the two bearing materials.

  17. Endogenous and enhanced oxidative cross-linking in wheat flour mill streams

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The oxidative cross-linking of arabinoxylan and protein polymers is partially responsible for variation in end-use quality of wheat flour; specifically, differences in batter viscosity as well as variation in bread and cookie quality. A better understanding of the variation in oxidative cross-linkin...

  18. Crosslink density, oxidation and chain scission in retrieved, highly cross-linked UHMWPE tibial bearings.

    PubMed

    Reinitz, Steven D; Currier, Barbara H; Levine, Rayna A; Van Citters, Douglas W

    2014-05-01

    Irradiated, thermally stabilized, highly cross-linked UHMWPE bearings have demonstrated superior wear performance and improved in vitro oxidation resistance compared with terminally gamma-sterilized bearings, yet retrieval analysis reveals unanticipated in vivo oxidation in these materials despite fewer or no measurable free radicals. There has been little evidence to date that the oxidation mechanism in thermally stabilized materials is the same as that in conventional materials, and so it is unknown whether oxidation in these materials is leading to chain scission and a degradation of mechanical properties, molecular weight, and crosslink density. The aim of this study was to determine whether measured in vivo oxidation in retrieved, highly cross-linked tibial bearings corresponds with a decreasing crosslink density. Analysis of three tibial bearing materials revealed that crosslink density decreased following in vivo duration, and that the change in crosslink density was strongly correlated with oxidation. The results suggest that oxidation in highly cross-linked materials is causing chain scissions that may, in time, impact the material properties. If in vivo oxidation continues over longer durations, there is potential for a clinically significant degradation of mechanical properties.

  19. Oxidation increases mucin polymer cross-links to stiffen airway mucus gels.

    PubMed

    Yuan, Shaopeng; Hollinger, Martin; Lachowicz-Scroggins, Marrah E; Kerr, Sheena C; Dunican, Eleanor M; Daniel, Brian M; Ghosh, Sudakshina; Erzurum, Serpel C; Willard, Belinda; Hazen, Stanley L; Huang, Xiaozhu; Carrington, Stephen D; Oscarson, Stefan; Fahy, John V

    2015-02-25

    Airway mucus in cystic fibrosis (CF) is highly elastic, but the mechanism behind this pathology is unclear. We hypothesized that the biophysical properties of CF mucus are altered because of neutrophilic oxidative stress. Using confocal imaging, rheology, and biochemical measures of inflammation and oxidation, we found that CF airway mucus gels have a molecular architecture characterized by a core of mucin covered by a web of DNA and a rheological profile characterized by high elasticity that can be normalized by chemical reduction. We also found that high levels of reactive oxygen species in CF mucus correlated positively and significantly with high concentrations of the oxidized products of cysteine (disulfide cross-links). To directly determine whether oxidation can cross-link mucins to increase mucus elasticity, we exposed induced sputum from healthy subjects to oxidizing stimuli and found a marked and thiol-dependent increase in sputum elasticity. Targeting mucin disulfide cross-links using current thiol-amino structures such as N-acetylcysteine (NAC) requires high drug concentrations to have mucolytic effects. We therefore synthesized a thiol-carbohydrate structure (methyl 6-thio-6-deoxy-α-D-galactopyranoside) and found that it had stronger reducing activity than NAC and more potent and fast-acting mucolytic activity in CF sputum. Thus, oxidation arising from airway inflammation or environmental exposure contributes to pathologic mucus gel formation in the lung, which suggests that it can be targeted by thiol-modified carbohydrates. PMID:25717100

  20. Oxidation increases mucin polymer cross-links to stiffen airway mucus gels.

    PubMed

    Yuan, Shaopeng; Hollinger, Martin; Lachowicz-Scroggins, Marrah E; Kerr, Sheena C; Dunican, Eleanor M; Daniel, Brian M; Ghosh, Sudakshina; Erzurum, Serpel C; Willard, Belinda; Hazen, Stanley L; Huang, Xiaozhu; Carrington, Stephen D; Oscarson, Stefan; Fahy, John V

    2015-02-25

    Airway mucus in cystic fibrosis (CF) is highly elastic, but the mechanism behind this pathology is unclear. We hypothesized that the biophysical properties of CF mucus are altered because of neutrophilic oxidative stress. Using confocal imaging, rheology, and biochemical measures of inflammation and oxidation, we found that CF airway mucus gels have a molecular architecture characterized by a core of mucin covered by a web of DNA and a rheological profile characterized by high elasticity that can be normalized by chemical reduction. We also found that high levels of reactive oxygen species in CF mucus correlated positively and significantly with high concentrations of the oxidized products of cysteine (disulfide cross-links). To directly determine whether oxidation can cross-link mucins to increase mucus elasticity, we exposed induced sputum from healthy subjects to oxidizing stimuli and found a marked and thiol-dependent increase in sputum elasticity. Targeting mucin disulfide cross-links using current thiol-amino structures such as N-acetylcysteine (NAC) requires high drug concentrations to have mucolytic effects. We therefore synthesized a thiol-carbohydrate structure (methyl 6-thio-6-deoxy-α-D-galactopyranoside) and found that it had stronger reducing activity than NAC and more potent and fast-acting mucolytic activity in CF sputum. Thus, oxidation arising from airway inflammation or environmental exposure contributes to pathologic mucus gel formation in the lung, which suggests that it can be targeted by thiol-modified carbohydrates.

  1. A strong integrated strength and toughness artificial nacre based on dopamine cross-linked graphene oxide.

    PubMed

    Cui, Wei; Li, Mingzhu; Liu, Jiyang; Wang, Ben; Zhang, Chuck; Jiang, Lei; Cheng, Qunfeng

    2014-09-23

    Demands of the strong integrated materials have substantially increased across various industries. Inspired by the relationship of excellent integration of mechanical properties and hierarchical nano/microscale structure of the natural nacre, we have developed a strategy for fabricating the strong integrated artificial nacre based on graphene oxide (GO) sheets by dopamine cross-linking via evaporation-induced assembly process. The tensile strength and toughness simultaneously show 1.5 and 2 times higher than that of natural nacre. Meanwhile, the artificial nacre shows high electrical conductivity. This type of strong integrated artificial nacre has great potential applications in aerospace, flexible supercapacitor electrodes, artificial muscle, and tissue engineering. PMID:25106494

  2. Oxidized pectin cross-linked carboxymethyl chitosan: a new class of hydrogels.

    PubMed

    Fan, Lihong; Sun, Yi; Xie, Weiguo; Zheng, Hua; Liu, Shuhua

    2012-01-01

    Oxidation of pectin was performed with sodium periodate to prepare pectin dialdehyde (PD). In this study we used the cross-linking reaction of the active aldehyde of PD and the amino of carboxymethyl chitosan (CMC) to prepare the hydrogels. By controlling the proportion of pectin dialdehyde and CMC we made different kinds of hydrogels. We systematically studied the characters of the hydrogels using Fourier transform infrared spectroscopy analysis of the pectin dialdehyde, CMC and the hydrogels, and also X-ray diffractometry and scanning electron microscopy analysis of the instrument of the hydrogels. Equilibrium swelling showed that the gels retained about 88-93% water. The water vapor transmission rate (WVTR) and the evaporation of water from gels showed that such hydrogels were optimal for maintaining a moist environment conducive for wound healing. Examination of the hemolytic potential showed that the hydrogels were nonhemolytic in nature. The hydrogels were non-toxic and blood-compatible. This hydrogel prepared from oxidized pectin and CMC without employing any extraneous cross-linking agents is expected to have potential as wound-dressing material.

  3. Oxidative degradation in highly cross-linked and conventional polyethylene after 2 years of real-time shelf aging.

    PubMed

    Willie, Bettina M; Bloebaum, Roy D; Ashrafi, Shadi; Dearden, Colette; Steffensen, Trina; Hofmann, Aaron A

    2006-04-01

    Previous studies have reported oxidative degradation of conventional polyethylene (PE) components during shelf aging, following radiation. However, no studies have yet reported data concerning the effect of real-time shelf aging in the manufacturer's packaging on the oxidative degradation of commercially available highly cross-linking PE components. The null hypothesis tested was that in either highly cross-linked or conventional PE acetabular components there would be no significant difference in the amount of oxidative degradation between time zero PE liners and PE liners that had been real-time shelf aged for 2 years in their respective packaging. The results of the study indicated that after 2 years of real-time shelf aging, negligible oxidative degradation occurred with minimal changes in oxidation index, density, and percent crystallinity in commercially available highly cross-linked and conventional PE acetabular liners. These data suggested that oxidative degradation was not a clinical issue in the highly cross-linked and conventional PE components examined after 2 years of real-time shelf aging. It is likely that current manufacturing and packaging technologies have limited the previous clinical concerns related to oxidative degradation during shelf aging of highly cross-linked and conventional PE components.

  4. New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean M.; Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

    2005-01-01

    A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

  5. Oxidation-induced unfolding facilitates Myosin cross-linking in myofibrillar protein by microbial transglutaminase.

    PubMed

    Li, Chunqiang; Xiong, Youling L; Chen, Jie

    2012-08-15

    Myofibrillar protein from pork Longissimus muscle was oxidatively stressed for 2 and 24 h at 4 °C with mixed 10 μM FeCl(3)/100 μM ascorbic acid/1, 5, or 10 mM H(2)O(2) (which produces hydroxyl radicals) and then treated with microbial transglutaminase (MTG) (E:S = 1:20) for 2 h at 4 °C. Oxidation induced significant protein structural changes (P < 0.05) as evidenced by suppressed K-ATPase activity, elevated Ca-ATPase activity, increased carbonyl and disulfide contents, and reduced conformational stability, all in a H(2)O(2) dose-dependent manner. The structural alterations, notably with mild oxidation, led to stronger MTG catalysis. More substantial amine reductions (19.8-27.6%) at 1 mM H(2)O(2) occurred as compared to 11.6% in nonoxidized samples (P < 0.05) after MTG treatment. This coincided with more pronounced losses of myosin in oxidized samples (up to 33.2%) as compared to 21.1% in nonoxidized (P < 0.05), which was attributed to glutamine-lysine cross-linking as suggested by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. PMID:22809283

  6. Physiologically relevant oxidative degradation of oligo(proline) cross-linked polymeric scaffolds.

    PubMed

    Yu, Shann S; Koblin, Rachel L; Zachman, Angela L; Perrien, Daniel S; Hofmeister, Lucas H; Giorgio, Todd D; Sung, Hak-Joon

    2011-12-12

    Chronic inflammation-mediated oxidative stress is a common mechanism of implant rejection and failure. Therefore, polymer scaffolds that can degrade slowly in response to this environment may provide a viable platform for implant site-specific, sustained release of immunomodulatory agents over a long time period. In this work, proline oligomers of varying lengths (P(n)) were synthesized and exposed to oxidative environments, and their accelerated degradation under oxidative conditions was verified via high performance liquid chromatography and gel permeation chromatography. Next, diblock copolymers of poly(ethylene glycol) (PEG) and poly(ε-caprolactone) (PCL) were carboxylated to form 100 kDa terpolymers of 4%PEG-86%PCL-10%cPCL (cPCL = poly(carboxyl-ε-caprolactone); i% indicates molar ratio). The polymers were then cross-linked with biaminated PEG-P(n)-PEG chains, where P(n) indicates the length of the proline oligomer flanked by PEG chains. Salt-leaching of the polymeric matrices created scaffolds of macroporous and microporous architecture, as observed by scanning electron microscopy. The degradation of scaffolds was accelerated under oxidative conditions, as evidenced by mass loss and differential scanning calorimetry measurements. Immortalized murine bone-marrow-derived macrophages were then seeded on the scaffolds and activated through the addition of γ-interferon and lipopolysaccharide throughout the 9-day study period. This treatment promoted the release of H(2)O(2) by the macrophages and the degradation of proline-containing scaffolds compared to the control scaffolds. The accelerated degradation was evidenced by increased scaffold porosity, as visualized through scanning electron microscopy and X-ray microtomography imaging. The current study provides insight into the development of scaffolds that respond to oxidative environments through gradual degradation for the controlled release of therapeutics targeted to diseases that feature chronic

  7. Self-Powered Electrochemistry for the Oxidation of Organic Molecules by a Cross-Linked Triboelectric Nanogenerator.

    PubMed

    Zheng, Xin; Su, Jingzhen; Wei, Xianjun; Jiang, Tao; Gao, Shuyan; Wang, Zhong Lin

    2016-07-01

    A cross-linked triboelectric nanogenerator with high performance is designed for the first time, which harvests vibrational energy to self-power the electrochemical oxidation of organic molecules. This system lays the groundwork for applications to an environmentally friendly production of important organic molecules and the waste treatment of organic pollutants. PMID:27145038

  8. Improved stability and cell response by intrinsic cross-linking of multilayers from collagen I and oxidized glycosaminoglycans.

    PubMed

    Zhao, Mingyan; Li, Lihua; Zhou, Changren; Heyroth, Frank; Fuhrmann, Bodo; Maeder, Karsten; Groth, Thomas

    2014-11-10

    Stability of surface coatings against environmental stress, such as pH, high ionic strength, mechanical forces, and so forth, is crucial for biomedical application of implants. Here, a novel extracellular-matrix-like polyelectrolyte multilayer (PEM) system composed of collagen I (Col I) and oxidized glycosaminoglycans (oGAGs) was stabilized by intrinsic cross-linking due to formation of imine bonds between aldehydes of oxidized chondroitin sulfate (oCS) or hyaluronan (oHA) and amino groups of Col I. It was also found that Col I contributed significantly more to overall mass in CS-Col I than in HA-Col I multilayer systems and fibrillized particularly in the presence of native and oxidized CS. Adhesion and proliferation studies with murine C3H10T1/2 embryonic fibroblasts demonstrated that covalent cross-linking of oGAG with Col I had no adverse effects on cell behavior. By contrast, it was found that cell size and polarization was more pronounced on oGAG-based multilayer systems, which corresponded also to the higher stiffness of cross-linked multilayers as observed by studies with quartz crystal microbalance (QCM). Overall, PEMs prepared from oGAG and Col I give rise to stable PEM constructs due to intrinsic cross-linking that may be useful for making bioactive coatings of implants and tissue engineering scaffolds.

  9. Oxidation of Second Generation Sequentially Irradiated and Annealed Highly Cross-Linked X3™ Polyethylene Tibial Bearings.

    PubMed

    Kop, Alan M; Pabbruwe, Moreica B; Keogh, Catherine; Swarts, Eric

    2015-10-01

    Since the first use of ultra-high-molecular-weight polyethylene as a bearing material, research and development efforts have sought to improve wear resistance, increase longevity and lessen the potential for debris mediated adverse tissue responses. A series of second generation sequentially cross-linked and annealed tibial bearings were analysed after several bearings sent for routine retrieval analysis showed oxidative degradation including subsurface whitening, cracking and gross material loss. Evaluation incorporated visual and white banding assessment, mechanical testing and spectroscopy analysis. Whilst visual observation and white banding assessment confirmed oxidative changes, a decrease in mechanical properties and increasing ketone oxidation index as a function of time in vivo suggest time dependent oxidative degradation. Clinically relevant degradation of the sequentially cross-linked and annealed tibial bearings was observed.

  10. Surface-gradient cross-linked polyethylene acetabular cups: oxidation resistance and wear against smooth and rough femoral balls.

    PubMed

    Shen, Fu-Wen; McKellop, Harry

    2005-01-01

    Two methods were developed and evaluated for cross-linking the bearing surface of a polyethylene acetabular cup to a limited depth, in order to improve its resistance to wear without degrading the mechanical properties of the bulk of the component. In the first method, low-energy electron beams were used to cross-link only the bearing surface of the cups to a maximum depth of about 2 mm. The cups then were annealed at 100 degrees C in vacuum for 3 or 6 days to reduce the residual free radicals, and the resultant resistance to oxidation was compared by artificially aging the cups at 80 degrees C in air. Chemically cross-linked surface layers were produced by coating the bearing surfaces of the cups with a thin layer of polyethylene powder mixed with 1% weight peroxide, and compressing them at 6.9 MPa (1000 psi) and 170 degrees C. This resulted in a cross-linked surface layer that extended about 3 mm deep, with a gradual transition to conventional (noncross-linked) polyethylene in the bulk of the implant. In hip simulator wear tests with highly polished (implant quality) femoral balls, both types of surface cross-linking were found to improve markedly the wear resistance of the acetabular cups. In tests with roughened femoral balls, the wear rates were much higher and were comparable to those obtained with similarly roughened balls against noncross-linked polyethylene cups in a previous study, indicating that the full benefit of cross-linking may not be realized under conditions of severe third-body abrasion. Nevertheless, these results show a promising approach for optimizing the wear resistance and the bulk mechanical properties of polyethylene components in total joint arthroplasty.

  11. Nucleotide Excision Repair of Chemically Stabilized Analogues of DNA Interstrand Cross-Links Produced from Oxidized Abasic Sites

    PubMed Central

    2015-01-01

    Nucleotide excision repair is a primary pathway in cells for coping with DNA interstrand cross-links (ICLs). Recently, C4′-oxidized (C4-AP) and C5′-oxidized abasic sites (DOB) that are produced following hydrogen atom abstraction from the DNA backbone were found to produce ICLs. Because some of the ICLs derived from C4-AP and DOB are too unstable to characterize in biochemical processes, chemically stable analogues were synthesized [Ghosh, S., and Greenberg, M. M. (2014) J. Org. Chem.79, 5948–5957]. UvrABC incision of DNA substrates containing stabilized analogues of the ICLs derived from C4-AP and DOB was examined. The incision pattern for the ICL related to the C4′-oxidized abasic site was typical for UvrABC substrates. UvrABC cleaved both strands of the substrate containing the C4-AP ICL analogue, but it was a poor substrate. UvrABC incised <30% of the C4-AP ICL analogue over an 8 h period, raising the possibility that this cross-link will be inefficiently repaired in cells. Furthermore, double-strand breaks were not detected upon incision of an internally labeled hairpin substrate containing the C4-AP ICL analogue. UvrABC incised the stabilized analogue of the DOB ICL more efficiently (∼20% in 1 h). Furthermore, the incision pattern was unique, and the cross-linked substrate was converted into a single product, a double-strand break. The template strand was exclusively incised on the template strand on the 3′-side of the cross-linked dA. Although the outcomes of the interaction between UvrABC and these two cross-linked substrates are different from one another, they provide additional examples of how seemingly simple lesions (C4-AP and DOB) can potentially exert significant deleterious effects on biochemical processes. PMID:25208227

  12. Nucleotide excision repair of chemically stabilized analogues of DNA interstrand cross-links produced from oxidized abasic sites.

    PubMed

    Ghosh, Souradyuti; Greenberg, Marc M

    2014-09-23

    Nucleotide excision repair is a primary pathway in cells for coping with DNA interstrand cross-links (ICLs). Recently, C4'-oxidized (C4-AP) and C5'-oxidized abasic sites (DOB) that are produced following hydrogen atom abstraction from the DNA backbone were found to produce ICLs. Because some of the ICLs derived from C4-AP and DOB are too unstable to characterize in biochemical processes, chemically stable analogues were synthesized [Ghosh, S., and Greenberg, M. M. (2014) J. Org. Chem. 79, 5948-5957]. UvrABC incision of DNA substrates containing stabilized analogues of the ICLs derived from C4-AP and DOB was examined. The incision pattern for the ICL related to the C4'-oxidized abasic site was typical for UvrABC substrates. UvrABC cleaved both strands of the substrate containing the C4-AP ICL analogue, but it was a poor substrate. UvrABC incised <30% of the C4-AP ICL analogue over an 8 h period, raising the possibility that this cross-link will be inefficiently repaired in cells. Furthermore, double-strand breaks were not detected upon incision of an internally labeled hairpin substrate containing the C4-AP ICL analogue. UvrABC incised the stabilized analogue of the DOB ICL more efficiently (~20% in 1 h). Furthermore, the incision pattern was unique, and the cross-linked substrate was converted into a single product, a double-strand break. The template strand was exclusively incised on the template strand on the 3'-side of the cross-linked dA. Although the outcomes of the interaction between UvrABC and these two cross-linked substrates are different from one another, they provide additional examples of how seemingly simple lesions (C4-AP and DOB) can potentially exert significant deleterious effects on biochemical processes.

  13. Study of the Photo-oxidation and Photolysis of Unsaturated and Cross-linked Polyesters (UP) in the Presence of Photoactive or not Inorganic Fillers

    NASA Astrophysics Data System (ADS)

    Khalil, Zahi; Koubaissy, Bachar; Akil, Mariam

    Disturbances of the photochemical evolution involved in the photolysis and in the photo-oxidation at long wavelengths (ë?300 nm) of poly(propylene glycol-maleatophtalate cross-linked by the styrene (UP),caused by the addition of photo-active pigment such as zinc sulphide or black iron oxides,and no photoactive inorganic fillers such as calcium carbonate have been analysed by means of FTIR and U.V. spectrophotometry. The photo-oxidation observed by FTIR of the polymer UP in the presence of inorganic fillers leads to the same photoproducts such as ones of the photo-oxidation of the virgin polymer, but the oxidation rate is greatly affected by the nature and the percentage of the inorganic filler. Zinc sulfide and black iron are incorporated in the film of polymers, the absorption spectra of ZnS reveals that this pigment is not as absorbent as titanium oxide in a more limited field. On the other hand, with a very low inner filter effect, black iron oxides promote the formation of absorbing photoproducts. The addition of Calcium carbonate non- absorbing filler to the UP, causes a slight decrease in the evolution of the I.R

  14. Silicification of genipin-cross-linked polypeptide hydrogels toward biohybrid materials and mesoporous oxides.

    PubMed

    Jan, Jeng-Shiung; Chen, Pei-Shan; Hsieh, Ping-Lun; Chen, Bo-Yu

    2012-12-01

    A simple and versatile approach is proposed to use cross-linked polypeptide hydrogels as templates for silica mineralization, allowing the synthesis of polypeptide-silica hybrid hydrogels and mesoporous silica (meso-SiO(2)) by subsequent calcination. The experimental data revealed that the cross-linked polypeptide hydrogels comprised of interconnected, membranous network served as templates for the high-fidelity transcription of silica replicas spanning from nanoscale to microscale, resulting in hybrid network comprised of interpenetrated polypeptide nanodomains and silica. The mechanical properties of these as-prepared polypeptide-silica hybrid hydrogels were found to vary with polypeptide chain length and composition. The synergy between cross-link, hydrophobic interaction, and silica deposition can lead to the enhancement of their mechanical properties. The polypeptide-silica hybrid hydrogel with polypeptide and silica content as low as 1.1 wt% can achieve 114 kN/m(2) of compressive strength. By removing the polypeptide nanodomains, mesoporous silicas with average pore sizes ranged between 2 nm and 6 nm can be obtained, depending on polypeptide chain length and composition. The polypeptide-silica hybrid hydrogels demonstrated good cell compatibility and can support cell attachment/proliferation. With the versatility of polymer chemistry and feasibility of amine-catalyzed sol-gel chemistry, the present method is facile for the synthesis of green nanocomposites and biomaterials.

  15. The effect of real-time aging on the oxidation and wear of highly cross-linked UHMWPE acetabular liners.

    PubMed

    Wannomae, Keith K; Christensen, Steven D; Freiberg, Andrew A; Bhattacharyya, Shayan; Harris, William H; Muratoglu, Orhun Kamil

    2006-03-01

    Irradiation decreases the wear of ultra-high molecular weight polyethylene (UHMWPE) but generates residual free radicals, precursors to long-term oxidation. Melting or annealing is used in quenching free radicals. We hypothesized that irradiated and once-annealed UHMWPE would oxidize while irradiated and melted UHMWPE would not, and that the oxidation in the former would increase wear. Acetabular liners were real-time aged by immersion in an aqueous environment that closely mimicked the temperature and oxygen concentration of synovial fluid. After 95 weeks of real-time aging, once-annealed components were oxidized; the melted components were not. The wear rate of the real-time aged irradiated and once-annealed components was higher than the literature reported values of other contemporary highly cross-linked UHMWPEs. Single annealing after irradiation used with terminal gamma sterilization may adversely affect the long-term oxidative stability of UHMWPE components.

  16. Dependence of DNA-protein cross-linking via guanine oxidation upon local DNA sequence as studied by restriction endonuclease inhibition.

    PubMed

    Madison, Amanda L; Perez, Zitadel A; To, Phuong; Maisonet, Tiffany; Rios, Eunice V; Trejo, Yuri; Ochoa-Paniagua, Carmen; Reno, Anita; Stemp, Eric D A

    2012-01-10

    Oxidative damage plays a causative role in many diseases, and DNA-protein cross-linking is one important consequence of such damage. It is known that GG and GGG sites are particularly prone to one-electron oxidation, and here we examined how the local DNA sequence influences the formation of DNA-protein cross-links induced by guanine oxidation. Oxidative DNA-protein cross-linking was induced between DNA and histone protein via the flash quench technique, a photochemical method that selectively oxidizes the guanine base in double-stranded DNA. An assay based on restriction enzyme cleavage was developed to detect the cross-linking in plasmid DNA. Following oxidation of pBR322 DNA by flash quench, several restriction enzymes (PpuMI, BamHI, EcoRI) were then used to probe the plasmid surface for the expected damage at guanine sites. These three endonucleases were strongly inhibited by DNA-protein cross-linking, whereas the AT-recognizing enzyme AseI was unaffected in its cleavage. These experiments also reveal the susceptibility of different guanine sites toward oxidative cross-linking. The percent inhibition observed for the endonucleases, and their pBR322 cleavage sites, decreased in the order: PpuMI (5'-GGGTCCT-3' and 5'-AGGACCC-3') > BamHI (5'-GGATCC-3') > EcoRI (5'-GAATTC-3'), a trend consistent with the observed and predicted tendencies for guanine to undergo one-electron oxidation: 5'-GGG-3' > 5'-GG-3' > 5'-GA-3'. Thus, it appears that in mixed DNA sequences the guanine sites most vulnerable to oxidative cross-linking are those that are easiest to oxidize. These results further indicate that equilibration of the electron hole in the plasmid DNA occurs on a time scale faster than that of cross-linking.

  17. Characterization of lysine-guanine cross-links upon one-electron oxidation of a guanine-containing oligonucleotide in the presence of a trilysine peptide.

    PubMed

    Perrier, Sandrine; Hau, Jörg; Gasparutto, Didier; Cadet, Jean; Favier, Alain; Ravanat, Jean-Luc

    2006-05-01

    Formation of DNA-protein cross-links involving the initial formation of a guanine radical cation was investigated. For this purpose, riboflavin-mediated photosensitization of a TGT oligonucleotide in aerated aqueous solution in the presence of the KKK tripeptide was performed. We have shown that the nucleophilic addition of the epsilon-amino group of the central lysine residue of KKK to the C8 atom of either the guanine radical cation or its deprotonated form gives rise to the efficient formation of a Nepsilon-(guanin-8-yl)-lysine cross-link. Interestingly, the time course of formation of the above-mentioned cross-link was found to be not linear with the time of irradiation, and its formation rapidly reached a plateau. This is explained by secondary decomposition of the initially generated cross-link which could be further oxidized more efficiently than starting TGT oligonucleotide. One-electron oxidation of the initially generated cross-link was found to produce mainly two diastereomeric cross-links exhibiting a spiroimino-trilysine-dihydantoin structure as inferred from enzymatic digestion, CD, UV, NMR and mass spectrometry measurements. In addition, other minor cross-links, for which formation was favored at acidic pH, were assigned as lysine-guanine adducts in which the modified guanine base exhibits a guanidino-trilysine-iminohydantoin structure. A proposed mechanism for the formation of the different detected oligonucleotide-peptide cross-links is given. The high yield of formation of the detected cross-links strongly suggests that a DNA-protein cross-link involving a lysine residue linked to the C8 position of guanine could be generated in cellular systems if a lysine is located in the close vicinity of a guanine radical cation.

  18. Thiol oxidation and protein cross-link formation during chill storage of pork patties added essential oil of oregano, rosemary, or garlic.

    PubMed

    Nieto, Gema; Jongberg, Sisse; Andersen, Mogens L; Skibsted, Leif H

    2013-10-01

    The effect of two levels (0.05% and 0.4%) of essential oil of rosemary, oregano, or garlic on protein oxidation in pork patties was studied during storage under modified atmosphere (MAP: 70% O2: 20% CO2: 10% N2) or under aerobic conditions (AE) at 4°C. The oxidative stability of the meat proteins was evaluated as loss of thiols for up to 9 days of storage, and as formation of myosin cross-links analyzed by SDS-PAGE after 12 days of storage. Protein thiols were lost during storage to yield myosin disulfide cross-links. Essential oils of rosemary and oregano were found to retard the loss of thiols otherwise resulting in myosin cross-links. Garlic essential oil, on the contrary, was found to promote protein oxidation, as seen by an extreme loss in thiol groups, and elevated myosin cross-link formation compared to control.

  19. Graphene oxide-immobilized NH₂-terminated silicon nanoparticles by cross-linked interactions for highly stable silicon negative electrodes.

    PubMed

    Sun, Cheng; Deng, Yuanfu; Wan, Lina; Qin, Xusong; Chen, Guohua

    2014-07-23

    There is a great interest in the utilization of silicon-based anodes for lithium-ion batteries. However, its poor cycling stability, which is caused by a dramatic volume change during lithium-ion intercalation, and intrinsic low electric conductivity hamper its industrial applications. A facile strategy is reported here to fabricate graphene oxide-immobilized NH2-terminated silicon nanoparticles (NPs) negative electrode (Si@NH2/GO) directed by hydrogen bonding and cross-linked interactions to enhance the capacity retention of the anode. The NH2-modified Si NPs first form strong hydrogen bonds and covalent bonds with GO. The Si@NH2/GO composite further forms hydrogen bonds and covalent bonds with sodium alginate, which acts as a binder, to yield a stable composite negative electrode. These two chemical cross-linked/hydrogen bonding interactions-one between NH2-modified Si NPs and GO, and another between the GO and sodium alginate-along with highly mechanically flexible graphene oxide, produced a robust network in the negative electrode system to stabilize the electrode during discharge and charge cycles. The as-prepared Si@NH2/GO electrode exhibits an outstanding capacity retention capability and good rate performance, delivering a reversible capacity of 1000 mAh g(-1) after 400 cycles at a current of 420 mA g(-1) with almost 100% capacity retention. The results indicated the importance of system-level strategy for fabricating stable electrodes with improved electrochemical performance.

  20. Abasic and oxidized abasic site reactivity in DNA: enzyme inhibition, cross-linking, and nucleosome catalyzed reactions.

    PubMed

    Greenberg, Marc M

    2014-02-18

    Abasic lesions are a family of DNA modifications that lack Watson-Crick bases. The parent member of this family, the apurinic/apyrimidinic lesion (AP), occurs as an intermediate during DNA repair, following nucleobase alkylation, and from random hydrolysis of native nucleotides. In a given day, each cell produces between 10000 and 50000 AP lesions. A variety of oxidants including γ-radiolysis produce oxidized abasic sites, such as C4-AP, from the deoxyribose backbone. A number of potent, cytotoxic antitumor agents, such as bleomycin and the enediynes (e.g., calicheamicin, esperamicin, and neocarzinostatin) also lead to oxidized abasic sites in DNA. The absence of Watson-Crick bases prevents DNA polymerases from properly determining which nucleotide to incorporate opposite abasic lesions. Consequently, several studies have revealed that (oxidized) abasic sites are highly mutagenic. Abasic lesions are also chemically unstable, are prone to strand scission, and possess electrophilic carbonyl groups. However, researchers have only uncovered the consequences of the inherent reactivity of these electrophiles within the past decade. The development of solid phase synthesis methods for oligonucleotides that both place abasic sites in defined positions and circumvent their inherent alkaline lability has facilitated this research. Chemically synthesized oligonucleotides containing abasic lesions provide substrates that have allowed researchers to discover a range of interesting chemical properties of potential biological importance. For instance, abasic lesions form DNA-DNA interstrand cross-links, a particularly important family of DNA damage because they block replication and transcription absolutely. In addition, bacterial repair enzymes can convert an interstrand cross-link derived from C4-AP into a double-strand break, the most deleterious form of DNA damage. Oxidized abasic lesions can also inhibit DNA repair enzymes that remove damaged nucleotides. DNA polymerase

  1. Flour mill stream blending affects sugar snap cookie and Japanese sponge cake quality and oxidative cross-linking potential of soft white wheat.

    PubMed

    Ramseyer, Daniel D; Bettge, Arthur D; Morris, Craig F

    2011-01-01

    The purpose of this research was to study the functional differences between straight grade (75% extraction rate) and patent (60% extraction rate) flour blends from 28 genetically pure soft white and club wheat grain lots, as evidenced by variation in sugar snap cookie and Japanese sponge cake quality. Functional differences were examined relative to arabinoxylan content, protein content, and oxidative cross-linking potential of flour slurries. Oxidative cross-linking measurements were obtained on flour slurries with a low shear Bostwick consistometer and considered endogenous oxidative cross-linking potential (water alone) or enhanced oxidative cross-linking potential (with added hydrogen peroxide-peroxidase). A 2-way ANOVA indicated that flour blend was the greater source of variation compared to grain lot for all response variables except water-extractable arabinoxylan content. Patent flours produced larger sugar snap cookies and Japanese sponge cakes, and contained significantly less total and water-unextractable arabinoxylans, protein, and ash than did straight grade flours. Patent flours produced more viscous slurries for endogenous and enhanced cross-linking measurements compared to the straight grade flours. The functional differences between patent and straight grade flours appear to be related to the particular mill streams that were utilized in the formulation of the 2 flour blends and compositional differences among those streams.

  2. Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

    PubMed

    Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

    2016-01-01

    Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups. PMID:26502361

  3. Oxidation resistant peroxide cross-linked UHMWPE produced by blending and surface diffusion

    NASA Astrophysics Data System (ADS)

    Gul, Rizwan M.; Oral, Ebru; Muratoglu, Orhun K.

    2014-06-01

    Ultra-high molecular weight polyethylene (UHMWPE) has been widely used as acetabular cup in total hip replacement (THR) and tibial component in total knee replacement (TKR). Crosslinking of UHMWPE has been successful used to improve its wear performance leading to longer life of orthopedic implants. Crosslinking can be performed by radiation or organic peroxides. Peroxide crosslinking is a convenient process as it does not require specialized equipment and the level of crosslinking can be manipulated by changing the amount of peroxide added. However, there is concern about the long-term stability of these materials due to possible presence of by-products. Vitamin E has been successfully used to promote long-term oxidative stability of UHMWPE. In this study, UHMWPE has been crosslinked using organic peroxide in the presence of Vitamin E to produce an oxidation resistant peroxide crosslinked material. Crosslinking was performed both in bulk by mixing peroxide and resin, and only on the surface using diffusion of peroxides.The results show that UHMWPE can be crosslinked using organic peroxides in the presence of vitamin E by both methods. However, the level of crosslinking decreases with the increase in vitamin E content. The wear resistance increases with the increase in crosslink density, and oxidation resistance significantly increases due to the presence of vitamin E.

  4. Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G.; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

    2016-05-01

    Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites.Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical

  5. Reverse osmosis desalination of chitosan cross-linked graphene oxide/titania hybrid lamellar membranes.

    PubMed

    Deng, Hui; Sun, Penzhan; Zhang, Yingjiu; Zhu, Hongwei

    2016-07-01

    With excellent mass transport properties, graphene oxide (GO)-based lamellar membranes are believed to have great potential in water desalination. In order to quantify whether GO-based membranes are indeed suitable for reverse osmosis (RO) desalination, three sub-micrometer thick GO-based lamellar membranes: GO-only, reduced GO (RGO)/titania (TO) nanosheets and RGO/TO/chitosan (CTS) are prepared, and their RO desalination performances are evaluated in a home-made RO test apparatus. The photoreduction of GO by TO improves the salt rejection, which increases slowly with the membrane thickness. The RGO/TO/CTS hybrid membranes exhibit higher rejection rates of only about 30% (greater than threefold improvement compared with a GO-only membrane) which is still inferior compared to other commercial RO membranes. The low rejection rates mainly arise from the pressure-induced weakening of the ion-GO interlayer interactions. Despite the advantages of simple, low-cost preparation, high permeability and selectivity of GO-based lamellar membranes, as the current desalination performances are not high enough to afford practical application, there still remains a great challenge to realize high performance separation membranes for water desalination applications.

  6. Reverse osmosis desalination of chitosan cross-linked graphene oxide/titania hybrid lamellar membranes

    NASA Astrophysics Data System (ADS)

    Deng, Hui; Sun, Penzhan; Zhang, Yingjiu; Zhu, Hongwei

    2016-07-01

    With excellent mass transport properties, graphene oxide (GO)-based lamellar membranes are believed to have great potential in water desalination. In order to quantify whether GO-based membranes are indeed suitable for reverse osmosis (RO) desalination, three sub-micrometer thick GO-based lamellar membranes: GO-only, reduced GO (RGO)/titania (TO) nanosheets and RGO/TO/chitosan (CTS) are prepared, and their RO desalination performances are evaluated in a home-made RO test apparatus. The photoreduction of GO by TO improves the salt rejection, which increases slowly with the membrane thickness. The RGO/TO/CTS hybrid membranes exhibit higher rejection rates of only about 30% (greater than threefold improvement compared with a GO-only membrane) which is still inferior compared to other commercial RO membranes. The low rejection rates mainly arise from the pressure-induced weakening of the ion–GO interlayer interactions. Despite the advantages of simple, low-cost preparation, high permeability and selectivity of GO-based lamellar membranes, as the current desalination performances are not high enough to afford practical application, there still remains a great challenge to realize high performance separation membranes for water desalination applications.

  7. Reverse osmosis desalination of chitosan cross-linked graphene oxide/titania hybrid lamellar membranes

    NASA Astrophysics Data System (ADS)

    Deng, Hui; Sun, Penzhan; Zhang, Yingjiu; Zhu, Hongwei

    2016-07-01

    With excellent mass transport properties, graphene oxide (GO)-based lamellar membranes are believed to have great potential in water desalination. In order to quantify whether GO-based membranes are indeed suitable for reverse osmosis (RO) desalination, three sub-micrometer thick GO-based lamellar membranes: GO-only, reduced GO (RGO)/titania (TO) nanosheets and RGO/TO/chitosan (CTS) are prepared, and their RO desalination performances are evaluated in a home-made RO test apparatus. The photoreduction of GO by TO improves the salt rejection, which increases slowly with the membrane thickness. The RGO/TO/CTS hybrid membranes exhibit higher rejection rates of only about 30% (greater than threefold improvement compared with a GO-only membrane) which is still inferior compared to other commercial RO membranes. The low rejection rates mainly arise from the pressure-induced weakening of the ion-GO interlayer interactions. Despite the advantages of simple, low-cost preparation, high permeability and selectivity of GO-based lamellar membranes, as the current desalination performances are not high enough to afford practical application, there still remains a great challenge to realize high performance separation membranes for water desalination applications.

  8. Reverse osmosis desalination of chitosan cross-linked graphene oxide/titania hybrid lamellar membranes.

    PubMed

    Deng, Hui; Sun, Penzhan; Zhang, Yingjiu; Zhu, Hongwei

    2016-07-01

    With excellent mass transport properties, graphene oxide (GO)-based lamellar membranes are believed to have great potential in water desalination. In order to quantify whether GO-based membranes are indeed suitable for reverse osmosis (RO) desalination, three sub-micrometer thick GO-based lamellar membranes: GO-only, reduced GO (RGO)/titania (TO) nanosheets and RGO/TO/chitosan (CTS) are prepared, and their RO desalination performances are evaluated in a home-made RO test apparatus. The photoreduction of GO by TO improves the salt rejection, which increases slowly with the membrane thickness. The RGO/TO/CTS hybrid membranes exhibit higher rejection rates of only about 30% (greater than threefold improvement compared with a GO-only membrane) which is still inferior compared to other commercial RO membranes. The low rejection rates mainly arise from the pressure-induced weakening of the ion-GO interlayer interactions. Despite the advantages of simple, low-cost preparation, high permeability and selectivity of GO-based lamellar membranes, as the current desalination performances are not high enough to afford practical application, there still remains a great challenge to realize high performance separation membranes for water desalination applications. PMID:27232262

  9. Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films.

    PubMed

    Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

    2016-05-19

    Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ∼160% compared to pristine chitosan, whereas their oxygen permeability reduces by ∼90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites. PMID:27168418

  10. Removal of direct dyes from aqueous solution by oxidized starch cross-linked chitosan/silica hybrid membrane.

    PubMed

    He, Xuemei; Du, Mei; Li, Hui; Zhou, Tianchi

    2016-01-01

    In this research, chitosan/oxidized starch/silica (CS/OSR/Silica) hybrid membrane was prepared by using oxidized starch and 3-aminopropyltriethoxysilane (APTES) as cross-linking agents. The characterizations of the hybrid membrane were investigated by using attenuated total reflection (ATR) spectroscopy, scanning electron microscopy (SEM), thermogravimetry (TG) analysis and swelling measurement. The CS/OSR/Silica hybrid membrane exhibited the improved thermal stability and low degree of swelling in water. The adsorption properties of the CS/OSR/Silica hybrid membrane were studied by using two direct dyes (Blue 71 and Red 31). The results indicated the adsorption capacity of the CS/OSR/Silica hybrid membrane was found optimal at pH 9.82 and temperature 60°C for Blue 71 and Red 31. The adsorption kinetic data followed pseudo-second order kinetic model and the adsorption behavior of the two dyes on the hybrid membrane fitted well with the Freundlich model. The CS/OSR/Silica hybrid membrane can be used as an appropriate biosorbent for removal of direct dyes from colored wastewater.

  11. Cross-linked gelatin/nanoparticles composite coating on micro-arc oxidation film for corrosion and drug release

    NASA Astrophysics Data System (ADS)

    Xu, Xinhua; Lu, Ping; Guo, Meiqing; Fang, Mingzhong

    2010-02-01

    A composite coating which could control drug release and biocorrosion of magnesium alloy stent materials WE42 was prepared. This composite coating was fabricated on the surface of the micro-arc oxidation (MAO) film of the magnesium alloy, WE42, by mixing different degrees of cross-linked gelatin with well-dispersed poly( DL-lactide-co-glycolide) (PLGA) nanoparticles. The PLGA nanoparticles were prepared by emulsion solvent evaporation/extraction technique. Nano ZS laser diffraction particle size analyzer detected that the size of the nanoparticles to be 150-300 nm. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) was used to analyze the morphology of the nanoparticles and the composite coating. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion behavior of the composite coating. Drug release was determined by ultraviolet-visible (UV-vis) spectrophotometer. The corrosion resistance of the composite coating was improved by preventing the corrosive ions from diffusing to the MAO films. The drug release rate of paclitaxel (PTX) exhibited a nearly linear sustained-release profile with no significant burst releases.

  12. pH-dependent cross-linking of catechols through oxidation via Fe(3+) and potential implications for mussel adhesion.

    PubMed

    Fullenkamp, Dominic E; Barrett, Devin G; Miller, Dusty R; Kurutz, Josh W; Messersmith, Phillip B

    2014-01-01

    The mussel byssus is a remarkable attachment structure that is formed by injection molding and rapid in-situ hardening of concentrated solutions of proteins enriched in the catecholic amino acid 3,4-dihydroxy-L-phenylalanine (DOPA). Fe(3+), found in high concentrations in the byssus, has been speculated to participate in redox reactions with DOPA that lead to protein polymerization, however direct evidence to support this hypothesis has been lacking. Using small molecule catechols, DOPA-containing peptides, and native mussel foot proteins, we report the first direct observation of catechol oxidation and polymerization accompanied by reduction of Fe(3+) to Fe(2+). In the case of the small molecule catechol, we identified two dominant dimer species and characterized their connectivities by nuclear magnetic resonance (NMR), with the C6-C6 and C5-C6 linked species as the major and minor products, respectively. For the DOPA-containing peptide, we studied the pH dependence of the reaction and demonstrated that catechol polymerization occurs readily at low pH, but is increasingly diminished in favor of metal-catechol coordination interactions at higher pH. Finally, we demonstrate that Fe(3+) can induce cross-links in native byssal mussel proteins mefp-1 and mcfp-1 at acidic pH. Based on these findings, we discuss the potential implications to the chemistry of mussel adhesion.

  13. Reactive electrospinning of composite nanofibers of carboxymethyl chitosan cross-linked by alginate dialdehyde with the aid of polyethylene oxide.

    PubMed

    Zhao, Xiujuan; Chen, Si; Lin, Zifeng; Du, Chang

    2016-09-01

    We have prepared carboxymethyl chitosan-alginate dialdehyde (CMCS-ADA) nanofibers via a reactive electrospinning process with the aid of polyethylene oxide (PEO). The presence of PEO delayed the gelation of CMCS and ADA, thus providing ease of use to adjust the mixing of CMCS-PEO and ADA-PEO blended solution. The mixed solution can be adjusted to come out from the needle before the gel formation or when the gel was just about to form. Defect-free CMCS-ADA-PEO nanofibers with average diameters ranging from 100nm to 900nm were obtained using water as a solvent. The in situ cross-linked CMCS-ADA nanofibers were then obtained following the extraction of water-soluble PEO. After immersion in phosphate-buffered saline (PBS) at a pH of 7.4 for up to 15days, the as-spun CMCS-ADA-PEO composite nanofibers maintained structural integrity, confirming the success of the crosslinking. The PEO-extracted CMCS-ADA nanofibers promoted the adhesion, proliferation and alkaline phosphatase activity of bone marrow stromal cells. PMID:27185120

  14. pH-dependent cross-linking of catechols through oxidation via Fe(3+) and potential implications for mussel adhesion.

    PubMed

    Fullenkamp, Dominic E; Barrett, Devin G; Miller, Dusty R; Kurutz, Josh W; Messersmith, Phillip B

    2014-01-01

    The mussel byssus is a remarkable attachment structure that is formed by injection molding and rapid in-situ hardening of concentrated solutions of proteins enriched in the catecholic amino acid 3,4-dihydroxy-L-phenylalanine (DOPA). Fe(3+), found in high concentrations in the byssus, has been speculated to participate in redox reactions with DOPA that lead to protein polymerization, however direct evidence to support this hypothesis has been lacking. Using small molecule catechols, DOPA-containing peptides, and native mussel foot proteins, we report the first direct observation of catechol oxidation and polymerization accompanied by reduction of Fe(3+) to Fe(2+). In the case of the small molecule catechol, we identified two dominant dimer species and characterized their connectivities by nuclear magnetic resonance (NMR), with the C6-C6 and C5-C6 linked species as the major and minor products, respectively. For the DOPA-containing peptide, we studied the pH dependence of the reaction and demonstrated that catechol polymerization occurs readily at low pH, but is increasingly diminished in favor of metal-catechol coordination interactions at higher pH. Finally, we demonstrate that Fe(3+) can induce cross-links in native byssal mussel proteins mefp-1 and mcfp-1 at acidic pH. Based on these findings, we discuss the potential implications to the chemistry of mussel adhesion. PMID:25243062

  15. Model reactions for insect cuticle sclerotization: cross-linking of recombinant cuticular proteins upon their laccase-catalyzed oxidative conjugation with catechols.

    PubMed

    Suderman, Richard J; Dittmer, Neal T; Kanost, Michael R; Kramer, Karl J

    2006-04-01

    The quinone-tanning hypothesis for insect cuticle sclerotization proposes that N-acylcatecholamines are oxidized by a phenoloxidase to quinones and quinone methides, which serve as electrophilic cross-linking agents to form covalent cross-links between cuticular proteins. We investigated model reactions for protein cross-linking that occurs during insect cuticle sclerotization using recombinant pupal cuticular proteins from the tobacco hornworm, Manduca sexta, fungal or recombinant hornworm laccase-type phenoloxidase, and the cross-linking agent precursor N-acylcatecholamines, N-beta-alanydopamine (NBAD) or N-acetyldopamine (NADA). Recombinant M. sexta pupal cuticular proteins MsCP36, MsCP20, and MsCP27 were expressed and purified to near homogeneity. Polyclonal antisera to these recombinant proteins recognized the native proteins in crude pharate brown-colored pupal cuticle homogenates. Furthermore, antisera to MsCP36, which contains a type-1 Rebers and Riddiford (RR-1) consensus sequence, also recognized an immunoreactive protein in homogenates of larval head capsule exuviae, indicating the presence of an RR-1 cuticular protein in a very hard, sclerotized and nonpigmented cuticle. All three of the proteins formed small and large oligomers stable to boiling SDS treatment under reducing conditions after reaction with laccase and the N-acylcatecholamines. The optimal reaction conditions for MsCP36 polymerization were 0.3mM MsCP36, 7.4mM NBAD and 1.0U/mul fungal laccase. Approximately 5-10% of the monomer reacted to yield insoluble oligomers and polymers during the reaction, and the monomer also became increasingly insoluble in SDS solution after reaction with the oxidized NBAD. When NADA was used instead of NBAD, less oligomer formation occurred, and most of the protein remained soluble. Radiolabeled NADA became covalently bound to the MsCP36 monomer and oligomers during cross-linking. Recombinant Manduca laccase (MsLac2) also catalyzed the polymerization of MsCP36

  16. Protein oxidation at different salt concentrations affects the cross-linking and gelation of pork myofibrillar protein catalyzed by microbial transglutaminase.

    PubMed

    Li, Chunqiang; Xiong, Youling L; Chen, Jie

    2013-06-01

    In a fabricated then restructured meat product, protein gelation plays an essential role in producing desirable binding and fat-immobilization properties. In the present study, myofibrillar protein (MFP) suspended in 0.15, 0.45, and 0.6 M NaCl was subjected to hydroxyl radical stress for 2 or 24 h and then treated with microbial transglutaminase (MTGase) in 0.6 M NaCl (E : S = 1 : 20) at 4 and 15 °C for 2 h. Protein cross-linking and dynamic rheological tests were performed to assess the efficacy of MTGase for mediating the gelation of oxidized MFP. MTGase treatments affected more remarkable polymerization of myosin in oxidized MFP than in nonoxidized, especially for samples oxidized at 0.6 M NaCl. Notably, the extent of MTGase-induced myosin cross-linking at 15 °C in oxidized MFP improved up to 46.8%, compared to 31.6% in nonoxidized MFP. MTGase treatment at 4 °C for MFP oxidized in 0.6 M NaCl, but not MFP oxidized in 0.15 M NaCl, produced stronger gels than nonoxidized MFP (P < 0.05). The final (75 °C) storage modulus (G') of oxidized MFP gels was significantly greater than that of nonoxidized, although the G' of the transient peak (∼44.5 °C) showed the opposite trend. Overall, oxidation at high salt concentrations significantly improved MTGase-mediated myosin cross-linking and MFP gelation. This might be because under this condition, MTGase had an increased accessibility to glutamine and lysine residues to effectively initiate protein-protein interactions and gel network formation. PMID:23627930

  17. Pro-oxidant effects of cross-linked haemoglobins explored using liposome and cytochrome c oxidase vesicle model membranes.

    PubMed Central

    Rogers, M S; Patel, R P; Reeder, B J; Sarti, P; Wilson, M T; Alayash, A I

    1995-01-01

    The therapeutic use of cell-free haemoglobin as a blood substitute has been hampered by toxicological effects. A model asolectin (phosphatidylcholine/phosphatidylethanolamine) liposome system was utilized to study the pro-oxidant efficiency of several chemically modified haemoglobins on biological membranes. Lipid peroxidation, resulting from the interactions between haemoglobin and liposomes, was measured by conjugated diene formation and the maximal rates of oxygen uptake. Spectral changes gave insight into the occurrence of the ferryl iron species. The residual reactivity of oxidatively damaged haemoglobins with ligands during incubation with liposomes was assessed from rapid kinetic carbon monoxide-binding experiments. Liposomes in which cytochrome c oxidase was embedded show both haemoglobin and the enzyme to be oxidatively damaged during incubation. The functional state of cytochrome c oxidase was monitored in the presence and absence of a free radical scavenger. Once in contact, both unmodified and modified haemoglobins triggered and maintained severe radical-mediated membrane damage. Differences in the pro-oxidant activities among haemoglobins may be explained by either the differential population of their ferryl intermediates or disparate dimerization and transfer of haem into the membrane with subsequent haem degradation. This study may contribute to a better understanding of the molecular determinants of haemoglobin interactions with a variety of biological membranes. Images Figure 2 PMID:7575415

  18. Oxidation in ultrahigh molecular weight polyethylene and cross-linked polyethylene acetabular cups tested against roughened femoral heads in a hip joint simulator.

    PubMed

    Taddei, Paola; Affatato, Saverio; Fagnano, Concezio; Toni, Aldo

    2006-06-01

    This study was aimed at comparing the oxidative degradation of commercial acetabular cups made of cross-linked polyethylene (XLPE) and conventional ultrahigh molecular weight polyethylene (UHMWPE). After testing against deliberately scratched CoCrMo femoral heads in a hip joint simulator, the cups, microtomed parallel to the articulating surface, were analyzed by IR spectroscopy. Due to the potential for artifacts caused by absorbed contaminants, the IR spectra were compared only after hexane extraction; actually, XLPE was found to absorb more serum than UHMWPE. The two sets of unworn acetabular cups showed different oxidation patterns with consequently different distributions of carbonyl species; unworn XLPE was characterized by lower contents of carbonyl species and hydrogen-bonded alcohols and higher contents of trans-vinylene species than unworn UHMWPE. Upon simulator testing, UHMWPE showed more significant changes in oxidation indexes and distribution of carbonyl compounds than XLPE, confirming a better wear behavior for XLPE under the adopted testing conditions.

  19. Mutagenic Bypass of an Oxidized Abasic Lesion-Induced DNA Interstrand Cross-Link Analogue by Human Translesion Synthesis DNA Polymerases.

    PubMed

    Xu, Wenyan; Ouellette, Adam; Ghosh, Souradyuti; O'Neill, Tylor C; Greenberg, Marc M; Zhao, Linlin

    2015-12-22

    5'-(2-Phosphoryl-1,4-dioxobutane) (DOB) is an oxidized abasic site that is produced by several antitumor agents and γ-radiolysis. DOB reacts reversibly with a dA opposite the 3'-adjacent nucleotide to form DNA interstrand cross-links (ICLs), genotoxic DNA lesions that can block DNA replication and transcription. Translesion synthesis (TLS) is an important step in several ICL repair pathways to bypass unhooked intermediates generated by endonucleolytic incision. The instability of DOB-ICLs has made it difficult to learn about their TLS-mediated repair capability and mutagenic potential. We recently developed a method for chemically synthesizing oligonucleotides containing a modified DOB-ICL analogue. Herein, we examined the capabilities of several highly relevant eukaryotic TLS DNA polymerases (pols), including human pol η, pol κ, pol ι, pol ν, REV1, and yeast pol ζ, to bypass this DOB-ICL analogue. The prelesion, translesion, and postlesion replication efficiency and fidelity were examined. Pol η showed moderate bypass activity when encountering the DOB-ICL, giving major products one or two nucleotides beyond the cross-linked template nucleotide. In contrast, DNA synthesis by the other pols was stalled at the position before the cross-linked nucleotide. Steady-state kinetic data and liquid chromatography-mass spectrometry sequencing of primer extension products by pol η unambiguously revealed that pol η-mediated bypass is highly error-prone. Together, our study provides the first set of in vitro evidence that the DOB-ICL is a replication-blocking and highly miscoding lesion. Compared to several other TLS pols examined, pol η is likely to contribute to the TLS-mediated repair of the DOB-ICL in vivo.

  20. Engineering Intracellular Delivery Nanocarriers and Nanoreactors from Oxidation-Responsive Polymersomes via Synchronized Bilayer Cross-Linking and Permeabilizing Inside Live Cells.

    PubMed

    Deng, Zhengyu; Qian, Yinfeng; Yu, Yongqiang; Liu, Guhuan; Hu, Jinming; Zhang, Guoying; Liu, Shiyong

    2016-08-24

    Reactive oxygen species (ROS) and oxidative stress are implicated in various physiological and pathological processes, and this feature provides a vital biochemical basis for designing novel therapeutic and diagnostic nanomedicines. Among them, oxidation-responsive micelles and vesicles (polymersomes) of amphiphilic block copolymers have been extensively explored; however, in previous works, oxidation by ROS including H2O2 exclusively leads to microstructural destruction of polymeric assemblies. For oxidation-responsive polymersomes, fast release of encapsulated hydrophilic drugs and bioactive macromolecules will occur upon microstructural disintegration. Under certain application circumstances, this does not meet design requirements for sustained-release drug nanocarriers and long-acting in vivo nanoreactors. Also note that conventional polymersomes possess thick hydrophobic bilayers and compromised membrane permeability, rendering them as ineffective nanocarriers and nanoreactors. We herein report the fabrication of oxidation-responsive multifunctional polymersomes exhibiting intracellular milieu-triggered vesicle bilayer cross-linking, permeability switching, and enhanced imaging/drug release features. Mitochondria-targeted H2O2 reactive polymersomes were obtained through the self-assembly of amphiphilic block copolymers containing arylboronate ester-capped self-immolative side linkages in the hydrophobic block, followed by surface functionalization with targeting peptides. Upon cellular uptake, intracellular H2O2 triggers cascade decaging reactions and generates primary amine moieties; prominent amidation reaction then occurs within hydrophobic bilayer membranes, resulting in concurrent cross-linking and hydrophobic-to-hydrophilic transition of polymersome bilayers inside live cells. This process was further utilized to achieve integrated functions such as sustained drug release, (combination) chemotherapy monitored by fluorescence and magnetic resonance (MR

  1. Optical properties and oxidation of carbonized and cross-linked structures formed in polycarbonate by plasma immersion ion implantation

    NASA Astrophysics Data System (ADS)

    Kosobrodova, E.; Kondyurin, A.; Chrzanowski, W.; McCulloch, D. G.; McKenzie, D. R.; Bilek, M. M. M.

    2014-06-01

    At ion fluences higher than 5 · 1015 ions/cm2, plasma immersion ion implantation (PIII) of polycarbonate (PC) results in a formation of a carbonized surface layer. The thickness of this layer is close to the depth of ion penetration. A comparison of PIII treated, spin-coated PC films with pre-treatment thicknesses designed to match and exceed the carbonized layer thickness is employed to study the properties of the carbonised layer independently from the less modified underlying structure. At ion fluencies higher than 1016 ions/cm2, the thinner PC film is completely transformed into an amorphous carbon-like material with no traces of the initial PC structure. The thicker films, however, incorporated two layers: a top carbonised layer and a cross-linked layer below. Compared to the two-layered PC film, the completely carbonized layer was found to have a much higher concentration of Cdbnd O bonds and much lower concentration of O-H bonds after exposure to atmospheric oxygen. The refractive index of the thicker PC films PIII treated with high ion fluencies is close to the refractive index of diamond-like carbon. Anomalous dispersion of the refractive index of the thicker PC films is observed after formation of the carbonised layer. The refractive index of the thinner PC film has normal dispersion at all ion fluences. At ion fluences of 2 · 1016 ions/cm2, both PC films were found to have the same etching rate as polystyrene. Washing in dichloromethane had no effect on the carbonised layer but affected the underlying material in the case of the thicker PC films leading to a wrinkled structure up to ion fluences of 2 · 1016 ions/cm2. At this and higher fluence, areas of an ordered island-like structure were observed.

  2. Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries.

    PubMed

    Khurana, Rachna; Schaefer, Jennifer L; Archer, Lynden A; Coates, Geoffrey W

    2014-05-21

    Solid polymer electrolyte (SPE) membranes are a critical component of high specific energy rechargeable Li-metal polymer (LMP) batteries. SPEs exhibit low volatility and thus increase the safety of Li-based batteries compared to current state-of-the-art Li-ion batteries that use flammable small-molecule electrolytes. However, most SPEs exhibit low ionic conductivity at room temperature, and often allow the growth of lithium dendrites that short-circuit the batteries. Both of these deficiencies are significant barriers to the commercialization of LMP batteries. Herein we report a cross-linked polyethylene/poly(ethylene oxide) SPE with both high ionic conductivity (>1.0 × 10(-4) S/cm at 25 °C) and excellent resistance to dendrite growth. It has been proposed that SPEs with shear moduli of the same order of magnitude as lithium could be used to suppress dendrite growth, leading to increased lifetime and safety for LMP batteries. In contrast to the theoretical predictions, the low-modulus (G' ≈ 1.0 × 10(5) Pa at 90 °C) cross-linked SPEs reported herein exhibit remarkable dendrite growth resistance. These results suggest that a high-modulus SPE is not a requirement for the control of dendrite proliferation.

  3. Enhanced Phosphate Removal by Nanosized Hydrated La(III) Oxide Confined in Cross-linked Polystyrene Networks.

    PubMed

    Zhang, Yanyang; Pan, Bingcai; Shan, Chao; Gao, Xiang

    2016-02-01

    A new nanocomposite adsorbent La-201 of extremely high capacity and specific affinity toward phosphate was fabricated and well characterized, where hydrated La(III) oxide (HLO) nanoclusters were immobilized inside the networking pores of the polystyrene anion exchanger D-201. La-201 exhibited enhanced phosphate adsorption in the presence of competing anions (chloride, sulfate, nitrate, bicarbonate, and silicate) at greater levels (up to molar ratio of 20), with working capacity 2-4 times higher than a commercial Fe(III) oxide-based nanocomposite HFO-201 in batch runs. Column adsorption runs by using La-201 could effectively treat ∼6500 bed volumes (BV) of a synthetic feeding solution before breakthrough occurred (from 2.5 mg P/L in influent to <0.5 mg P/L in effluent), approximately 11 times higher magnitude than that of HFO-201. The exhausted La-201 could be regenerated with NaOH-NaCl binary solution at 60 °C for repeated use without any significant capacity loss. The underlying mechanism for the specific sorption of phosphate by La-201 was revealed with the aid of STEM-EDS, XPS, XRD, and SSNMR analysis, and the formation of LaPO4·xH2O is verified to be the dominant pathway for selective phosphate adsorption by the immobilized nano-HLO. The results indicated that La-201 was very promising in highly efficient removal of phosphate from contaminated waters. PMID:26730837

  4. Borate cross-linking chitosan/graphene oxide films: Toward the simultaneous enhancement of gases barrier and mechanical properties

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Capezzuto, Filomena; Buonocore, Giovanna G.; Tescione, Fabiana; Lavorgna, Marino; Xia, Hesheng; Ambrosio, Luigi

    2015-12-01

    Borate adducts, originated from hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan (CS) and graphene oxide (GO) nanosheets for the production of innovative composite sustainable materials. CS/GO film consisting of 10wt% borax and 1wt% GO exhibits a significant improvement of both toughness and oxygen barrier properties in comparison to pristine chitosan. In particular the tensile strength increases by about 100% and 150% after thermal annealing of samples at 90°C for 50min whereas the oxygen permeability reduces of about 90% compared to pristine chitosan. The enhancement of both mechanical and barrier properties is ascribed to the formation of a resistant network due to the chemical crosslinking, including borate orthoester bonds and hydroxyl moieties complexes, formed among borate ions, chitosan, and GO nanoplatelets. The crosslinked graphene-based chitosan material with its enhanced mechanical and barrier properties may significantly broad the range of applications of chitosan based-materials which presently are very limited and addressed only to packaging.

  5. Iron chelators can protect against oxidative stress through ferryl heme reduction.

    PubMed

    Reeder, Brandon J; Hider, Robert C; Wilson, Michael T

    2008-02-01

    Iron chelators such as desferrioxamine have been shown to ameliorate oxidative damage in vivo. The mechanism of this therapeutic action under non-iron-overload conditions is, however, complex, as desferrioxamine has properties that can impact on oxidative damage independent of its capacity to act as an iron chelator. Desferrioxamine can act as a reducing agent to remove cytotoxic ferryl myoglobin and hemoglobin and has recently been shown to prevent the formation of a highly cytotoxic heme-to-protein cross-linked derivative of myoglobin. In this study we have examined the effects of a wide range of iron chelators, including the clinically used hydroxypyridinone CP20 (deferriprone), on the stability of ferryl myoglobin and on the formation of heme-to-protein cross-linking. We show that all hydroxypyridinones, as well as many other iron chelators, are efficient reducing agents of ferryl myoglobin. These compounds are also effective at preventing the formation of cytotoxic derivatives of myoglobin such as heme-to-protein cross-linking. These results show that the use of iron chelators in vivo may ameliorate oxidative damage under conditions of non-iron overload by at least two mechanisms. The antioxidant effects of chelators in vivo cannot, therefore, be attributed solely to iron chelation. PMID:18215735

  6. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  7. Chemoprotective Effect of Taurine on Potassium Bromate-Induced DNA Damage, DNA-Protein Cross-Linking and Oxidative Stress in Rat Intestine

    PubMed Central

    Ahmad, Mir Kaisar; Khan, Aijaz Ahmed; Ali, Shaikh Nisar; Mahmood, Riaz

    2015-01-01

    Potassium bromate (KBrO3) is widely used as a food additive and is a major water disinfection by-product. It induces multiple organ toxicity in humans and experimental animals and is a probable human carcinogen. The present study reports the protective effect of dietary antioxidant taurine on KBrO3-induced damage to the rat intestine. Animals were randomly divided into four groups: control, KBrO3 alone, taurine alone and taurine+ KBrO3. Administration of KBrO3 alone led to decrease in the activities of intestinal brush border membrane enzymes while those of antioxidant defence and carbohydrate metabolism were also severely altered. There was increase in DNA damage and DNA-protein cross-linking. Treatment with taurine, prior to administration of KBrO3, resulted in significant attenuation in all these parameters but the administration of taurine alone had no effect. Histological studies supported these biochemical results showing extensive intestinal damage in KBrO3-treated animals and greatly reduced tissue injury in the taurine+ KBrO3 group. These results show that taurine ameliorates bromate induced tissue toxicity and oxidative damage by improving the antioxidant defence, tissue integrity and energy metabolism. Taurine can, therefore, be potentially used as a therapeutic/protective agent against toxicity of KBrO3 and related compounds. PMID:25748174

  8. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  9. Radiation cross-linked polyolefin-insulated wire

    NASA Astrophysics Data System (ADS)

    Sano, K.; Ishitani, H.

    Because radiation cross-linked polyolefin has excellent mechanical heat resistance, its application limit can be expanded extremely by improving the resistance against heat oxidation and flame. This paper is concerning a halogen free radiation cross-linked polyolefin-insulated wire having excellent heat resistance and flameretardant property, which is used for appliances.

  10. Corneal Collagen Cross-Linking

    PubMed Central

    Jankov II, Mirko R.; Jovanovic, Vesna; Nikolic, Ljubisa; Lake, Jonathan C.; Kymionis, Georgos; Coskunseven, Efekan

    2010-01-01

    Corneal collagen cross-linking (CXL) with riboflavin and ultraviolet-A (UVA) is a new technique of corneal tissue strengthening by using riboflavin as a photosensitizer and UVA to increase the formation of intra and interfibrillar covalent bonds by photosensitized oxidation. Keratocyte apoptosis in the anterior segment of the corneal stroma all the way down to a depth of about 300 microns has been described and a demarcation line between the treated and untreated cornea has been clearly shown. It is important to ensure that the cytotoxic threshold for the endothelium has not been exceeded by strictly respecting the minimal corneal thickness. Confocal microscopy studies show that repopulation of keratocytes is already visible 1 month after the treatment, reaching its pre-operative quantity and quality in terms of functional morphology within 6 months after the treatment. The major indication for the use of CXL is to inhibit the progression of corneal ectasias, such as keratoconus and pellucid marginal degeneration. CXL may also be effective in the treatment and prophylaxis of iatrogenic keratectasia, resulting from excessively aggressive photoablation. This treatment has also been used to treat infectious corneal ulcers with apparent favorable results. Combination with other treatments, such as intracorneal ring segment implantation, limited topography-guided photoablation and conductive keratoplasty have been used with different levels of success. PMID:20543933

  11. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Iron oxides. 186.1374 Section 186.1374 Food and... Substances Affirmed as GRAS § 186.1374 Iron oxides. (a) Iron oxides (oxides of iron, CAS Reg. No. 1332-37-2) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron...

  12. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Iron oxides. 186.1374 Section 186.1374 Food and... Substances Affirmed as GRAS § 186.1374 Iron oxides. (a) Iron oxides (oxides of iron, CAS Reg. No. 1332-37-2) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron...

  13. Interfacial Bioorthogonal Cross-Linking

    PubMed Central

    2015-01-01

    Described herein is interfacial bioorthogonal cross-linking, the use of bioorthogonal chemistry to create and pattern biomaterials through diffusion-controlled gelation at the liquid-gel interface. The basis is a rapid (k2 284000 M–1 s–1) reaction between strained trans-cyclooctene (TCO) and tetrazine (Tz) derivatives. Syringe delivery of Tz-functionalized hyaluronic acid (HA-Tz) to a bath of bis-TCO cross-linker instantly creates microspheres with a cross-linked shell through which bis-TCO diffuses freely to introduce further cross-linking at the interface. Tags can be introduced with 3D resolution without external triggers or templates. Water-filled hydrogel channels were prepared by simply reversing the order of addition. Prostate cancer cells encapsulated in the microspheres have 99% viability, proliferate readily, and form aggregated clusters. This process is projected to be useful in the fabrication of cell-instructive matrices for in vitro tissue models. PMID:25177528

  14. Cross-linked polyvinyl alcohol films as alkaline battery separators

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Manzo, M. A.; Gonzalez-Sanabria, O. D.

    1982-01-01

    Cross-linking methods were investigated to determine their effect on the performance of polyvinyl alcohol (PVA) films as alkaline battery separators. The following types of cross-linked PVA films are discussed: (1) PVA-dialdehyde blends post-treated with an acid or acid periodate solution (two-step method) and (2) PVA-dialdehyde blends cross-linked during film formation (drying) by using a reagent with both aldehyde and acid functionality (one-step method). Laboratory samples of each cross-linked type of film were prepared and evaluated in standard separator screening tests. The pilot-plant batches of films were prepared and compared to measure differences due to the cross-linking method. The pilot-plant materials were then tested in nickel oxide - zinc cells to compare the two methods with respect to performance characteristics and cycle life. Cell test results are compared with those from tests with Celgard.

  15. Cross-linked polyvinyl alcohol films as alkaline battery separators

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Manzo, M. A.; Gonzalez-Sanabria, O. D.

    1983-01-01

    Cross-linking methods have been investigated to determine their effect on the performance of polyvinyl alcohol (PVA) films as alkaline battery separators. The following types of cross-linked PVA films are discussed: (1) PVA-dialdehyde blends post-treated with an acid or acid periodate solution (two-step method) and (2) PVA-dialdehyde blends cross-linked during film formation (drying) by using a reagent with both aldehyde and acid functionality (one-step method). Laboratory samples of each cross-linked type of film were prepared and evaluated in standard separator screening tests. Then pilot-plant batches of films were prepared and compared to measure differences due to the cross-linking method. The pilot-plant materials were then tested in nickel oxide-zinc cells to compare the two methods with respect to performance characteristics and cycle life. Cell test results are compared with those from tests with Celgard.

  16. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including...

  17. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including...

  18. Well-Constructed Single-Layer Molybdenum Disulfide Nanorose Cross-Linked by Three Dimensional-Reduced Graphene Oxide Network for Superior Water Splitting and Lithium Storage Property

    NASA Astrophysics Data System (ADS)

    Zhao, Yanyan; Kuai, Long; Liu, Yanguo; Wang, Pengpeng; Arandiyan, Hamidreza; Cao, Sufeng; Zhang, Jie; Li, Fengyun; Wang, Qing; Geng, Baoyou; Sun, Hongyu

    2015-03-01

    A facile one-step solution reaction route for growth of novel MoS2 nanorose cross-linked by 3D rGO network, in which the MoS2 nanorose is constructed by single-layered or few-layered MoS2 nanosheets, is presented. Due to the 3D assembled hierarchical architecture of the ultrathin MoS2 nanosheets and the interconnection of 3D rGO network, as well as the synergetic effects of MoS2 and rGO, the as-prepared MoS2-NR/rGO nanohybrids delivered high specific capacity, excellent cycling and good rate performance when evaluated as an anode material for lithium-ion batteries. Moreover, the nanohybrids also show excellent hydrogen-evolution catalytic activity and durability in an acidic medium, which is superior to MoS2 nanorose and their nanoparticles counterparts.

  19. Well-Constructed Single-Layer Molybdenum Disulfide Nanorose Cross-Linked by Three Dimensional-Reduced Graphene Oxide Network for Superior Water Splitting and Lithium Storage Property

    PubMed Central

    Zhao, Yanyan; Kuai, Long; Liu, Yanguo; Wang, Pengpeng; Arandiyan, Hamidreza; Cao, Sufeng; Zhang, Jie; Li, Fengyun; Wang, Qing; Geng, Baoyou; Sun, Hongyu

    2015-01-01

    A facile one-step solution reaction route for growth of novel MoS2 nanorose cross-linked by 3D rGO network, in which the MoS2 nanorose is constructed by single-layered or few-layered MoS2 nanosheets, is presented. Due to the 3D assembled hierarchical architecture of the ultrathin MoS2 nanosheets and the interconnection of 3D rGO network, as well as the synergetic effects of MoS2 and rGO, the as-prepared MoS2-NR/rGO nanohybrids delivered high specific capacity, excellent cycling and good rate performance when evaluated as an anode material for lithium-ion batteries. Moreover, the nanohybrids also show excellent hydrogen-evolution catalytic activity and durability in an acidic medium, which is superior to MoS2 nanorose and their nanoparticles counterparts. PMID:25735416

  20. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with §...

  1. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...) are undefined mixtures of iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with §...

  2. Electrospinning formaldehyde cross-linked zein solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order to develop zein fibers with improved physical properties and solvent resistance, formaldehyde was used as the cross-linking reagent before spinning. The cross-linking reaction was carried out in either acetic acid or ethanolic-HCl where the amount of cross-linking reagent was between 1 and...

  3. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section... § 148.275 Iron oxide, spent; iron sponge, spent. (a) Before spent iron oxide or spent iron sponge is... been cooled and weathered for at least eight weeks. (b) Both spent iron oxide and spent iron sponge...

  4. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform...

  5. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform...

  6. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and specifications. The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform...

  7. Iron oxidation by Thiobacillus ferrooxidans

    SciTech Connect

    Kang, Sunki; Sproull, R.D.

    1991-12-31

    Several investigators have shown that microorganisms are involved in many naturally occurring oxidation processes. At present, microbial leaching, which is the solubilization of metals catalyzed by microorganisms, is widely used commercially to produce copper, and to a lesser extent uranium, from low-grade mining wastes. Microbial leaching can also be used as a pretreatment step in the mining of precious metals, such as gold and silver. In this application, the solubilization of pyrite makes the precious metals more accessible for cyanide leaching. Because ferrous iron oxidation is such an important reaction in microbial leaching operations, this study was undertaken to examine factors affecting the rate of ferrous iron oxidation in the presence of T. ferrooxidans.

  8. High temperature oxidation of iron-iron oxide core-shell nanowires composed of iron nanoparticles.

    PubMed

    Krajewski, M; Brzozka, K; Lin, W S; Lin, H M; Tokarczyk, M; Borysiuk, J; Kowalski, G; Wasik, D

    2016-02-01

    This work describes an oxidation process of iron-iron oxide core-shell nanowires at temperatures between 100 °C and 800 °C. The studied nanomaterial was synthesized through a simple chemical reduction of iron trichloride in an external magnetic field under a constant flow of argon. The electron microscopy investigations allowed determining that the as-prepared nanowires were composed of self-assembled iron nanoparticles which were covered by a 3 nm thick oxide shell and separated from each other by a thin interface layer. Both these layers exhibited an amorphous or highly-disordered character which was traced by means of transmission electron microscopy and Mössbauer spectroscopy. The thermal oxidation was carried out under a constant flow of argon which contained the traces of oxygen. The first stage of process was related to slow transformations of amorphous Fe and amorphous iron oxides into crystalline phases and disappearance of interfaces between iron nanoparticles forming the studied nanomaterial (range: 25-300 °C). After that, the crystalline iron core and iron oxide shell became oxidized and signals for different compositions of iron oxide sheath were observed (range: 300-800 °C) using X-ray diffraction, Raman spectroscopy and Mössbauer spectroscopy. According to the thermal gravimetric analysis, the nanowires heated up to 800 °C under argon atmosphere gained 37% of mass with respect to their initial weight. The structure of the studied nanomaterial oxidized at 800 °C was mainly composed of α-Fe2O3 (∼ 93%). Moreover, iron nanowires treated above 600 °C lost their wire-like shape due to their shrinkage and collapse caused by the void coalescence. PMID:26766540

  9. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing...

  10. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing...

  11. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing...

  12. High-Relaxivity Superparamagnetic Iron Oxide Nanoworms with Decreased Immune Recognition and Long-Circulating Properties

    PubMed Central

    Wang, Guankui; Inturi, Swetha; Serkova, Natalie J.; Merkulov, Sergey; McCrae, Keith; Russek, Stephen E.; Banda, Nirmal K.; Simberg, Dmitri

    2015-01-01

    One of the core issues of nanotechnology involves masking the foreignness of nanomaterials to enable in vivo longevity and long-term immune evasion. Dextran-coated superparamagnetic iron oxide nanoparticles are very effective magnetic resonance imaging (MRI) contrast agents, and strategies to prevent immune recognition are critical for their clinical translation. Here we prepared 20 kDa dextran-coated SPIO nanoworms (NWs) of 250 nm diameter and a high molar transverse relaxivity rate R2 (~400 mM−1 s−1) to study the effect of cross-linking-hydrogelation with 1-chloro-2,3-epoxypropane (epichlorohydrin) on the immune evasion both in vitro and in vivo. Cross-linking was performed in the presence of different concentrations of NaOH (0.5 to 10 N) and different temperatures (23 and 37 °C). Increasing NaOH concentration and temperature significantly decrease the binding of anti-dextran antibody and dextran-binding lectin conconavalin A to the NWs. The decrease in dextran immunoreactivity correlated with the decrease in opsonization by complement component 3 (C3) and with the decrease in the binding of the lectin pathway factor MASP-2 in mouse serum, suggesting that cross-linking blocks the lectin pathway of complement. The decrease in C3 opsonization correlated with the decrease in NW uptake by murine peritoneal macrophages. Optimized NWs demonstrated up to 10 h circulation half-life in mice and minimal uptake by the liver, while maintaining the large 250 nm size in the blood. We demonstrate that immune recognition of large iron oxide nanoparticles can be efficiently blocked by chemical cross-linking-hydrogelation, which is a promising strategy to improve safety and bioinertness of MRI contrast agents. PMID:25419856

  13. Thermo-cross-linked elastomeric opal films.

    PubMed

    Schäfer, Christian G; Viel, Benjamin; Hellmann, Goetz P; Rehahn, Matthias; Gallei, Markus

    2013-11-13

    An efficient and convenient thermal cross-linking protocol in elastomeric opal films leading to fully reversible and stretch-tunable optical materials is reported. In this study, functional monodisperse core-shell particles were arranged in a face-centered cubic (fcc) lattice structure by a melt flow process. A problem up to now was that un-cross-linked films could not be drawn fully reversibly and hence lost their optical and mechanical performance. After thermal cross-linking reaction, the obtained films can be drawn like rubbers and the color of their Bragg reflection changes because of controlled lattice deformation, which makes the cross-linked films mechanochromic sensors. Different techniques were developed for the cross-linking of the films a posteriori, after their preparation in the melt flow process. A photo-cross-linking approach was reported earlier. This study now deals with a very efficient thermo-cross-linking approach based on the chemistry of hydroxyl- and isocyanate-functionalities that form urethane bridges. The focus of the present work is the mechanism and efficiency of this cross-linking process for elastomeric opal films with excellent mechanical and optical properties. PMID:24134322

  14. Disruption of heme-peptide covalent cross-linking in mammalian peroxidases by hypochlorous acid

    PubMed Central

    Abu-Soud, Husam M.; Maitra, Dhiman; Shaeib, Faten; Khan, Sana; Byun, Jaeman; Abdulhamid, Ibrahim; Yang, Zhe; Saed, Ghassan M.; Diamond, Michael P.; Andreana, Peter R.; Pennathur, Subramaniam

    2015-01-01

    Myeloperoxidase (MPO), lactoperoxidase (LPO) and eosinophil peroxidase (EPO) play a central role in oxidative damage in inflammatory disorders by utilizing hydrogen peroxide and halides/pseudo halides to generate the corresponding hypohalous acid. The catalytic sites of these enzymes contain a covalently modified heme group, which is tethered to the polypeptide chain at two ester linkages via the methyl group (MPO, EPO and LPO) and one sulfonium bond via the vinyl group (MPO only). Covalent cross-linking of the catalytic site heme to the polypeptide chain in peroxidases is thought to play a protective role, since it renders the heme moiety less susceptible to the oxidants generated by these enzymes. Mass-spectrometric analysis revealed the following possible pathways by which hypochlorous acid (HOCl) disrupts the heme-protein cross-linking: (1) the methyl-ester bond is cleaved to form an alcohol; (2) the alcohol group undergoes an oxygen elimination reaction via the formation of an aldehyde intermediate or undergoes a demethylation reaction to lose the terminal CH2 group; and (3) the oxidative cleavage of the vinyl-sulfonium linkage. Once the heme moiety is released it undergoes cleavage at the carbon-methyne bridge either along the δ-β or a α-γ axis to form different pyrrole derivatives. These results indicate that covalent cross-linking is not enough to protect the enzymes from HOCl mediated heme destruction and free iron release. Thus, the interactions of mammalian peroxidases with HOCl modulates their activity and sets a stage for initiation of the Fenton reaction, further perpetuating oxidative damage at sites of inflammation. PMID:25193127

  15. Reactive electrospinning and biodegradation of cross-linked methacrylated polycarbonate nanofibers.

    PubMed

    Wu, Ruizhi; Zhang, Jian-Feng; Fan, Yuwei; Stoute, Diana; Lallier, Thomas; Xu, Xiaoming

    2011-06-01

    The objectives of this study were to fabricate cross-linked biodegradable polycarbonate nanofibers and to investigate their biodegradability by different enzymes. Poly(2,3-dihydroxycarbonate) was synthesized from naturally occurring l-tartaric acid. The hydroxyl groups on the functional polycarbonate were converted to methacrylate groups to enable the polymer to cross-link under UV irradiation. Smooth cross-linked methacrylated polycarbonate nanofibers (300-1800 nm) were fabricated by a reactive electrospinning process with in situ UV radiation from a mixed solution of linear methacrylated polycarbonate (MPC) and poly(ethylene oxide) (PEO) (MPC:PEO = 9:1) in methanol/chloroform (50/50). These cross-linked nanofibers have shown excellent solvent resistance and their solubility decreases with increasing degree of cross-linking. The thermal properties of linear and cross-linked polycarbonate nanofibers were investigated by differential scanning calorimetry and thermogravimetric analysis. The cross-linked polycarbonate nanofibers show no melting point below 200 °C and their decomposition temperature increases with increasing cross-linking degree. Their biodegradation products by five different enzymes were analyzed using liquid chromatography-mass spectrometry (LC-MS). The biodegradability of the polycarbonate nanofibers decreases with increasing cross-linking degree. These nanofibers were found to support human fibroblast survival and to promote cell attachment. This study demonstrates that cross-linked biodegradable polycarbonate nanofibers with different chemical properties and biodegradability can be fabricated using the novel reactive electrospinning technology to meet the needs of different biomedical applications.

  16. Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction.

    PubMed

    Weber, Karrie A; Achenbach, Laurie A; Coates, John D

    2006-10-01

    Iron (Fe) has long been a recognized physiological requirement for life, yet for many microorganisms that persist in water, soils and sediments, its role extends well beyond that of a nutritional necessity. Fe(II) can function as an electron source for iron-oxidizing microorganisms under both oxic and anoxic conditions and Fe(III) can function as a terminal electron acceptor under anoxic conditions for iron-reducing microorganisms. Given that iron is the fourth most abundant element in the Earth's crust, iron redox reactions have the potential to support substantial microbial populations in soil and sedimentary environments. As such, biological iron apportionment has been described as one of the most ancient forms of microbial metabolism on Earth, and as a conceivable extraterrestrial metabolism on other iron-mineral-rich planets such as Mars. Furthermore, the metabolic versatility of the microorganisms involved in these reactions has resulted in the development of biotechnological applications to remediate contaminated environments and harvest energy.

  17. Porous Cross-Linked Polyimide Networks

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Guo, Haiquan (Inventor)

    2015-01-01

    Porous cross-linked polyimide networks are provided. The networks comprise an anhydride end-capped polyamic acid oligomer. The oligomer (i) comprises a repeating unit of a dianhydride and a diamine and terminal anhydride groups, (ii) has an average degree of polymerization of 10 to 50, (iii) has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups, and (iv) has been chemically imidized to yield the porous cross-linked polyimide network. Also provided are porous cross-linked polyimide aerogels comprising a cross-linked and imidized anhydride end-capped polyamic acid oligomer, wherein the oligomer comprises a repeating unit of a dianhydride and a diamine, and the aerogel has a density of 0.10 to 0.333 g/cm.sup.3 and a Young's modulus of 1.7 to 102 MPa. Also provided are thin films comprising aerogels, and methods of making porous cross-linked polyimide networks.

  18. Enhanced retention of encapsulated ions in cross-linked polymersomes.

    PubMed

    Wang, Guanglin; Hoornweg, Arentien; Wolterbeek, Hubert T; Franken, Linda E; Mendes, Eduardo; Denkova, Antonia G

    2015-03-19

    Polymer vesicles (polymersomes) composed of poly(butadiene-b-poly(ethylene oxide)) (PB-b-PEO) are known for their stability and limited permeability. However, when these vesicles are diluted, substances, such as ions, encapsulated in the aqueous cavity can be released due to vesicle disruption. In previous studies, we have shown that these vesicles can be loaded efficiently with sufficient quantities of radionuclides to allow application in radionuclide therapy and pharmacokinetics evaluation, provided that there is no loss of the encapsulated radionuclides when diluted in the bloodstream. In this paper, in order to stabilize the carriers, we propose to cross-link the hydrophobic part of the polymersome membrane and to investigate whether such cross-linking induced by γ radiation can enhance the retention of ions (radionuclides). Retention of ions encapsulated in the lumen in such cross-linked carriers has not been previously quantitatively evaluated, although it is of ultimate importance in any medical application. Here, we also investigate how cross-linking affects the transport of radionuclides (loading) through the membrane of the vesicles. The integrity of the vesicles as a function of the radiation dose is also investigated, including morphological changes. The results show that cross-linking hinders the transport of ions through the membrane, which also leads to higher retention of ions encapsulated prior to cross-linking in the vesicles. Electron micrographs show that the shape of the polymersomes is not greatly affected by γ radiation when left in the original solvent (phosphate buffered saline (PBS) or Milli-Q water), but when diluted in a good solvent for both blocks, i.e., tetrahydrofuran (THF), disintegration of the vesicles and the appearance of droplet-like structures is observed, which had not been reported previously. The results of the present study help to formulate polymersomes as carriers for radionuclide therapy, demonstrating a way to

  19. Indium Sorption to Iron Oxides

    NASA Astrophysics Data System (ADS)

    White, S. J.; Sacco, S. A.; Hemond, H.; Hussain, F. A.; Runkel, R. L.; Walton-Day, K. E.; Kimball, B. A.; Shine, J. P.

    2014-12-01

    Indium is an increasingly important metal in semiconductors and electronics, and its use is growing rapidly as a semiconductive coating (as indium tin oxide) for liquid crystal displays (LCDs) and flat panel displays. It also has uses in important energy technologies such as light emitting diodes (LEDs) and photovoltaic cells. Despite its rapid increase in use, very little is known about the environmental behavior of indium, and concerns are being raised over the potential health effects of this emerging metal contaminant. One source of indium to the environment is acid mine drainage from the mining of lead, zinc, and copper sulfides. In our previous studies of a stream in Colorado influenced by acid mine drainage from lead and zinc mining activities, indium concentrations were found to be 10,000 times those found in uncontaminated rivers. However, the speciation and mobility of indium could not be reliably modeled because sorption constants to environmental sorbents have not been determined. In this study, we generate sorption constants for indium to ferrihydrite in the laboratory over a range of pHs, sorbent to sorbate ratios, and ionic strengths. Ferrihydrite is one of the most important sorbents in natural systems, and sorption to amorphous iron oxides such as ferrihydrite is thought to be one of the main removal mechanisms of metals from the dissolved phase in aqueous environments. Because of its relatively low solubility, we also find that indium hydroxide precipitation can dominate indium's partitioning at micromolar concentrations of indium. This precipitation may be important in describing indium's behavior in our study stream in Colorado, where modeling sorption to iron-oxides does not explain the complete removal of indium from the dissolved phase when the pH of the system is artificially raised to above 8. This study contributes much-needed data about indium's aqueous behavior, in order to better understand its fate, transport, and impacts in the

  20. Conquering the Dark Side: Colloidal Iron Oxide Nanoparticles

    PubMed Central

    Senpan, Angana; Caruthers, Shelton D.; Rhee, Ilsu; Mauro, Nicholas A.; Pan, Dipanjan; Hu, Grace; Scott, Michael J.; Fuhrhop, Ralph W.; Gaffney, Patrick J.; Wickline, Samuel A.; Lanza, Gregory M.

    2009-01-01

    Nanomedicine approaches to atherosclerotic disease will have significant impact on the practice and outcomes of cardiovascular medicine. Iron oxide nanoparticles have been extensively used for nontargeted and targeted imaging applications based upon highly sensitive T2* imaging properties, which typically result in negative contrast effects that can only be imaged 24 or more hours after systemic administration due to persistent blood pool interference. Although recent advances involving MR pulse sequences have converted these dark contrast voxels into bright ones, the marked delays in imaging from persistent magnetic background interference and prominent dipole blooming effects of the magnetic susceptibility remain barriers to overcome. We report a T1-weighted (T1w) theranostic colloidal iron oxide nanoparticle platform, CION, which is achieved by entrapping oleate-coated magnetite particles within a cross-linked phospholipid nanoemulsion. Contrary to expectations, this formulation decreased T2 effects thus allowing positive T1w contrast detection down to low nanomolar concentrations. CION, a vascular constrained nanoplatform administered in vivo permitted T1w molecular imaging 1 hour after treatment without blood pool interference, although some T2 shortening effects on blood, induced by the superparamagnetic particles persisted. Moreover, CION was shown to encapsulate antiangiogenic drugs, like fumagillin, and retained them under prolonged dissolution, suggesting significant theranostic functionality. Overall, CION is a platform technology, developed with generally recognized as safe components, that overcomes the temporal and spatial imaging challenges associated with current iron oxide nanoparticle T2 imaging agents, and which has theranostic potential in vascular diseases for detecting unstable ruptured plaque or treating atherosclerotic angiogenesis. PMID:19908850

  1. Iron biomineralization by anaerobic neutrophilic iron-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Miot, Jennyfer; Benzerara, Karim; Morin, Guillaume; Kappler, Andreas; Bernard, Sylvain; Obst, Martin; Férard, Céline; Skouri-Panet, Fériel; Guigner, Jean-Michel; Posth, Nicole; Galvez, Matthieu; Brown, Gordon E., Jr.; Guyot, François

    2009-02-01

    Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate-dependent iron-oxidizing bacterium Acidovorax sp. strain BoFeN1 in the presence of dissolved Fe(II) using electron microscopy and Scanning Transmission X-ray Microscopy (STXM). All detected minerals consisted mainly of amorphous iron phosphates, but based on their morphology and localization, three types of precipitates could be discriminated: (1) mineralized filaments at distance from the cells, (2) globules of 100 ± 25 nm in diameter, at the cell surface and (3) a 40-nm thick mineralized layer within the periplasm. All of those phases were shown to be intimately associated with organic molecules. Periplasmic encrustation was accompanied by an accumulation of protein moieties. In the same way, exopolysaccharides were associated with the extracellular mineralized filaments. The evolution of cell encrustation was followed by TEM over the time course of a culture: cell encrustation proceeded progressively, with rapid precipitation in the periplasm (in a few tens of minutes), followed by the formation of surface-bound globules. Moreover, we frequently observed an asymmetric mineral thickening at the cell poles. In parallel, the evolution of iron oxidation was quantified by STXM: iron both contained in the bacteria and in the extracellular precipitates reached complete oxidation within 6 days. While a progressive oxidation of Fe in the bacteria and in the medium could be observed, spatial redox (oxido-reduction state) heterogeneities were detected at the cell poles and in the extracellular precipitates after 1 day. All these findings provide new information to further the understanding of molecular processes involved in iron biomineralization by anaerobic iron-oxidizing bacteria and

  2. Tannin biosynthesis of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Herrera-Becerra, R.; Rius, J. L.; Zorrilla, C.

    2010-08-01

    In this work, iron oxide nanoparticles synthesized with gallic acid and tannic acid are characterized using High-Resolution Transmission Electron Microscopy (HRTEM). Its size, form, and structure are compared with nanoparticles obtained previously using alfalfa biomass in order to find a simpler, consistent, and environmentally friendly method in the production of iron oxide nanoparticles.

  3. 21 CFR 73.3125 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3125 Iron oxides. (a) Identity and...

  4. 21 CFR 186.1374 - Iron oxides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... iron (II) oxide (CAS Reg. No. 1345-25-1, black cubic crystals) and iron (III) oxide (CAS Reg. No. 1309-37-1, red-brown to black trigonal crystals). (b) In accordance with § 186.1(b)(1), the ingredient...

  5. The effect of cross-link distributions in axially-ordered, cross-linked networks

    PubMed Central

    Bennett, C. Brad; Kruczek, James; Rabson, D. A.; Matthews, W. Garrett; Pandit, Sagar A.

    2013-01-01

    Cross-linking between the constituent chains of biopolymers has a marked effect on their materials properties. In certain of these materials, such as fibrillar collagen, increases in cross-linking lead to an increase in the melting temperature. Fibrillar collagen is an axially-ordered network of cross-linked polymer chains exhibiting a broadened denaturation transition, which has been explained in terms of the successive denaturation with temperature of multiple species. We model axially-ordered cross-linked materials as stiff chains with distinct arrangements of cross-link-forming sites. Simulations suggest that systems composed of chains with identical arrangements of cross-link-forming sites exhibit critical behavior. In contrast, systems composed of non-identical chains undergo a crossover. This model suggests that the arrangement of cross-link-forming sites may contribute to the broadening of the denaturation transition in fibrillar collagen. PMID:23751928

  6. Enzymatic iron oxidation by Leptothrix discophora: identification of an iron-oxidizing protein.

    PubMed Central

    Corstjens, P L; de Vrind, J P; Westbroek, P; de Vrind-de Jong, E W

    1992-01-01

    An iron-oxidizing factor was identified in the spent culture medium of the iron- and manganese-oxidizing bacterial strain Leptothrix discophora SS-1. It appeared to be a protein, with an apparent molecular weight of approximately 150,000. Its activity could be demonstrated after fractionation of the spent medium by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. A spontaneous mutant of L. discophora SS-1 was isolated which excreted neither manganese- nor iron-oxidizing activity, whereas excretion of other proteins seemed to be unaffected. Although the excretion of both metal-oxidizing factors was probably linked, the difference in other properties suggests that manganese and iron oxidation represent two different pathways. With a dot-blot assay, it was established that different bacterial species have different metal-oxidizing capacities. Whereas L. discophora oxidized both iron and manganese, Sphaerotilus natans oxidized only iron and two Pseudomonas spp. oxidized only manganese. Images PMID:1610168

  7. Enzymatic iron oxidation by Leptothrix discophora: identification of an iron-oxidizing protein.

    PubMed

    Corstjens, P L; de Vrind, J P; Westbroek, P; de Vrind-de Jong, E W

    1992-02-01

    An iron-oxidizing factor was identified in the spent culture medium of the iron- and manganese-oxidizing bacterial strain Leptothrix discophora SS-1. It appeared to be a protein, with an apparent molecular weight of approximately 150,000. Its activity could be demonstrated after fractionation of the spent medium by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. A spontaneous mutant of L. discophora SS-1 was isolated which excreted neither manganese- nor iron-oxidizing activity, whereas excretion of other proteins seemed to be unaffected. Although the excretion of both metal-oxidizing factors was probably linked, the difference in other properties suggests that manganese and iron oxidation represent two different pathways. With a dot-blot assay, it was established that different bacterial species have different metal-oxidizing capacities. Whereas L. discophora oxidized both iron and manganese, Sphaerotilus natans oxidized only iron and two Pseudomonas spp. oxidized only manganese. PMID:1610168

  8. Peroxidase induced oligo-tyrosine cross-links during polymerization of α-lactalbumin.

    PubMed

    Dhayal, Surender Kumar; Sforza, Stefano; Wierenga, Peter A; Gruppen, Harry

    2015-12-01

    Horseradish peroxidase (HRP) induced cross-linking of proteins has been reported to proceed through formation of di-tyrosine cross-links. In the case of low molar mass phenolic substrates, the enzymatic oxidation is reported to lead to polymerization of the phenols. The aim of this work was to investigate if during oxidative cross-linking of proteins oligo-tyrosine cross-links are formed in addition to dityrosine. To this end, α-lactalbumin (α-LA) was cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H₂O₂). The reaction products were acid hydrolysed, after which the cross-linked amino acids were investigated by LC-MS and MALDI-MS. To test the effect of the size of the substrate, the cross-linking reaction was also performed with L-tyrosine, N-acetyl L-tyrosinamide and angiotensin. These products were analyzed by LC-MS directly, as well as after acid hydrolysis. In the acid hydrolysates of all samples oligo-tyrosine (Yn, n=3-8) was found in addition to di-tyrosine (Y2). Two stages of cross-linking of α-LA were identified: a) 1-2 cross-links were formed per monomer until the monomers were converted into oligomers, and b) subsequent cross-linking of oligomers formed in the first stage to form nanoparticles containing 3-4 cross-links per monomer. The transition from first stage to the second stage coincided with the point where di-tyrosine started to decrease and more oligo-tyrosines were formed. In conclusion, extensive polymerization of α-LA using HRP via oligo-tyrosine cross-links is possible, as is the case for low molar mass tyrosine containing substrates. PMID:26282909

  9. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1997-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  10. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1998-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  11. Facile and sustainable synthesis of shaped iron oxide nanoparticles: effect of iron precursor salts on the shapes of iron oxides.

    PubMed

    Sayed, Farheen N; Polshettiwar, Vivek

    2015-05-05

    A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner.

  12. Facile and Sustainable Synthesis of Shaped Iron Oxide Nanoparticles: Effect of Iron Precursor Salts on the Shapes of Iron Oxides

    PubMed Central

    Sayed, Farheen N.; Polshettiwar, Vivek

    2015-01-01

    A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner. PMID:25939969

  13. Cross-linked biopolymer bundles: Cross-link reversibility leads to cooperative binding/unbinding phenomena

    NASA Astrophysics Data System (ADS)

    Vink, Richard L. C.; Heussinger, Claus

    2012-01-01

    We consider a biopolymer bundle consisting of filaments that are cross-linked together. The cross-links are reversible: they can dynamically bind and unbind adjacent filament pairs as controlled by a binding enthalpy. The bundle is subjected to a bending deformation and the corresponding distribution of cross-links is measured. For a bundle consisting of two filaments, upon increasing the bending amplitude, a first-order transition is observed. The transition is from a state where the filaments are tightly coupled by many bound cross-links, to a state of nearly independent filaments with only a few bound cross-links. For a bundle consisting of more than two filaments, a series of first-order transitions is observed. The transitions are connected with the formation of an interface between regions of low and high cross-link densities. Combining umbrella sampling Monte Carlo simulations with analytical calculations, we present a detailed picture of how the competition between cross-link shearing and filament stretching drives the transitions. We also find that, when the cross-links become soft, collective behavior is not observed: the cross-links then unbind one after the other leading to a smooth decrease of the average cross-link density.

  14. Specific covalent immobilization of proteins through dityrosine cross-links.

    PubMed

    Endrizzi, Betsy J; Huang, Gang; Kiser, Patrick F; Stewart, Russell J

    2006-12-19

    Dityrosine cross-links are widely observed in nature in structural proteins such as elastin and silk. Natural oxidative cross-linking between tyrosine residues is catalyzed by a diverse group of metalloenzymes. Dityrosine formation is also catalyzed in vitro by metal-peptide complexes such as Gly-Gly-His-Ni(II). On the basis of these observations, a system was developed to specifically and covalently surface immobilize proteins through dityrosine cross-links. Methacrylate monomers of the catalytic peptide Gly-Gly-His-Tyr-OH (GGHY) and the Ni(II)-chelating group nitrilotriacetic acid (NTA) were copolymerized with acrylamide into microbeads. Green fluorescent protein (GFP), as a model protein, was genetically tagged with a tyrosine-modified His6 peptide on its carboxy terminus. GFP-YGH6, specifically associated with the NTA-Ni(II) groups, was covalently coupled to the bead surface through dityrosine bond formation catalyzed by the colocalized GGHY-Ni(II) complex. After extensive washing with EDTA to disrupt metal coordination bonds, we observed that up to 75% of the initially bound GFP-YGH6 remained covalently bound to the bead while retaining its structure and activity. Dityrosine cross-linking was confirmed by quenching the reaction with free tyrosine. The method may find particular utility in the construction and optimization of protein microarrays. PMID:17154619

  15. Cross-linking reconsidered: binding and cross-linking fields and the cellular response.

    PubMed Central

    Sulzer, B; De Boer, R J; Perelson, A S

    1996-01-01

    We analyze a model for the reversible cross-linking of cell surface receptors by a collection of bivalent ligands with different affinities for the receptor as would be found in a polyclonal anti-receptor serum. We assume that the amount of cross-linking determines, via a monotonic function, the rate at which cells become activated and divide. In addition to the density of receptors on the cell surface, two quantities, the binding field and the cross-linking field, are needed to characterize the cross-linking curve, i.e., the equilibrium concentration of cross-linked receptors plotted as a function of the total ligand site concentration. The binding field is the sum of all ligand site concentrations weighted by their respective binding affinities, and the cross-linking field is the sum of all ligand site concentrations weighted by the product of their respective binding and cross-linking affinity and the total receptor density. Assuming that the cross-linking affinity decreases if the binding affinity decreases, we find that the height of the cross-linking curve decreases, its width narrows, and its center shifts to higher ligand site concentrations as the affinities decrease. Moreover, when we consider cross-linking-induced proliferation, we find that there is a minimum cross-linking affinity that must be surpassed before a clone can expand. We also show that under many circumstances a polyclonal antiserum would be more likely than a monoclonal antibody to lead to cross-linking-induced proliferation. Images FIGURE 1 FIGURE 2 FIGURE 5 PMID:8785275

  16. Modified gum arabic cross-linked gelatin scaffold for biomedical applications.

    PubMed

    Sarika, P R; Cinthya, Kuriakose; Jayakrishnan, A; Anilkumar, P R; James, Nirmala Rachel

    2014-10-01

    The present work deals with development of modified gum arabic cross-linked gelatin scaffold for cell culture. A new biocompatible scaffold was developed by cross-linking gelatin (Gel) with gum arabic, a polysaccharide. Gum arabic was subjected to periodate oxidation to obtain gum arabic aldehyde (GAA). GAA was reacted with gelatin under appropriate pH to prepare the cross-linked hydrogel. Cross-linking occurred due to Schiff's base reaction between aldehyde groups of oxidized gum arabic and amino groups of gelatin. The scaffold prepared from the hydrogel was characterized by swelling properties, degree of cross-linking, in vitro degradation and scanning electron microscopy (SEM). Cytocompatibility evaluation using L-929 and HepG2 cells confirmed non-cytotoxic and non-adherent nature of the scaffold. These properties are essential for generating multicellular spheroids and hence the scaffold is proposed to be a suitable candidate for spheroid cell culture. PMID:25175214

  17. On the formation of iron(III) oxides via oxidation of iron(II)

    SciTech Connect

    Bongiovanni, R.; Pelizzetti, E.; Borgarello, E.; Meisel, D.

    1994-09-01

    Formation of iron oxides in aqueous salt solutions is reviewed. The discussion is focused on the oxidation of iron(II) and the following hydrolysis process that leads to the formation of a solid phase from homogeneous solutions. Results from our own studies on the kinetics of the oxidation reactions and the ensuing growth processes are presented.

  18. Arsenic Adsorption Onto Iron Oxides Minerals

    NASA Astrophysics Data System (ADS)

    Aredes, S.; Klein, B.; Pawlik, M.

    2004-12-01

    The predominant form of arsenic in water is as an inorganic ion. Under different redox conditions arsenic in water is stable in the +5 and +3 oxidation states. Arsenic oxidation state governs its toxicity, chemical form and solubility in natural and disturbed environments. As (III) is found in anoxic environments such as ground water , it is toxic and the common species is the neutral form, H3AsO3. As (V) is found in aerobic conditions such as surface water, it is less toxic and the common species in water are: H2AsO4 - and HAsO4 {- 2}. The water pH determines the predominant arsenate or arsenite species, however, both forms of arsenic can be detected in natural water systems. Iron oxides minerals often form in natural waters and sediments at oxic-anoxic boundaries. Over time they undergo transformation to crystalline forms, such as goethite or hematite. Both As(V) and As(III) sorbs strongly to iron oxides, however the sorption behavior of arsenic is dependent on its oxidation state and the mineralogy of the iron oxides. Competition between arsenic and others ions, such fluoride, sulphate and phosphate also play a role. On the other hand, calcium may increase arsenic adsorption onto iron oxides. Electrokinetic studies and adsorption experiments were carried out in order to determine which conditions favour arsenic adsorption. Hematite, goethite and magnetite as iron based sorbents were used. Test were also conducted with a laterite soil rich in iron minerals. The focus of this study is to evaluate physical and chemical conditions which favour arsenic adsorption onto iron oxides minerals, the results contribute to an understanding of arsenic behaviour in natural and disturbed environments. Furthermore, results could contribute in developing an appropriate remediation technology for arsenic removal in water using iron oxides minerals.

  19. In Situ Cross-Linking of Stimuli-Responsive Hemicellulose Microgels during Spray Drying

    PubMed Central

    2015-01-01

    Chemical cross-linking during spray drying offers the potential for green fabrication of microgels with a rapid stimuli response and good blood compatibility and provides a platform for stimuli-responsive hemicellulose microgels (SRHMGs). The cross-linking reaction occurs rapidly in situ at elevated temperature during spray drying, enabling the production of microgels in a large scale within a few minutes. The SRHMGs with an average size range of ∼1–4 μm contain O-acetyl-galactoglucomannan as a matrix and poly(acrylic acid), aniline pentamer (AP), and iron as functional additives, which are responsive to external changes in pH, electrochemical stimuli, magnetic field, or dual-stimuli. The surface morphologies, chemical compositions, charge, pH, and mechanical properties of these smart microgels were evaluated using scanning electron microscopy, IR, zeta potential measurements, pH evaluation, and quantitative nanomechanical mapping, respectively. Different oxidation states were observed when AP was introduced, as confirmed by UV spectroscopy and cyclic voltammetry. Systematic blood compatibility evaluations revealed that the SRHMGs have good blood compatibility. This bottom-up strategy to synthesize SRHMGs enables a new route to the production of smart microgels for biomedical applications. PMID:25630464

  20. In situ cross-linking of stimuli-responsive hemicellulose microgels during spray drying.

    PubMed

    Zhao, Weifeng; Nugroho, Robertus Wahyu N; Odelius, Karin; Edlund, Ulrica; Zhao, Changsheng; Albertsson, Ann-Christine

    2015-02-25

    Chemical cross-linking during spray drying offers the potential for green fabrication of microgels with a rapid stimuli response and good blood compatibility and provides a platform for stimuli-responsive hemicellulose microgels (SRHMGs). The cross-linking reaction occurs rapidly in situ at elevated temperature during spray drying, enabling the production of microgels in a large scale within a few minutes. The SRHMGs with an average size range of ∼ 1-4 μm contain O-acetyl-galactoglucomannan as a matrix and poly(acrylic acid), aniline pentamer (AP), and iron as functional additives, which are responsive to external changes in pH, electrochemical stimuli, magnetic field, or dual-stimuli. The surface morphologies, chemical compositions, charge, pH, and mechanical properties of these smart microgels were evaluated using scanning electron microscopy, IR, zeta potential measurements, pH evaluation, and quantitative nanomechanical mapping, respectively. Different oxidation states were observed when AP was introduced, as confirmed by UV spectroscopy and cyclic voltammetry. Systematic blood compatibility evaluations revealed that the SRHMGs have good blood compatibility. This bottom-up strategy to synthesize SRHMGs enables a new route to the production of smart microgels for biomedical applications. PMID:25630464

  1. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, W.P. Jr.; Apen, P.G.; Mitchell, M.A.

    1998-01-20

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes. 1 fig.

  2. Cross-linked structure of network evolution

    SciTech Connect

    Bassett, Danielle S.; Wymbs, Nicholas F.; Grafton, Scott T.; Porter, Mason A.; Mucha, Peter J.

    2014-03-15

    We study the temporal co-variation of network co-evolution via the cross-link structure of networks, for which we take advantage of the formalism of hypergraphs to map cross-link structures back to network nodes. We investigate two sets of temporal network data in detail. In a network of coupled nonlinear oscillators, hyperedges that consist of network edges with temporally co-varying weights uncover the driving co-evolution patterns of edge weight dynamics both within and between oscillator communities. In the human brain, networks that represent temporal changes in brain activity during learning exhibit early co-evolution that then settles down with practice. Subsequent decreases in hyperedge size are consistent with emergence of an autonomous subgraph whose dynamics no longer depends on other parts of the network. Our results on real and synthetic networks give a poignant demonstration of the ability of cross-link structure to uncover unexpected co-evolution attributes in both real and synthetic dynamical systems. This, in turn, illustrates the utility of analyzing cross-links for investigating the structure of temporal networks.

  3. The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean

    PubMed Central

    Emerson, David

    2016-01-01

    Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157

  4. The Irony of Iron - Biogenic Iron Oxides as an Iron Source to the Ocean.

    PubMed

    Emerson, David

    2015-01-01

    Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity.

  5. The Irony of Iron - Biogenic Iron Oxides as an Iron Source to the Ocean.

    PubMed

    Emerson, David

    2015-01-01

    Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157

  6. Removal of metallic iron on oxide slags

    SciTech Connect

    Shannon, G.N.; Fruehan, R.J.; Sridhar, S.

    2009-10-15

    It is possible, in some cases, for ground coal particles to react with gasifier gas during combustion, allowing the ash material in the coal to form phases besides the expected slag phase. One of these phases is metallic iron, because some gasifiers are designed to operate under a reducing atmosphere (pO{sub 2}) of approximately 10{sup -4} atm). Metallic iron can become entrained in the gas stream and deposit on, and foul, downstream equipment. To improve the understanding of the reaction between different metallic iron particles and gas, which eventually oxidizes them, and the slag that the resulting oxide dissolves in, the kinetics of iron reaction on slag were predicted using gas-phase mass-transfer limitations for the reaction and were compared with diffusion in the slag; the reaction itself was observed under confocal scanning laser microscopy. The expected rates for iron droplet removal are provided based on the size and effective partial pressure of oxygen, and it is found that decarburization occurs before iron reaction, leading to an extra 30- to 100-second delay for carbon-saturated particles vs pure iron particles. A pure metallic iron particle of 0.5 mg should be removed in about 220 seconds at 1400{sup o}C and in 160 seconds at 1600{sup o}C.

  7. Exploring Microbial Iron Oxidation in Wetland Soils

    NASA Astrophysics Data System (ADS)

    Wang, J.; Muyzer, G.; Bodelier, P. L. E.; den Oudsten, F.; Laanbroek, H. J.

    2009-04-01

    Iron is one of the most abundant elements on earth and is essential for life. Because of its importance, iron cycling and its interaction with other chemical and microbial processes has been the focus of many studies. Iron-oxidizing bacteria (FeOB) have been detected in a wide variety of environments. Among those is the rhizosphere of wetland plants roots which release oxygen into the soil creating suboxic conditions required by these organisms. It has been reported that in these rhizosphere microbial iron oxidation proceeds up to four orders of magnitude faster than strictly abiotic oxidation. On the roots of these wetland plants iron plaques are formed by microbial iron oxidation which are involved in the sequestering of heavy metals as well organic pollutants, which of great environmental significance.Despite their important role being catalysts of iron-cycling in wetland environments, little is known about the diversity and distribution of iron-oxidizing bacteria in various environments. This study aimed at developing a PCR-DGGE assay enabling the detection of iron oxidizers in wetland habitats. Gradient tubes were used to enrich iron-oxidizing bacteria. From these enrichments, a clone library was established based on the almost complete 16s rRNA gene using the universal bacterial primers 27f and 1492r. This clone library consisted of mainly α- and β-Proteobacteria, among which two major clusters were closely related to Gallionella spp. Specific probes and primers were developed on the basis of this 16S rRNA gene clone library. The newly designed Gallionella-specific 16S rRNA gene primer set 122f/998r was applied to community DNA obtained from three contrasting wetland environments, and the PCR products were used in denaturing gradient gel electrophoresis (DGGE) analysis. A second 16S rRNA gene clone library was constructed using the PCR products from one of our sampling sites amplified with the newly developed primer set 122f/998r. The cloned 16S rRNA gene

  8. Cross-Linking Studies of Lysozyme Nucleation

    NASA Technical Reports Server (NTRS)

    Forsythe, Elizabeth; Pusey, Marc

    2000-01-01

    Tetragonal chicken egg white crystals consist of 4(sub 3) helices running in alternating directions, the helix rows having a two fold symmetry with each other. The unit cell consists of one complete tetrameric turn from each of two adjacent helices (an octamer). PBC analysis indicates that the helix intermolecular bonds are the strongest in the crystal, therefore likely formed first. AFM analysis of the (110) surface shows only complete helices, no half steps or bisected helices being found, while AFM line scans to measure the growth step increments show that they are multiples of the 4(sub 3) helix tetramer dimensions. This supports our thesis that the growth units are in fact multiples of the four molecule 4(sub 3) helix unit, the "average" growth unit size for the (110) face being an octamer (two turns about the helix) and the (101) growth unit averaging about the size of a hexamer. In an effort to better understand the species involved in the crystal nucleation and growth process, we have initiated an experimental program to study the species formed in solution compared to what is found in the crystal through covalent cross-linking studies. These experiments use the heterobifunctional cross-linking agent aminoethyl-4-azidonitroanaline (AEANA). An aliphatic amine at one end is covalently attached to the protein by a carbodiimide-mediated reaction, and a photo reactive group at the other can be used to initiate crosslinking. Modifications to the parent structure can be used to alter the distance between the two reactive groups and thus the cross-linking agents "reach". In practice, the cross-linking agent is first coupled to the asp101 side chain through the amine group. Asp101 lies within the active site cleft, and previous work with fluorescent probes had shown that derivatives at this site still crystallize in the tetragonal space group. This was also found to be the case with the AEANA derivative, which gave red tetragonal crystals. The protein now has a

  9. Thermodynamics of Iron Oxidation in Metallurgical Slags

    NASA Astrophysics Data System (ADS)

    Matousek, Jan

    2012-11-01

    The state of oxidation of a pyrometallurgical process, given by the partial pressure of oxygen and the temperature, is one of the important properties monitored and controlled in the smelting and refining of iron and the nonferrous metals. This article reviews the thermodynamic background for this quantity and examines some empirical methods for its estimation and use. The emphasis is on copper smelting, but the same principles apply to iron, nickel, lead, and zinc processes.

  10. Laboratory experiments on the weathering of iron meteorites and carbonaceous chondrites by iron-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Gronstal, A.; Pearson, V.; Kappler, A.; Dooris, C.; Anand, M.; Poitrasson, F.; Kee, T. P.; Cockell, C. S.

    2009-03-01

    Batch culture experiments were performed to investigate the weathering of meteoritic material by iron-oxidizing bacteria. The aerobic, acidophilic iron oxidizer (A. ferrooxidans) was capable of oxidizing iron from both carbonaceous chondrites (Murchison and Cold Bokkeveld) and iron meteorites (York and Casas Grandes). Preliminary iron isotope results clearly show contrasted iron pathways during oxidation with and without bacteria suggesting that a biological role in meteorite weathering could be distinguished isotopically. Anaerobic iron-oxidizers growing under pH-neutral conditions oxidized iron from iron meteorites. These results show that rapid biologicallymediated alteration of extraterrestrial materials can occur in both aerobic and anaerobic environments. These results also demonstrate that iron can act as a source of energy for microorganisms from both iron and carbonaceous chondrites in aerobic and anaerobic conditions with implications for life on the early Earth and the possible use of microorganisms to extract minerals from asteroidal material.

  11. Thermodynamic constraints on microbial iron oxide reduction

    NASA Astrophysics Data System (ADS)

    Bonneville, S.; Behrends, T.; Haese, R.; van Cappellen, P.

    2003-04-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit large surface areas which bind trace metals, nutrients and organic molecules. Under suboxic conditions, iron oxides can reductively dissolve via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. The aim of our study was to determine the thermodynamic energy yields of dissimilatory iron reduction for different Fe(III) substrates. We used the facultative anaerobic gram-positive bacterium Shewanella putrefaciens as model iron reducing bacterium, with ferrihydrite, hematite, goethite or Fe(III)-salicylate as electron acceptor, and lactate as electron donor. Experiments were conducted in an anaerobic pH-stat batch reactor, equipped with a polarographic electrode to monitor in situ the dissolved ferrous iron activity. The stoichiometry of total Fe(II) production and acid consumption during the experiments indicated that lactate was oxidized to acetate. From the Fe(II) activity and redox potential measurements, free energy yields were calculated for Fe(III) reduction coupled to lactate oxidation. The results showed that the redox potential of the overall reaction was poised by equilibrium between the Fe(III)-substrate and aqueous Fe(II). Hence, the energy yields decreased in the order ferrihydrite > Fe(III)-salicylate > hematite > goethite. Accumulation of Fe(II) in solution only caused small decreases in the energy yields over the course of the experiments. Cessation of iron reduction, which was observed in all experiments, was therefore not due to thermodynamic limitation, but more likely reflected the decline in cell level of activity.

  12. Chitosan-cross-linked osmium polymer composites as an efficient platform for electrochemical biosensors.

    PubMed

    Jirimali, Harishchandra Digambar; Nagarale, Rajaram Krishna; Lee, Jong Myung; Saravanakumar, Durai; Shin, Woonsup

    2013-07-22

    A new family of chitosan-cross-linked osmium polymer composites was prepared and its electrochemical properties were examined. The composites were prepared by quaternization of the poly(4-vinylpyridine) osmium bipyridyl polymer (PVP-Os) which was then cross-linked with chitosan, yielding PVP-Os/chitosan. Films made of the composites showed improved mass and electron transport owing to the porous and hydrophilic structure which is derived from the cross-links between the Os polymer and chitosan. The rate for glucose oxidation was enhanced four times when glucose oxidase (GOx) was immobilized on PVP-Os/chitosan compared immobilization on PVP-Os.

  13. Complications of Corneal Collagen Cross-Linking

    PubMed Central

    Dhawan, Shikha; Rao, Kavita; Natrajan, Sundaram

    2011-01-01

    Cross-linking of corneal collagen (CXL) is a promising approach for the treatment of keratoconus and secondary ectasia. Several long-term and short-term complications of CXL have been studied and documented. The possibility of a secondary infection after the procedure exists because the patient is subjected to epithelial debridement and the application of a soft contact lens. Formation of temporary corneal haze, permanent scars, endothelial damage, treatment failure, sterile infiltrates, and herpes reactivation are the other reported complications of this procedure. Cross-linking is a low-invasive procedure with low complication and failure rate but it may have direct or primary complications due to incorrect technique application or incorrect patient's inclusion and indirect or secondary complications related to therapeutic soft contact lens, patient's poor hygiene, and undiagnosed concomitant ocular surface diseases. PMID:22254130

  14. Positive tone cross-linked resists based on photoacid inhibition of cross linking

    NASA Astrophysics Data System (ADS)

    Lawson, Richard A.; Chun, Jun Sung; Neisser, Mark; Tolbert, Laren M.; Henderson, Clifford L.

    2014-03-01

    A resist imaging design that utilizes photoacid inhibition of cationic polymerization and cross-linking during a postexposure bake step has been studied. The key to the design approach is the use of two different polymerization catalysts/initiators: (1) a photoacid produced from a photoacid generator (PAG) upon exposure of the resist that can result in polymerization and cross-linking of the resist matrix and (2) a thermal cross-linking catalyst (TCC) designed to thermally catalyze epoxide-phenol cross-linking. The TCC can be chosen from a variety of compounds such as triphenylphosphine (TPP) or imidazole. When only one of these catalysts (e.g TPP or photoacid) is present in an epoxide and phenol containing resist matrix, it will individually catalyze cross-linking. When they are present together, they effectively quench one another and little to no cross-linking occurs. This approach can be used to switch the tone of a resist from negative (photoacid catalyzed) to positive (TCC catalyzed and photoacid inhibited). The effect of the ratio of TCC:PAG was examined and the optimal ratio for positive tone behavior was determined. Resist contrast can be modified by optimization of epoxide:phenol ratio in the formulation. Dual tone behavior with positive tone at low dose and negative tone at higher doses can be observed in certain formulation conditions. Initial EUV patterning shows poor results, but the source of the poor imaging is not yet understood.

  15. Collagen cross-linking in thin corneas

    PubMed Central

    Padmanabhan, Prema; Dave, Abhishek

    2013-01-01

    Collagen cross-linking (CXL) has become the standard of care for progressive keratoconus, after numerous clinical studies have established its efficacy and safety in suitably selected eyes. The standard protocol is applicable in eyes which have a minimum corneal thickness of 400 μm after epithelial debridement. This prerequisite was stipulated to protect the corneal endothelium and intraocular tissues from the deleterious effect of ultraviolet-A (UVA) radiation. However, patients with keratoconus often present with corneal thickness of less than 400 μm and could have otherwise benefited from this procedure. A few modifications of the standard procedure have been suggested to benefit these patients without a compromise in safety. Transepithelial cross-linking, pachymetry-guided epithelial debridement before cross-linking, and the use of hypoosmolar riboflavin are some of the techniques that have been attempted. Although clinical data is limited at the present time, these techniques are worth considering in patients with thin corneas. Further studies are needed to scientifically establish their efficacy and safety. PMID:23925328

  16. Iron oxides in human spleen.

    PubMed

    Kopáni, Martin; Miglierini, Marcel; Lančok, Adriana; Dekan, Július; Čaplovicová, Mária; Jakubovský, Ján; Boča, Roman; Mrazova, Hedviga

    2015-10-01

    Iron is an essential element for fundamental cell functions and a catalyst for chemical reactions. Three samples extracted from the human spleen were investigated by scanning (SEM) and transmission electron microscopy (TEM), Mössbauer spectrometry (MS), and SQUID magnetometry. The sample with diagnosis of hemosiderosis (H) differs from that referring to hereditary spherocytosis and the reference sample. SEM reveals iron-rich micrometer-sized aggregate of various structures-tiny fibrils in hereditary spherocytosis sample and no fibrils in hemochromatosis. Hematite and magnetite particles from 2 to 6 μm in TEM with diffraction in all samples were shown. The SQUID magnetometry shows different amount of diamagnetic, paramagnetic and ferrimagnetic structures in the tissues. The MS results indicate contribution of ferromagnetically split sextets for all investigated samples. Their occurrence indicates that at least part of the sample is magnetically ordered below the critical temperature. The iron accumulation process is different in hereditary spherocytosis and hemosiderosis. This fact may be the reason of different iron crystallization.

  17. Iron oxides in human spleen.

    PubMed

    Kopáni, Martin; Miglierini, Marcel; Lančok, Adriana; Dekan, Július; Čaplovicová, Mária; Jakubovský, Ján; Boča, Roman; Mrazova, Hedviga

    2015-10-01

    Iron is an essential element for fundamental cell functions and a catalyst for chemical reactions. Three samples extracted from the human spleen were investigated by scanning (SEM) and transmission electron microscopy (TEM), Mössbauer spectrometry (MS), and SQUID magnetometry. The sample with diagnosis of hemosiderosis (H) differs from that referring to hereditary spherocytosis and the reference sample. SEM reveals iron-rich micrometer-sized aggregate of various structures-tiny fibrils in hereditary spherocytosis sample and no fibrils in hemochromatosis. Hematite and magnetite particles from 2 to 6 μm in TEM with diffraction in all samples were shown. The SQUID magnetometry shows different amount of diamagnetic, paramagnetic and ferrimagnetic structures in the tissues. The MS results indicate contribution of ferromagnetically split sextets for all investigated samples. Their occurrence indicates that at least part of the sample is magnetically ordered below the critical temperature. The iron accumulation process is different in hereditary spherocytosis and hemosiderosis. This fact may be the reason of different iron crystallization. PMID:26292972

  18. Elucidation of protein-protein interactions using chemical cross-linking or label transfer techniques.

    PubMed

    Fancy, D A

    2000-02-01

    Understanding the architectures of multiprotein complexes is a central problem in biology. Of the many chemical methods available, label transfer and cross-linking are becoming more popular. Recently, label transfer has been applied to very large protein complexes with great success, and new oxidative methods for protein cross-linking have been developed that are fast and highly efficient. Advances in these techniques should increase the understanding of biological structures and mechanisms.

  19. Controlled degradation of hydrogels using multi-functional cross-linking molecules.

    PubMed

    Lee, Kuen Yong; Bouhadir, Kamal H; Mooney, David J

    2004-06-01

    Hydrogels, chemically cross-linked or physically entangled, have found a number of applications as novel delivery vehicles of drugs and cells. However, the narrow ranges of degradation rates and mechanical strength currently available from many hydrogels limits their applications. We have hypothesized that utilization of multi-functional cross-linking molecules to form hydrogels could provide a wider range and tighter control over the degradation rates and mechanical stiffness of gels than bi-functional cross-linking molecules. To address the possibility, we isolated alpha-L-guluronate residues of sodium alginate, and oxidized them to prepare poly(aldehyde guluronate) (PAG). Hydrogels were formed with either poly(acrylamide-co-hydrazide) (PAH) as a multi-functional cross-linking molecule or adipic acid dihydrazide (AAD) as a bi-functional cross-linking molecule. The initial properties and degradation behavior of both PAG gel types were monitored. PAG/PAH hydrogels showed higher mechanical stiffness before degradation and degraded more slowly than PAG/AAD gels, at the same concentration of cross-linking functional groups. The enhanced mechanical stiffness and prolonged degradation behavior could be attributed to the multiple attachment points of PAH in the gel at the same concentration of functional groups. This approach to regulating gel properties with multifunctional cross-linking molecules could be broadly used in hydrogels. PMID:14751730

  20. Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

    DOEpatents

    Shen, Ming-Shing; Yang, Ralph T.

    1980-01-01

    Lime utilization for sulfurous oxides absorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. It is found that iron oxide present in the spent limestone acts as a catalyst to regenerate the spent limestone in a reducing environment. With only small quantities of iron oxide the calcium can be recycled at a significantly increased rate.

  1. Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

    SciTech Connect

    Shen, M.; Yang, R.T.

    1980-09-30

    Lime utilization for sulfurous oxides absorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. It is found that iron oxide present in the spent limestone acts as a catalyst to regenerate the spent limestone in a reducing environment. With only small quantities of iron oxide the calcium can be recycled at a significantly increased rate.

  2. Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

    NASA Astrophysics Data System (ADS)

    Evans, K.; Ferris, F.

    2009-05-01

    At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the

  3. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  4. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  5. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  6. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  7. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  8. 21 CFR 73.200 - Synthetic iron oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  9. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  10. 21 CFR 73.1200 - Synthetic iron oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The color additive synthetic iron oxide consists of any one or any combination of synthetically...

  11. Chemical design of biocompatible iron oxide nanoparticles for medical applications.

    PubMed

    Ling, Daishun; Hyeon, Taeghwan

    2013-05-27

    Iron oxide nanoparticles are one of the most versatile and safe nanomaterials used in medicine. Recent progress in nanochemistry enables fine control of the size, crystallinity, uniformity, and surface properties of iron oxide nanoparticles. In this review, the synthesis of chemically designed biocompatible iron oxide nanoparticles with improved quality and reduced toxicity is discussed for use in diverse biomedical applications.

  12. Acid monolayer functionalized iron oxide nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  13. Contraction of cross-linked actomyosin bundles

    NASA Astrophysics Data System (ADS)

    Yoshinaga, Natsuhiko; Marcq, Philippe

    2012-08-01

    Cross-linked actomyosin bundles retract when severed in vivo by laser ablation, or when isolated from the cell and micromanipulated in vitro in the presence of ATP. We identify the timescale for contraction as a viscoelastic time τ, where the viscosity is due to (internal) protein friction. We obtain an estimate of the order of magnitude of the contraction time τ ≈ 10-100 s, consistent with available experimental data for circumferential microfilament bundles and stress fibers. Our results are supported by an exactly solvable, hydrodynamic model of a retracting bundle as a cylinder of isotropic, active matter, from which the order of magnitude of the active stress is estimated.

  14. Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer

    PubMed Central

    Udum, Yasemin; Denk, Patrick; Adam, Getachew; Apaydin, Dogukan H.; Nevosad, Andreas; Teichert, Christian; S. White, Matthew.; S. Sariciftci, Niyazi.; Scharber, Markus C.

    2014-01-01

    We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium–tin–oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor–acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process. PMID:24817837

  15. Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer.

    PubMed

    Udum, Yasemin; Denk, Patrick; Adam, Getachew; Apaydin, Dogukan H; Nevosad, Andreas; Teichert, Christian; S White, Matthew; S Sariciftci, Niyazi; Scharber, Markus C

    2014-05-01

    We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium-tin-oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor-acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process. PMID:24817837

  16. Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer.

    PubMed

    Udum, Yasemin; Denk, Patrick; Adam, Getachew; Apaydin, Dogukan H; Nevosad, Andreas; Teichert, Christian; S White, Matthew; S Sariciftci, Niyazi; Scharber, Markus C

    2014-05-01

    We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium-tin-oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor-acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process.

  17. Reversible and irreversible cross-linking of immunoglobulin heavy chains through their carbohydrate residues.

    PubMed Central

    Heimgartner, U; Kozulić, B; Mosbach, K

    1990-01-01

    After periodate oxidation and incubation with a dihydrazide, cross-linking of the two heavy chains of immunoglobulins G from several species proceeds specifically through their oligosaccharides. We have used malonic acid dihydrazide, adipic acid dihydrazide and dithiodipropionic acid dihydrazide. The last compound is introduced in this work as a cleavable-carbohydrate-specific cross-linker. It was found that in rabbit and human immunoglobulins the degree of cross-linking was strongly dependent on the oxidation conditions but only very weakly dependent on the concentration and size of the dihydrazides. Papain cleavage of the cross-linked rabbit IgG indicated that the cross-linking occurred predominantly, if not exclusively, in the Fc region, probably through the two glycans linked to Asn-297 in the CH2 domain of each of the two heavy chains. The immunoglobulins from sheep, pig, goat and guinea pig show a comparable cross-linking pattern, indicating that the sugar chains from these immunoglobulins have a spatial structure closely related to that of rabbit and human IgG. When dithiodipropionic acid dihydrazide was used as the cross-linker, the cross-link could be cleaved by mercaptoethanol. Images Fig. 1. Fig. 2. Fig. 3. Fig. 4. Fig. 5. Fig. 6. PMID:2111130

  18. Modulatory Role of Surface Coating of Superparamagnetic Iron Oxide Nanoworms in Complement Opsonization and Leukocyte Uptake.

    PubMed

    Inturi, Swetha; Wang, Guankui; Chen, Fangfang; Banda, Nirmal K; Holers, V Michael; Wu, LinPing; Moghimi, Seyed Moein; Simberg, Dmitri

    2015-11-24

    Notwithstanding rapid advances of nanotechnology in diagnostic imaging and drug delivery, the engineered nanocarriers still exhibit substantial lack of hemocompatibility. Thus, when injected systemically, nanoparticles are avidly recognized by blood leukocytes and platelets, but the mechanisms of immune recognition are not well understood and strategies to mitigate these phenomena remain underexplored. Using superparamagnetic dextran iron oxide (SPIO) nanoworms (NWs) we demonstrate an efficient and predominantly complement-dependent uptake by mouse lymphocytes, neutrophils and monocytes from normal and tumor bearing mice in vitro. Following intravenous injection into wild type mice, blood leukocytes as well as platelets became magnetically labeled, while the labeling was decreased by 95% in complement C3-deficient mice. Using blood cells from healthy and cancer patient donors, we demonstrated that neutrophils, monocytes, lymphocytes and eosinophils took up SPIO NWs, and the uptake was prevented by EDTA (a general complement inhibitor) and by antiproperdin antibody (an inhibitor of the alternative pathway of the complement system). Cross-linking and hydrogelation of SPIO NWs surface by epichlorohydrin decreased C3 opsonization in mouse serum, and consequently reduced the uptake by mouse leukocytes by more than 70% in vivo. Remarkably, the cross-linked particles did not show a decrease in C3 opsonization in human serum, but showed a significant decrease (over 60%) of the uptake by human leukocytes. The residual uptake of cross-linked nanoparticles was completely blocked by EDTA. These findings demonstrate species differences in complement-mediated nanoparticle recognition and uptake by leukocytes, and further show that human hemocompatibility could be improved by inhibitors of complement alternative pathway and by nanoparticle surface coating. These results provide important insights into the mechanisms of hemocompatibility of nanomedicines.

  19. Modulatory Role of Surface Coating of Superparamagnetic Iron Oxide Nanoworms in Complement Opsonization and Leukocyte Uptake.

    PubMed

    Inturi, Swetha; Wang, Guankui; Chen, Fangfang; Banda, Nirmal K; Holers, V Michael; Wu, LinPing; Moghimi, Seyed Moein; Simberg, Dmitri

    2015-11-24

    Notwithstanding rapid advances of nanotechnology in diagnostic imaging and drug delivery, the engineered nanocarriers still exhibit substantial lack of hemocompatibility. Thus, when injected systemically, nanoparticles are avidly recognized by blood leukocytes and platelets, but the mechanisms of immune recognition are not well understood and strategies to mitigate these phenomena remain underexplored. Using superparamagnetic dextran iron oxide (SPIO) nanoworms (NWs) we demonstrate an efficient and predominantly complement-dependent uptake by mouse lymphocytes, neutrophils and monocytes from normal and tumor bearing mice in vitro. Following intravenous injection into wild type mice, blood leukocytes as well as platelets became magnetically labeled, while the labeling was decreased by 95% in complement C3-deficient mice. Using blood cells from healthy and cancer patient donors, we demonstrated that neutrophils, monocytes, lymphocytes and eosinophils took up SPIO NWs, and the uptake was prevented by EDTA (a general complement inhibitor) and by antiproperdin antibody (an inhibitor of the alternative pathway of the complement system). Cross-linking and hydrogelation of SPIO NWs surface by epichlorohydrin decreased C3 opsonization in mouse serum, and consequently reduced the uptake by mouse leukocytes by more than 70% in vivo. Remarkably, the cross-linked particles did not show a decrease in C3 opsonization in human serum, but showed a significant decrease (over 60%) of the uptake by human leukocytes. The residual uptake of cross-linked nanoparticles was completely blocked by EDTA. These findings demonstrate species differences in complement-mediated nanoparticle recognition and uptake by leukocytes, and further show that human hemocompatibility could be improved by inhibitors of complement alternative pathway and by nanoparticle surface coating. These results provide important insights into the mechanisms of hemocompatibility of nanomedicines. PMID:26488074

  20. Formulations for iron oxides dissolution

    DOEpatents

    Horwitz, Earl P.; Chiarizia, Renato

    1992-01-01

    A mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

  1. Nitric oxide and plant iron homeostasis.

    PubMed

    Buet, Agustina; Simontacchi, Marcela

    2015-03-01

    Like all living organisms, plants demand iron (Fe) for important biochemical and metabolic processes. Internal imbalances, as a consequence of insufficient or excess Fe in the environment, lead to growth restriction and affect crop yield. Knowledge of signals and factors affecting each step in Fe uptake from the soil and distribution (long-distance transport, remobilization from old to young leaves, and storage in seeds) is necessary to improve our understanding of plant mineral nutrition. In this context, the role of nitric oxide (NO) is discussed as a key player in maintaining Fe homeostasis through its cross talk with hormones, ferritin, and frataxin and the ability to form nitrosyl-iron complexes.

  2. Corneal collagen cross-linking: A review

    PubMed Central

    O’Brart, David P.S.

    2014-01-01

    The aim was to review the published literature on corneal collagen cross-linking. The emphasis was on the seminal publications, systemic reviews, meta-analyses and randomized controlled trials. Where such an evidence did not exist, selective large series cohort studies, case controlled studies and case series with follow-up preferably greater than 12 months were included. Riboflavin/Ultraviolet A (UVA) corneal collagen cross-linking appears to be the first treatment modality to halt the progression of keratoconus and other corneal ectatic disorders with improvement in visual, keratometric and topographic parameters documented by most investigators. Its precise mechanism of action at a molecular level is as yet not fully determined. Follow-up is limited to 4–6 years at present but suggests continued stability and improvement in corneal shape with time. Most published data are with epithelium-off techniques. Epithelium-on studies suggest some efficacy but less than with the epithelium-off procedures and long-term data are not currently available. The use of Riboflavin/UVA CXL for the management of infectious and non-infectious keratitis appears very promising. Its use in the management of bullous keratopathy is equivocal. Investigation of other methodologies for CXL are under investigation. PMID:25000866

  3. Starch vermicelli template for synthesis of magnetic iron oxide nanoclusters

    NASA Astrophysics Data System (ADS)

    Chairam, Sanoe; Somsook, Ekasith

    A novel method for fabricating magnetic iron oxide nanoparticles was achieved by using transparent vermicelli template as a new stabilizing material. The morphology of the as-prepared magnetic iron oxide deposited on the surface of vermicelli was observed as nanoclusters. The magnetization of the magnetic iron oxide nanoparticles at room temperature was decreased after carbonization at 200 °C. Therefore the thermal decomposition of iron oxide nanoparticles stabilized by starch vermicelli template yielded iron oxide/carbon nanocomposites with the soft magnetic behavior which are useful for biomedical applications.

  4. Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme

    NASA Technical Reports Server (NTRS)

    Meador, Ann B.; Capadona, Lynn A.

    2008-01-01

    A document discusses a new, simplified method for cross-linking silica and other oxide aerogels, with a polymeric material to increase strength of such materials without adversely affecting porosity or low density. This innovation introduces the polymer precursor into the sol before gelation either as an agent, which co-reacts with the oxide gel, or as soluble polymer precursors, which do not interact with the oxide gel in any way. Subsequent exposure to heat, light, catalyst or other method of promoting polymerization causes cross-linking without any additional infiltration steps.

  5. Optical properties of iron oxides

    NASA Astrophysics Data System (ADS)

    Musfeldt, Janice

    2012-02-01

    Magnetoelectric coupling in materials like multiferroics, dilute magnetic semiconductors, and topological insulators has attracted a great deal of attention, although most work has been done in the static limit. Optical spectroscopy offers a way to investigate the dynamics of charge-spin coupling, an area where there has been much less effort. Using these techniques, we discovered that charge fluctuation in LuFe2O4, the prototypical charge ordered multiferroic, has an onset well below the charge ordering transition, supporting the ``order by fluctuation'' mechanism for the development of charge order superstructure. Bragg splitting and large magneto-optical contrast suggest a low temperature monoclinic distortion that can be driven by both temperature and magnetic field. At the same time, dramatic splitting of the LuO2 layer phonon mode is attributed to charge-rich/poor proximity effects, and its temperature dependence reveals the antipolar nature of the W layer pattern. Using optical techniques, we also discovered that α-Fe2O3, a chemically-similar parent compound and one of the world's oldest and most iconic antiferromagnetic materials, appears more red in applied magnetic field than in zero field conditions. This effect is driven by a field-induced reorientation of magnetic order. The oscillator strength lost in the color band is partially transferred to the magnon side band, a process that also reveals a new exciton pattern induced by the modified exchange coupling. Analysis of the exciton pattern exposes C2/c monoclinic symmetry in the high field phase of hematite. Taken together, these findings advance our understanding of iron-based materials under extreme conditions. [4pt] Collaborators include: X. S. Xu, P. Chen, Q. -C. Sun, T. V. Brinzari (Tennessee); S. McGill (NHMFL); J. De Groot, M. Angst, R. P. Hermann (Julich); A. D. Christianson, B. C. Sales, D. Mandrus (ORNL); A. P. Litvinchuk (Houston); J. -W. Kim (Ames); Z. Islam (Argonne); N. Lee, S. -W. Cheong

  6. Oxidation Potentials in Iron and Steel Making

    NASA Astrophysics Data System (ADS)

    Matousek, J. W.

    2013-11-01

    The state of oxidation of a pyrometallurgical process given by the partial pressure of oxygen and the temperature (the oxidation potential) is one of the important properties monitored and controlled in the smelting and refining of iron and the nonferrous metals. Solid electrolyte sensors based on ZrO2 and a reference electrode such as Cr/Cr2O3 to measure the oxygen pressure found early application in the steel industry, followed soon after in copper, nickel, lead, and zinc smelting. Similar devices are installed in automobile postcombustion/exhaust trains as part of emission control systems. The current discussion reviews this technology as applied in the primary steps of iron and steel making and refining.

  7. Fibromodulin Interacts with Collagen Cross-linking Sites and Activates Lysyl Oxidase*

    PubMed Central

    Bihan, Dominique; Bonna, Arkadiusz; Rubin, Kristofer; Farndale, Richard W.

    2016-01-01

    The hallmark of fibrotic disorders is a highly cross-linked and dense collagen matrix, a property driven by the oxidative action of lysyl oxidase. Other fibrosis-associated proteins also contribute to the final collagen matrix properties, one of which is fibromodulin. Its interactions with collagen affect collagen cross-linking, packing, and fibril diameter. We investigated the possibility that a specific relationship exists between fibromodulin and lysyl oxidase, potentially imparting a specific collagen matrix phenotype. We mapped the fibromodulin-collagen interaction sites using the collagen II and III Toolkit peptide libraries. Fibromodulin interacted with the peptides containing the known collagen cross-linking sites and the MMP-1 cleavage site in collagens I and II. Interestingly, the interaction sites are closely aligned within the quarter-staggered collagen fibril, suggesting a multivalent interaction between fibromodulin and several collagen helices. Furthermore, we detected an interaction between fibromodulin and lysyl oxidase (a major collagen cross-linking enzyme) and mapped the interaction site to 12 N-terminal amino acids on fibromodulin. This interaction also increases the activity of lysyl oxidase. Together, the data suggest a fibromodulin-modulated collagen cross-linking mechanism where fibromodulin binds to a specific part of the collagen domain and also forms a complex with lysyl oxidase, targeting the enzyme toward specific cross-linking sites. PMID:26893379

  8. Fibromodulin Interacts with Collagen Cross-linking Sites and Activates Lysyl Oxidase.

    PubMed

    Kalamajski, Sebastian; Bihan, Dominique; Bonna, Arkadiusz; Rubin, Kristofer; Farndale, Richard W

    2016-04-01

    The hallmark of fibrotic disorders is a highly cross-linked and dense collagen matrix, a property driven by the oxidative action of lysyl oxidase. Other fibrosis-associated proteins also contribute to the final collagen matrix properties, one of which is fibromodulin. Its interactions with collagen affect collagen cross-linking, packing, and fibril diameter. We investigated the possibility that a specific relationship exists between fibromodulin and lysyl oxidase, potentially imparting a specific collagen matrix phenotype. We mapped the fibromodulin-collagen interaction sites using the collagen II and III Toolkit peptide libraries. Fibromodulin interacted with the peptides containing the known collagen cross-linking sites and the MMP-1 cleavage site in collagens I and II. Interestingly, the interaction sites are closely aligned within the quarter-staggered collagen fibril, suggesting a multivalent interaction between fibromodulin and several collagen helices. Furthermore, we detected an interaction between fibromodulin and lysyl oxidase (a major collagen cross-linking enzyme) and mapped the interaction site to 12 N-terminal amino acids on fibromodulin. This interaction also increases the activity of lysyl oxidase. Together, the data suggest a fibromodulin-modulated collagen cross-linking mechanism where fibromodulin binds to a specific part of the collagen domain and also forms a complex with lysyl oxidase, targeting the enzyme toward specific cross-linking sites.

  9. Facile fabrication of core cross-linked micelles by RAFT polymerization and enzyme-mediated reaction.

    PubMed

    Wu, Yukun; Lai, Quanyong; Lai, Shuqi; Wu, Jing; Wang, Wei; Yuan, Zhi

    2014-06-01

    Polymeric micelles formed in aqueous solution by assembly of amphiphilic block copolymers have been extensively investigated due to their great potential as drug carriers. However, the stability of polymeric assembly is still one of the major challenges in delivering drugs to tissues and cells. Here, we report a facile route to fabricate core cross-linked (CCL) micelles using an enzymatic polymerization as the cross-linking method. We present synthesis of poly(ethylene glycol)-block-poly(N-isopropyl acrylamide-co-N-(4-hydroxyphenethyl) acrylamide) diblock copolymer PEG-b-P(NIPAAm-co-NHPAAm) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diblock copolymer was then self-assembled into non-cross-linked (NCL) micelles upon heating above the lower critical solution temperature (LCST), and subsequently cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) as enzyme and oxidant. The characterization of the diblock copolymer and micelles were studied by NMR, DLS, UV-vis, and fluorescence spectroscopy. The fluorescence study reveals that the cross-linking process endows the micelles with much lower critical micelle concentration (CMC). In addition, the drug release study shows that the CCL micelles have lower release amount of doxorubicin (DOX) than the NCL micelles due to the enhanced stability of the CCL micelles by core cross-linking process. PMID:24768266

  10. Method for preparing hydrous iron oxide gels and spherules

    DOEpatents

    Collins, Jack L.; Lauf, Robert J.; Anderson, Kimberly K.

    2003-07-29

    The present invention is directed to methods for preparing hydrous iron oxide spherules, hydrous iron oxide gels such as gel slabs, films, capillary and electrophoresis gels, iron monohydrogen phosphate spherules, hydrous iron oxide spherules having suspendable particles homogeneously embedded within to form composite sorbents and catalysts, iron monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent, iron oxide spherules having suspendable particles homogeneously embedded within to form a composite of hydrous iron oxide fiber materials, iron oxide fiber materials, hydrous iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, dielectric spherules of barium, strontium, and lead ferrites and mixtures thereof, and composite catalytic spherules of barium or strontium ferrite embedded with oxides of Mg, Zn, Pb, Ce and mixtures thereof. These variations of hydrous iron oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters, dielectrics, and ceramics.

  11. [Riboflavin UVA cross-linking for keratoconus].

    PubMed

    Maier, P; Reinhard, T

    2013-09-01

    Keratoconus is a progressive, ectatic disease of the cornea leading to thinning and highly irregular astigmatism. Until recently all treatment options, such as prescription of glasses or contact lenses were symptomatic and neither keratoplasty nor the implantation of intracorneal rings can heal the disease. Riboflavin ultraviolet A (UVA) collagen cross-linking (CXL) cannot heal keratoconus either but promises to halt the progression. The therapeutic principle is a photochemical reaction of riboflavin and UVA light leading to free oxygen radicals in the corneal stroma that induce covalent linking of the collagen fibrils. This stiffening effect should stop the progression. After the first reports at the end of the 1990s the treatment was widely used and many case series show that CXL can be effective in stopping disease progression in some patients. However, randomized, controlled multicenter trials showing high evidence of the treatment effectiveness are rare. This report includes a review of the literature regarding treatment effectiveness, indications and new developments. PMID:23760423

  12. Corneal cross-linking treatment of keratoconus

    PubMed Central

    Farjadnia, Mahgol; Naderan, Mohammad

    2015-01-01

    Keratoconus as the most common cause of ectasia is one of the leading cause of corneal transplants worldwide. The current available therapies do not modify the underlying pathogenesis of the disease, and none of the available approaches but corneal transplant hinder the ongoing ectasia. Several studies document Crosslink defect between collagen fibrils in the pathogenesis of keratoconus. Collagen cross link is a relatively new approach that with the application of the riboflavin and ultraviolet A, new covalent bands reform. Subjective and objective results following this method seem to be promising. Endothelial damage besides other deep structural injury, which is the major concern of this technique have not yet been reported, when applying the standard method. PMID:26622134

  13. Riboflavin for corneal cross-linking.

    PubMed

    O'Brart, D P S

    2016-06-01

    Corneal collagen cross-linking (CXL) with riboflavin and ultraviolet A (UVA) radiation is the first therapeutic modality that appears to arrest the progression of keratoconus and other corneal ectasias. Riboflavin is central to the process, acting as a photosensitizer for the production of oxygen singlets and riboflavin triplets. These free radicals drive the CXL process within the proteins of the corneal stroma, altering its biomechanical properties. Riboflavin also absorbs the majority of the UVA radiation, which is potentially cytotoxic and mutagenic, within the anterior stroma, preventing damage to internal ocular structures, such as the corneal endothelium, lens and retina. Clinical studies report cessation of ectatic progression in over 90% of cases and the majority document significant improvements in visual, keratometric and topographic parameters. Clinical follow-up is limited to 5-10 years, but suggests sustained stability and enhancement in corneal shape. Sight-threatening complications are rare. The optimal stromal riboflavin dosage for CXL is as yet undetermined. PMID:27458610

  14. Glutaraldehyde cross-linked magnetic chitosan nanocomposites: Reduction precipitation synthesis, characterization, and application for removal of hazardous textile dyes.

    PubMed

    Kadam, Avinash A; Lee, Dae Sung

    2015-10-01

    Magnetic chitosan nanocomposites (MCNCs) were synthesized by an inexpensive reduction precipitation technique using a glutaraldehyde cross-linking agent at room temperature. Successful chitosan coating of iron oxide nanoparticles was confirmed by X-ray photoemission spectroscopy. X-ray diffraction data revealed crystalline particle sizes for the iron oxide and MCNCs to be around 6-7 and 8-9 nm, respectively. In addition, the MCNCs exhibited supermagnetic properties having magnetic saturation of 17.5 emu/g. The synthesized MCNCs showed 91.60% absorption of Acid Red 2, while iron oxide 16.40% absorption; enhanced performance in MCNCs was resulted from presence of free amino and hydroxyl groups. Furthermore, the optimum pH and adsorbent concentration were 3 and 1.0 g/L, respectively. The Redlich-Peterson isotherm fit experimental data better than Langmuir and Freundlich models, based on non-linear regression. Finally, MCNCs showed 96% American Dye Manufacturing Institute (ADMI) value removal and gave recovery efficiency of 100%, making them attractive for further practical applications.

  15. Cross-link guided molecular modeling with ROSETTA.

    PubMed

    Kahraman, Abdullah; Herzog, Franz; Leitner, Alexander; Rosenberger, George; Aebersold, Ruedi; Malmström, Lars

    2013-01-01

    Chemical cross-links identified by mass spectrometry generate distance restraints that reveal low-resolution structural information on proteins and protein complexes. The technology to reliably generate such data has become mature and robust enough to shift the focus to the question of how these distance restraints can be best integrated into molecular modeling calculations. Here, we introduce three workflows for incorporating distance restraints generated by chemical cross-linking and mass spectrometry into ROSETTA protocols for comparative and de novo modeling and protein-protein docking. We demonstrate that the cross-link validation and visualization software Xwalk facilitates successful cross-link data integration. Besides the protocols we introduce XLdb, a database of chemical cross-links from 14 different publications with 506 intra-protein and 62 inter-protein cross-links, where each cross-link can be mapped on an experimental structure from the Protein Data Bank. Finally, we demonstrate on a protein-protein docking reference data set the impact of virtual cross-links on protein docking calculations and show that an inter-protein cross-link can reduce on average the RMSD of a docking prediction by 5.0 Å. The methods and results presented here provide guidelines for the effective integration of chemical cross-link data in molecular modeling calculations and should advance the structural analysis of particularly large and transient protein complexes via hybrid structural biology methods. PMID:24069194

  16. Planktonic marine iron oxidizers drive iron mineralization under low-oxygen conditions.

    PubMed

    Field, E K; Kato, S; Findlay, A J; MacDonald, D J; Chiu, B K; Luther, G W; Chan, C S

    2016-09-01

    Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypothesis was that cyanobacteria produced oxygen which oxidized iron abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to banded iron formations (BIFs) and other ferruginous deposits. However, there is currently little evidence for planktonic marine iron oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 μm O2 , <0.2 μm H2 S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Cyanobacteria may be providing oxygen for microaerophilic iron oxidation through a symbiotic relationship; at high Fe(II) levels, cyanobacteria would gain protection against Fe(II) toxicity. A Zetaproteobacteria isolate from this site oxidized iron at rates sufficient to account for deposition of geologic iron formations. In sum, our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron oxidizers were likely important drivers of iron mineralization in ancient oceans. PMID:27384464

  17. Knee-simulator testing of conventional and cross-linked polyethylene tibial inserts.

    PubMed

    Muratoglu, Orhun K; Bragdon, Charles R; Jasty, Murali; O'Connor, Daniel O; Von Knoch, Rebecca S; Harris, William H

    2004-10-01

    We compared the resistance to delamination and to adhesive/abrasive wear of conventional and highly cross-linked polyethylene tibial inserts of a cruciate-retaining total knee design using a knee simulator. Both groups were tested after aggressive, accelerated aging, and 1 set of conventional inserts was studied without aging. Aging oxidized the conventional, but not the highly cross-linked, inserts. The simulated normal gait testing lasted for 5 and 10 million cycles for the conventional and highly cross-linked inserts, respectively. Aged conventional inserts showed delaminations, whereas none were observed in the unaged conventional and aged cross-linked inserts. Wear rates measured by the gravimetric method were 9 +/- 2 mm3, 10 +/- 4 mm3, and 1 +/- 0 mm3 per million cycles; by the metrologic method, they were 8 +/- 1 mm3, 9 +/- 2 mm3, and 3 +/- 0 mm3 for the unaged conventional, aged conventional, and aged highly crosslinked inserts, respectively. In the test model used, oxidation led to delamination, whereas increased cross-link density resulted in reduced adhesive/abrasive wear of tibial inserts.

  18. Site-specific cross-linking of proteins through tyrosine hexahistidine tags.

    PubMed

    Stayner, R Scott; Min, Dong-Joon; Kiser, Patrick F; Stewart, Russell J

    2005-01-01

    The genetic addition of hexahistidine (H(6)) tags is widely used to isolate recombinant proteins by immobilized metal-affinity chromatography (IMAC). Addition of a tyrosine residue to H(6) tags enabled proteins to be covalently cross-linked under mild conditions in a manner similar to the natural, site-specific cross-linking of tyrosines into dityrosine. A series of seven hexahistidine tags with tyrosines placed in various positions (H(6)Y tags) were added to the amino terminus of the I28 immunoglobulin domain of the human cardiac titin. The H(6)Y-tagged I28 dimerized in the presence of excess Ni(2+) with a K(D) of 200 microM. Treatment of Ni(2+)-dimerized H(6)Y-I28 with an oxidant, monoperoxyphthalic acid (MMPP) or sodium sulfite, resulted in covalent protein multimerization through chelated Ni(2+)-catalyzed cross-linking of the Y residues engineered into the H(6) tag. The protein oligomerization was observed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE). The presence of dityrosine in the cross-linked proteins was confirmed by fluorescence emission at 410 nm. Proteins lacking the Y residue in the H(6) tag treated with the same oxidative conditions did not cross-link or exhibit dityrosine fluorescence, despite the presence of an endogenous Y residue. The method may have potential uses in other protein conjugation applications such as protein labeling and interfacial immobilization of proteins on artificial surfaces. PMID:16287262

  19. Nitric oxide and plant iron homeostasis.

    PubMed

    Buet, Agustina; Simontacchi, Marcela

    2015-03-01

    Like all living organisms, plants demand iron (Fe) for important biochemical and metabolic processes. Internal imbalances, as a consequence of insufficient or excess Fe in the environment, lead to growth restriction and affect crop yield. Knowledge of signals and factors affecting each step in Fe uptake from the soil and distribution (long-distance transport, remobilization from old to young leaves, and storage in seeds) is necessary to improve our understanding of plant mineral nutrition. In this context, the role of nitric oxide (NO) is discussed as a key player in maintaining Fe homeostasis through its cross talk with hormones, ferritin, and frataxin and the ability to form nitrosyl-iron complexes. PMID:25612116

  20. Corneal Cross-Linking and Safety Issues

    PubMed Central

    Spoerl, Eberhard; Hoyer, Anne; Pillunat, Lutz E; Raiskup, Frederik

    2011-01-01

    Purpose: To compile the safety aspects of the corneal collagen cross-linking (CXL) by means of the riboflavin/UVA (370 nm) approach. Materials and Methodology: Analysis of the current treatment protocol with respect to safety during CXL. Results: The currently used UVA dose density of 5.4 J/cm2 and the corresponding irradiance of 3 mW/cm2 are below the known damage thresholds of UVA for the corneal endothelium, lens, and retina. Regarding the photochemical damages due to the free radicals the damage threshold for endothelial cells is 0.35 mW/cm2. In a 400μm thick corneal stroma saturated with riboflavin, the irradiance at the endothelial level is about 0.18 mW/cm2, which is a factor of 2 smaller than the damage threshold. Conclusion: As long as the corneal stroma treated has a minimal thickness of 400 microns (as recommended), neither corneal endothelium nor deeper structures such as lens and retina will suffer any damages. The light source should provide a homogenous irradiance avoiding hot spots. PMID:21399770

  1. Collagen cross-linking and resorption: effect of glutaraldehyde concentration.

    PubMed

    Roe, S C; Milthorpe, B K; Schindhelm, K

    1990-12-01

    Cross-linked collagen bioprostheses usually are designed to be inert and nonresorbable, resulting in fatigue and wear failure in high-stress environments. Eventual replacement of the implant, although minimizing strength loss during resorption, would result in a graft with reparative ability. Kangaroo tail tendon (KTT) partially cross-linked with glutaraldehyde (GA) was evaluated in vitro for resistance to bacterial collagenase digestion and in vivo for biocompatibility and resorbability in an intramuscular implant assay. Cross-linking was quantified by thermal denaturation studies. Incomplete cross-linking was achieved with concentrations of GA less than 0.1% (w/v). KTT cross-linked in greater than or equal to 0.05% GA were collagenase resistant being incompletely digested after 240 h. Cross-linking of KTT with low concentrations of GA resulted in partial collagenase resistance and slowed resorption. PMID:2126427

  2. Water clustering on nanostructured iron oxide films

    NASA Astrophysics Data System (ADS)

    Merte, Lindsay R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Lægsgaard, Erik; Wendt, Stefan; Mavrikakis, Manos; Besenbacher, Flemming

    2014-06-01

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule-molecule and molecule-surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moiré-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the bare film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moiré structure.

  3. Water Clustering on Nanostructured Iron Oxide Films

    SciTech Connect

    Merte, L. R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Laegsgaard, E.; Wendt, Stefen; Mavrikakis, Manos; Besenbacher, Fleming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule–molecule and molecule–surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire´-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the are film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moire´ structure.

  4. Cross-Linking Aromatic Polymers With Ionizing Radiation

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L.; Havens, Stephen J.

    1987-01-01

    Resistance to heat and solvents increased. Certain aromatic polymers containing radiation-sensitive methylene groups cross-linked through methylene groups upon exposure to ionizing radiation. Cross-linked polymers resistant to most organic solvents and generally more resistant to high temperatures, with less tendency to creep under load. No significant embrittlement of parts fabricated from these polymers when degree of cross-linking, as controlled by irradiation dose, kept at moderate level.

  5. Phase Formation Behavior in Ultrathin Iron Oxide.

    PubMed

    Jõgi, Indrek; Jacobsson, T Jesper; Fondell, Mattis; Wätjen, Timo; Carlsson, Jan-Otto; Boman, Mats; Edvinsson, Tomas

    2015-11-17

    Nanostructured iron oxides, and especially hematite, are interesting for a wide range of applications ranging from gas sensors to renewable solar hydrogen production. A promising method for deposition of low-dimensional films is atomic layer deposition (ALD). Although a potent technique, ALD of ultrathin films is critically sensitive to the substrate and temperature conditions where initial formation of islands and crystallites influences the properties of the films. In this work, deposition at the border of the ALD window forming a hybrid ALD/pulsed CVD (pCVD) deposition is utilized to obtain a deposition less sensitive to the substrate. A thorough analysis of iron oxide phases formation on two different substrates, Si(100) and SiO2, was performed. Films between 3 and 50 nm were deposited and analyzed with diffraction techniques, high-resolution Raman spectroscopy, and optical spectroscopy. Below 10 nm nominal film thickness, island formation and phase dependent particle crystallization impose constraints for deposition of phase pure iron oxides on non-lattice-matching substrates. Films between 10 and 20 nm thickness on SiO2 could effectively be recrystallized into hematite whereas for the corresponding films on Si(100), no recrystallization occurred. For films thicker than 20 nm, phase pure hematite can be formed directly with ALD/pCVD with very low influence of the substrate on either Si or SiO2. For more lattice matched substrates such as SnO2:F, Raman spectroscopy indicated formation of the hematite phase already for films with 3 nm nominal thickness and clearly for 6 nm films. Analysis of the optical properties corroborated the analysis and showed a quantum confined blue-shift of the absorption edge for the thinnest films. PMID:26506091

  6. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    SciTech Connect

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  7. Magnetic iron oxide nanoparticles for biomedical applications.

    PubMed

    Laurent, Sophie; Bridot, Jean-Luc; Elst, Luce Vander; Muller, Robert N

    2010-03-01

    Due to their high magnetization, superparamagnetic iron oxide nanoparticles induce an important decrease in the transverse relaxation of water protons and are, therefore, very efficient negative MRI contrast agents. The knowledge and control of the chemical and physical characteristics of nanoparticles are of great importance. The choice of the synthesis method (microemulsions, sol-gel synthesis, laser pyrolysis, sonochemical synthesis or coprecipitation) determines the magnetic nanoparticle's size and shape, as well as its size distribution and surface chemistry. Nanoparticles can be used for numerous in vivo applications, such as MRI contrast enhancement and hyperthermia drug delivery. New developments focus on targeting through molecular imaging and cell tracking. PMID:21426176

  8. Modified iron oxide nanomaterials: Functionalization and application

    NASA Astrophysics Data System (ADS)

    Bagheri, Samira; Julkapli, Nurhidayatullaili Muhd

    2016-10-01

    Iron oxide magnetic nanoparticles have aroused the interest of researchers of materials' chemistry due to its exceptional properties such as decent magnetic, electric, catalytic, biocompatibility, and low toxicity. However, these magnetic nanoparticles are predisposed towards aggregation and forming larger particles, due to its strong anisotropic dipolar interactions, particularly in the aqueous phase, consequently depriving them of dispersibility and particular properties, ultimately degrading their performance. Hence, this review focuses on modified magnetic nanoparticles that are stable, easily synthesized, possess a high surface area and could be facile-separated via magnetic forces, and are of low toxicity and costs for applications such as catalyst/catalyst support, food security, biomedical, and pollutant remediation.

  9. The Sulfide Capacity of Iron Oxide-Rich Slags

    NASA Astrophysics Data System (ADS)

    Motlagh, M.

    1988-03-01

    The relationship between the sulfide capacity of slags rich in iron oxide and the sulfur partition ratio between the metal and slag is strongly related to the slag's iron oxide concentration. For slags containing little or no lime, this relationship is linear for a constant concentration of iron oxide in the slag. The effect of silica on changes in the sulfide capacity of slags rich in iron oxide is similar to that of basic steel-making slags, particularly at low activity of silica in slag.

  10. Mineral resource of the month: iron oxide pigments

    USGS Publications Warehouse

    ,

    2008-01-01

    The article discusses iron oxide pigments, which have been used as colorants since human began painting as they resist color change due to sunlight exposure, have good chemical resistance and are stable under normal ambient conditions. Cyprus, Italy and Spain are among the countries that are known for the production of iron oxide pigments. Granular forms of iron oxides and nano-sized materials are cited as developments in the synthetic iron oxide pigment industry which are being used in computer disk drives and nuclear magnetic resonance imaging.

  11. A Diatom Ferritin Optimized for Iron Oxidation but Not Iron Storage*

    PubMed Central

    Pfaffen, Stephanie; Bradley, Justin M.; Abdulqadir, Raz; Firme, Marlo R.; Moore, Geoffrey R.; Le Brun, Nick E.; Murphy, Michael E. P.

    2015-01-01

    Ferritin from the marine pennate diatom Pseudo-nitzschia multiseries (PmFTN) plays a key role in sustaining growth in iron-limited ocean environments. The di-iron catalytic ferroxidase center of PmFTN (sites A and B) has a nearby third iron site (site C) in an arrangement typically observed in prokaryotic ferritins. Here we demonstrate that Glu-44, a site C ligand, and Glu-130, a residue that bridges iron bound at sites B and C, limit the rate of post-oxidation reorganization of iron coordination and the rate at which Fe3+ exits the ferroxidase center for storage within the mineral core. The latter, in particular, severely limits the overall rate of iron mineralization. Thus, the diatom ferritin is optimized for initial Fe2+ oxidation but not for mineralization, pointing to a role for this protein in buffering iron availability and facilitating iron-sparing rather than only long-term iron storage. PMID:26396187

  12. Inhibition of bacterial growth by iron oxide nanoparticles with and without attached drug: Have we conquered the antibiotic resistance problem?

    NASA Astrophysics Data System (ADS)

    Armijo, Leisha M.; Jain, Priyanka; Malagodi, Angelina; Fornelli, F. Zuly; Hayat, Allison; Rivera, Antonio C.; French, Michael; Smyth, Hugh D. C.; Osiński, Marek

    2015-03-01

    Pseudomonas aeruginosa is among the top three leading causative opportunistic human pathogens, possessing one of the largest bacterial genomes and an exceptionally large proportion of regulatory genes therein. It has been known for more than a decade that the size and complexity of the P. aeruginosa genome is responsible for the adaptability and resilience of the bacteria to include its ability to resist many disinfectants and antibiotics. We have investigated the susceptibility of P. aeruginosa bacterial biofilms to iron oxide (magnetite) nanoparticles (NPs) with and without attached drug (tobramycin). We also characterized the susceptibility of zero-valent iron NPs, which are known to inactivate microbes. The particles, having an average diameter of 16 nm were capped with natural alginate, thus doubling the hydrodynamic size. Nanoparticle-drug conjugates were produced via cross-linking drug and alginate functional groups. Drug conjugates were investigated in the interest of determining dosage, during these dosage-curve experiments, NPs unbound to drug were tested in cultures as a negative control. Surprisingly, we found that the iron oxide NPs inhibited bacterial growth, and thus, biofilm formation without the addition of antibiotic drug. The inhibitory dosages of iron oxide NPs were investigated and the minimum inhibitory concentrations are presented. These findings suggest that NP-drug conjugates may overcome the antibiotic drug resistance common in P. aeruginosa infections.

  13. X-Ray Diffraction Studies of Cross Linked Chitosan With Different Cross Linking Agents For Waste Water Treatment Application

    NASA Astrophysics Data System (ADS)

    Julkapli, Nurhidayatullaili Muhd; Ahmad, Zulkifli; Akil, Hazizan Md

    2010-01-01

    Chitosan is a polysaccharide derived from N-deacetylation of chitin and receiving increased attention as metal ion absorbent in wastewater treatment application. To improve the performance of chitosan as an absorbent, the cross linking approach was applied. Introduction of cross-linking agent would break the crystal zone in chitosan system, making it less crystal and consequently enhanced the absorption area. Therefore, in this study, cross-linked chitosan were prepared using different of cross-linking agents. The chitosan powder was weighed, dissolved in acetic acid (0.1 M), and dropped slowly into absolute N-methyl pyyrolidone solvent containing cross-linking agent. The cross linking reaction was carried out in N2 environment at 150° C for 6 hours. X-ray diffraction (XRD) analysis was applied to characterize the crystallinity of native and cross linked chitosan. Generally, the XRD patterns of all types of chitosan show two crystalline peaks approximately at 10° and 20° (2θ). However, the cross linked chitosan with longer length of cross linking agents show lower and broader crystalline peaks as compare to those with shorter length. Similarly, the calculated crystalline index (Cr I) also showed this decreasing tendency.

  14. THE EFFECTS OF HIGH DOSE IRRADIATION ON THE CROSS-LINKING OF VITAMIN E-BLENDED ULTRAHIGH MOLECULAR WEIGHT POLYETHYLENE

    PubMed Central

    Oral, Ebru; Beckos, Christine Godleski; Malhi, Arnaz S.; Muratoglu, Orhun K.

    2008-01-01

    Vitamin E-stabilized, highly cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is a promising oxidation and wear resistant UHMWPE with improved mechanical strength in comparison with the first generation, irradiated and melted UHMWPE. One approach of incorporating vitamin E in UHMWPE is through blending of vitamin E in UHMWPE powder followed by consolidation and radiation crosslinking. However radiation crosslinking efficiency of UHMWPE decreases in the presence of vitamin E. Therefore an optimum vitamin E concentration and radiation dose level needs to be determined to achieve a cross-link density comparable to 100-kGy irradiated and melted UHMWPE, which has shown excellent wear properties in vivo. We investigated the cross-link density and mechanical properties of vitamin E-blended UHMWPEs as a function of vitamin E concentration in the blend and gamma irradiation doses up to 200 kGy. We found that 0.3 wt% vitamin E-blended UHMWPE could not be cross-linked above a cross-link density achieved at a radiation dose of 65 kGy for virgin UHMWPE and 1.0 wt% vitamin E-blended UHMWPE could not be cross-linked above a cross-link density achieved at a radiation dose of 25 kGy for virgin UHMWPE even when the former were irradiated to a radiation dose of 200 kGy. In addition, higher plasticity at vitamin E concentrations at and above 0.3 wt% indicated that increased chain scissioning may be prevalent. Since the wear resistance of this irradiated UHMWPE would be expected to be low, vitamin E concentrations equal to or above 0.3 wt% are not recommended for subsequent irradiation to achieve a wear resistant cross-linked UHMWPE. The long–term oxidative stability of irradiated blends with low vitamin E concentrations has yet to be studied to determine an optimum between cross-link density and long-term oxidative stability. PMID:18514813

  15. Insight into the evolution of the iron oxidation pathways.

    PubMed

    Ilbert, Marianne; Bonnefoy, Violaine

    2013-02-01

    Iron is a ubiquitous element in the universe. Ferrous iron (Fe(II)) was abundant in the primordial ocean until the oxygenation of the Earth's atmosphere led to its widespread oxidation and precipitation. This change of iron bioavailability likely put selective pressure on the evolution of life. This element is essential to most extant life forms and is an important cofactor in many redox-active proteins involved in a number of vital pathways. In addition, iron plays a central role in many environments as an energy source for some microorganisms. This review is focused on Fe(II) oxidation. The fact that the ability to oxidize Fe(II) is widely distributed in Bacteria and Archaea and in a number of quite different biotopes suggests that the dissimilatory Fe(II) oxidation is an ancient energy metabolism. Based on what is known today about Fe(II) oxidation pathways, we propose that they arose independently more than once in evolution and evolved convergently. The iron paleochemistry, the phylogeny, the physiology of the iron oxidizers, and the nature of the cofactors of the redox proteins involved in these pathways suggest a possible scenario for the timescale in which each type of Fe(II) oxidation pathways evolved. The nitrate dependent anoxic iron oxidizers are likely the most ancient iron oxidizers. We suggest that the phototrophic anoxic iron oxidizers arose in surface waters after the Archaea/Bacteria-split but before the Great Oxidation Event. The neutrophilic oxic iron oxidizers possibly appeared in microaerobic marine environments prior to the Great Oxidation Event while the acidophilic ones emerged likely after the advent of atmospheric O(2). This article is part of a Special Issue entitled: The evolutionary aspects of bioenergetic systems. PMID:23044392

  16. Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

    PubMed

    Kucheryavy, Pavel; He, Jibao; John, Vijay T; Maharjan, Pawan; Spinu, Leonard; Goloverda, Galina Z; Kolesnichenko, Vladimir L

    2013-01-15

    Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

  17. In vitro degradation of covalently cross-linked arabinoxylan hydrogels by bifidobacteria.

    PubMed

    Martínez-López, Ana L; Carvajal-Millan, Elizabeth; Micard, Valérie; Rascón-Chu, Agustín; Brown-Bojorquez, Francisco; Sotelo-Cruz, Norberto; López-Franco, Yolanda L; Lizardi-Mendoza, Jaime

    2016-06-25

    Arabinoxylan gels with different cross-linking densities, swelling ratios, and rheological properties were obtained by increasing the concentration of arabinoxylan from 4 to 6% (w/v) during oxidative gelation by laccase. The degradation of these covalently cross-linked gels by a mixture of two Bifidobacterium strains (Bifidobacterium longum and Bifidobacterium adolescentis) was investigated. The kinetics of the evolution of structural morphology of the arabinoxylan gel, the carbohydrate utilization profiles and the bacterial production of short-acid fatty acid (SCFA) were measured. Scanning electron microscopy analysis of the degraded gels showed multiple cavity structures resulting from the bacterial action. The total SCFA decreased when the degree of cross-linking increased in the gels. A slower fermentation of arabinoxylan chains was obtained for arabinoxylan gels with more dense network structures. These results suggest that the differences in the structural features and properties studied in this work affect the degradation time of the arabinoxylan gels. PMID:27083795

  18. Thermochemistry of iron manganese oxide spinels

    SciTech Connect

    Guillemet-Fritsch, Sophie; Navrotsky, Alexandra . E-mail: anavrotsky@ucdavis.edu; Tailhades, Philippe; Coradin, Herve; Wang Miaojun

    2005-01-15

    Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (Mn{sub x}Fe{sub 1-x}){sub 3}O{sub 4} at 298K from the oxides, tetragonal Mn{sub 3}O{sub 4} (hausmannite) and cubic Fe{sub 3}O{sub 4} (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.670.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation-reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. {delta}S{sub mix}, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4.

  19. Multi-Scale Modeling of Cross-Linked Nanotube Materials

    NASA Technical Reports Server (NTRS)

    Frankland, S. J. V.; Odegard, G. M.; Herzog, M. N.; Gates, T. S.; Fay, C. C.

    2005-01-01

    The effect of cross-linking single-walled carbon nanotubes on the Young's modulus of a nanotube-reinforced composite is modeled with a multi-scale method. The Young's modulus is predicted as a function of nanotube volume fraction and cross-link density. In this method, the constitutive properties of molecular representative volume elements are determined using molecular dynamics simulation and equivalent-continuum modeling. The Young's modulus is subsequently calculated for cross-linked nanotubes in a matrix which consists of the unreacted cross-linking agent. Two different cross-linking agents are used in this study, one that is short and rigid (Molecule A), and one that is long and flexible (Molecule B). Direct comparisons between the predicted elastic constants are made for the models in which the nanotubes are either covalently bonded or not chemically bonded to the cross-linking agent. At a nanotube volume fraction of 10%, the Young's modulus of Material A is not affected by nanotube crosslinking, while the Young's modulus of Material B is reduced by 64% when the nanotubes are cross-linked relative to the non-cross-linked material with the same matrix.

  20. Battles with iron: manganese in oxidative stress protection.

    PubMed

    Aguirre, J Dafhne; Culotta, Valeria C

    2012-04-20

    The redox-active metal manganese plays a key role in cellular adaptation to oxidative stress. As a cofactor for manganese superoxide dismutase or through formation of non-proteinaceous manganese antioxidants, this metal can combat oxidative damage without deleterious side effects of Fenton chemistry. In either case, the antioxidant properties of manganese are vulnerable to iron. Cellular pools of iron can outcompete manganese for binding to manganese superoxide dismutase, and through Fenton chemistry, iron may counteract the benefits of non-proteinaceous manganese antioxidants. In this minireview, we highlight ways in which cells maximize the efficacy of manganese as an antioxidant in the midst of pro-oxidant iron.

  1. Cross-linked polyvinyl alcohol and method of making same

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Sheibley, D. W.; Philipp, W. H. (Inventor)

    1981-01-01

    A film-forming polyvinyl alcohol polymer is mixed with a polyaldehyde-polysaccharide cross-linking agent having at least two monosaccharide units and a plurality of aldehyde groups per molecule, perferably an average of at least one aldehyde group per monosaccharide units. The cross-linking agent, such as a polydialdehyde starch, is used in an amount of about 2.5 to 20% of the theoretical amount required to cross-link all of the available hydroxyl groups of the polyvinyl alcohol polymer. Reaction between the polymer and cross-linking agent is effected in aqueous acidic solution to produce the cross-linked polymer. The polymer product has low electrical resistivity and other properties rendering it suitable for making separators for alkaline batteries.

  2. Comparison of iron-catalyzed DNA and lipid oxidation.

    PubMed

    Djuric, Z; Potter, D W; Taffe, B G; Strasburg, G M

    2001-01-01

    Lipid and DNA oxidation catalyzed by iron(II) were compared in HEPES and phosphate buffers. Lipid peroxidation was examined in a sensitive liposome system constructed with a fluorescent probe that allowed us to examine the effects of both low and high iron concentrations. With liposomes made from synthetic 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine or from rat liver microsomal lipid, lipid peroxidation increased with iron concentration up to the range of 10--20 microM iron(II), but then rates decreased with further increases in iron concentration. This may be due to the limited amount of lipid peroxides available in liposomes for oxidation of iron(II) to generate equimolar iron(III), which is thought to be important for the initation of lipid peroxidation. Addition of hydrogen peroxide to incubations with 1--10 microM iron(II) decreased rates of lipid peroxidation, whereas addition of hydrogen peroxide to incubations with higher iron concentrations increased rates of lipid peroxidation. Thus, in this liposome system, sufficient peroxide from either within the lipid or from exogenous sources must be present to generate equimolar iron(II) and iron(III). With iron-catalyzed DNA oxidation, hydrogen peroxide always stimulated product formation. Phosphate buffer, which chelates iron but still allows for generation of hydroxyl radicals, inhibited lipid peroxidation but not DNA oxidation. HEPES buffer, which scavenges hydroxyl radicals, inhibited DNA oxidation, whereas lipid peroxidation was unaffected since presumably iron(II) and iron(III) were still available for reaction with liposomes in HEPES buffer. PMID:11284053

  3. TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

    EPA Science Inventory

    Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

  4. Ecological succession among iron-oxidizing bacteria

    PubMed Central

    Fleming, Emily J; Cetinić, Ivona; Chan, Clara S; Whitney King, D; Emerson, David

    2014-01-01

    Despite over 125 years of study, the factors that dictate species dominance in neutrophilic iron-oxidizing bacterial (FeOB) communities remain unknown. In a freshwater wetland, we documented a clear ecological succession coupled with niche separation between the helical stalk-forming Gallionellales (for example, Gallionella ferruginea) and tubular sheath-forming Leptothrix ochracea. Changes in the iron-seep community were documented using microscopy and cultivation-independent methods. Quantification of Fe-oxyhydroxide morphotypes by light microscopy was coupled with species-specific fluorescent in situ hybridization (FISH) probes using a protocol that minimized background fluorescence caused by the Fe-oxyhydroxides. Together with scanning electron microscopy, these techniques all indicated that Gallionellales dominated during early spring, with L. ochracea becoming more abundant for the remainder of the year. Analysis of tagged pyrosequencing reads of the small subunit ribosomal RNA gene (SSU rRNA) collected during seasonal progression supported a clear Gallionellales to L. ochracea transition, and community structure grouped according to observed dominant FeOB forms. Axis of redundancy analysis of physicochemical parameters collected from iron mats during the season, plotted with FeOB abundance, corroborated several field and microscopy-based observations and uncovered several unanticipated relationships. On the basis of these relationships, we conclude that the ecological niche of the stalk-forming Gallionellales is in waters with low organic carbon and steep redoxclines, and the sheath-forming L. ochracea is abundant in waters that contain high concentrations of complex organic carbon, high Fe and Mn content and gentle redoxclines. Finally, these findings identify a largely unexplored relationship between FeOB and organic carbon. PMID:24225888

  5. Microbially Induced Iron Oxidation: What, Where, How

    SciTech Connect

    SCHIERMEYER,ELISA M.; PROVENCIO,PAULA P.; NORTHUP,DIANA E.

    2000-08-15

    From the results of the different bacterial cells seen, it is fairly certain that Gallionella is present because of the bean-shaped cells and twisted stalks found with the TEM. The authors cannot confirm, though, what other iron-oxidizing genera exist in the tubes, since the media was only preferential and not one that isolated a specific genus of bacteria. Based on the environment in which they live and the source of the water, they believe their cultures contain Gallionella, Leptothrix, and possibly Crenothrix and Sphaerotilus. They believe the genus Leptothrix rather than Sphaerotilus exist in the tubes because the water source was fresh, unlike the polluted water in which Sphaerotilus are usually found. The TEM preparations worked well. The cryogenic method rapidly froze the cells in place and allowed them to view their morphology. The FAA method, as stated previously, was the best of the three methods because it gave the best contrast. The gluteraldehyde samples did not come out as well. It is possible that the gluteraldehyde the authors prepared was still too concentrated and did not mix well. Although these bacteria were collected from springs and then cultured in an environment containing a presumably pure iron-bearing metal, it seems the tube already containing Manganese Gradient Medium could be used with a piece of metal containing these bacteria. A small piece of corroding metal could then be inserted into the test tube and cultured to study the bacteria.

  6. Oxidation inhibits iron-induced blood coagulation.

    PubMed

    Pretorius, Etheresia; Bester, Janette; Vermeulen, Natasha; Lipinski, Boguslaw

    2013-01-01

    Blood coagulation under physiological conditions is activated by thrombin, which converts soluble plasma fibrinogen (FBG) into an insoluble clot. The structure of the enzymatically-generated clot is very characteristic being composed of thick fibrin fibers susceptible to the fibrinolytic degradation. However, in chronic degenerative diseases, such as atherosclerosis, diabetes mellitus, cancer, and neurological disorders, fibrin clots are very different forming dense matted deposits (DMD) that are not effectively removed and thus create a condition known as thrombosis. We have recently shown that trivalent iron (ferric ions) generates hydroxyl radicals, which subsequently convert FBG into abnormal fibrin clots in the form of DMDs. A characteristic feature of DMDs is their remarkable and permanent resistance to the enzymatic degradation. Therefore, in order to prevent thrombotic incidences in the degenerative diseases it is essential to inhibit the iron-induced generation of hydroxyl radicals. This can be achieved by the pretreatment with a direct free radical scavenger (e.g. salicylate), and as shown in this paper by the treatment with oxidizing agents such as hydrogen peroxide, methylene blue, and sodium selenite. Although the actual mechanism of this phenomenon is not yet known, it is possible that hydroxyl radicals are neutralized by their conversion to the molecular oxygen and water, thus inhibiting the formation of dense matted fibrin deposits in human blood.

  7. Iron oxidation and its impact on MR behavior

    NASA Astrophysics Data System (ADS)

    Sunkara, S. R.; Root, T. W.; Ulicny, J. C.; Klingenberg, D. J.

    2009-02-01

    The oxidation of particles in MR fluids and its impact on rheology are investigated. The oxidation of iron spheres in an aliphatic oil follows a linear growth law, suggesting that the oxide forms a nonadherent layer. The magnetic field-induced yield stress decreases with increasing extent of oxidation. The rheological behavior is consistent with that predicted using a core-shell model.

  8. Multifunctional iron oxide nanoparticles for biomedical applications

    NASA Astrophysics Data System (ADS)

    Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.

    2015-03-01

    Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.

  9. Multiple hearth furnace for reducing iron oxide

    DOEpatents

    Brandon, Mark M.; True, Bradford G.

    2012-03-13

    A multiple moving hearth furnace (10) having a furnace housing (11) with at least two moving hearths (20) positioned laterally within the furnace housing, the hearths moving in opposite directions and each moving hearth (20) capable of being charged with at least one layer of iron oxide and carbon bearing material at one end, and being capable of discharging reduced material at the other end. A heat insulating partition (92) is positioned between adjacent moving hearths of at least portions of the conversion zones (13), and is capable of communicating gases between the atmospheres of the conversion zones of adjacent moving hearths. A drying/preheat zone (12), a conversion zone (13), and optionally a cooling zone (15) are sequentially positioned along each moving hearth (30) in the furnace housing (11).

  10. Washing effect on superparamagnetic iron oxide nanoparticles

    PubMed Central

    Mireles, Laura-Karina; Sacher, Edward; Yahia, L’Hocine; Laurent, Sophie; Stanicki, Dimitri

    2016-01-01

    Much recent research on nanoparticles has occurred in the biomedical area, particularly in the area of superparamagnetic iron oxide nanoparticles (SPIONs); one such area of research is in their use as magnetically directed prodrugs. It has been reported that nanoscale materials exhibit properties different from those of materials in bulk or on a macro scale [1]. Further, an understanding of the batch-to-batch reproducibility and uniformity of the SPION surface is essential to ensure safe biological applications, as noted in the accompanying article [2], because the surface is the first layer that affects the biological response of the human body. Here, we consider a comparison of the surface chemistries of a batch of SPIONs, before and after the supposedly gentle process of dialysis in water. PMID:27141527

  11. Rheological Properties of Iron Oxide Based Ferrofluids

    NASA Astrophysics Data System (ADS)

    Devi, M.; Mohanta, D.

    2009-06-01

    In the present work, we report synthesis and magneto-viscous properties of cationic and anionic surfactant coated, iron oxide nanoparticles based ferrofluids. Structural and morphological aspects are revealed by x-ray diffraction (XRD) and transmission electron microscopy (TEM) studies. We compare the rheological/magneto-viscous properties of different ferrofluids for various shear rates (2-450 sec-1) and applied magnetic fields (0-100 gauss). In the absence of a magnetic field, and under no shear case, the ferrofluid prepared with TMAH coated particle is found to be 12% more viscous compared to its counterpart. The rheological properties are governed by non-Newtonian features, and for a definite shear rate, viscosity of a given ferrofluid is found to be strongly dependent on the applied magnetic field as well as nature of the surfactant.

  12. Gold supported iron oxide-hydroxide derived from iron ore tailings for CO oxidation

    NASA Astrophysics Data System (ADS)

    Sakthivel, R.; Das, B.; Satpati, B.; Mishra, B. K.

    2009-04-01

    Iron ore tailing, a waste material of iron ore industry, has been used to prepare iron oxide-hydroxide support for anchoring nano-gold particles. FeOOH was prepared from iron chloride solution obtained from acid digestion of iron ore tailing. Precipitation deposition method was used to prepare Au supported FeOOH. The samples were characterized by XRD, TEM, TG-DTA and FTIR. The XRD studies have confirmed the FeOOH phase and the TEM studies reveal the anchoring of gold particles on FeOOH whose size is about 5 nm. FTIR spectra showed the vibration mode of metal-oxygen bond and the presence of hydroxyl group in FeOOH and Au/FeOOH. TG-DTA results confirmed dehydration of FeOOH and the process is retarded by the presence of Au particles. The catalytic conversion of carbon monoxide by Au/FeOOH was around 55% but the catalyst became inactive after pretreatment at 300 °C in presence of oxygen which led to agglomeration of Au particles and removal of hydroxyl groups from the surface of FeOOH.

  13. “Zero-length” Cross-linking in Solid State as an Approach for Analysis of Protein -Protein Interactions

    SciTech Connect

    Elshafey, Ahmed; Tolic, Nikola; Young, Malin M.; Sale, Kenneth L.; Smith, Richard D.; Kery, Vladimir

    2006-03-01

    (II)Bpy32+ catalyzed, oxidative ?zero-length? cross-linking, confirming that it is feasible to use our strategy for analyzing the molecular interfaces of interacting proteins or peptides.

  14. Controlling barrier penetration via exothermic iron oxidation.

    PubMed

    Wood, Daniel G; Brown, Marc B; Jones, Stuart A

    2011-02-14

    Exothermic iron oxidation is an elegant means to generate heat, with the potential to modulate barrier penetration if reaction kinetics can be controlled. This aim of this study was to gain a fundamental understanding of how these temperature change kinetics influenced barrier diffusion rate. Lidocaine transport through a hydrophilic carboxymethyl cellulose (CMC) gel was compared using two rapid iron oxidation reactions initiated by water (ExoRap(50), T(max)-47.7 ± 0.6 °C, t(max)-3.3 ± 0.6 min, ExoRap(60), T(max)-60.4 ± 0.3 °C, t(max)-9.3 ± 0.6 min) and a slower reaction initiated by oxygen (ExoSl(45)T(max)-ca. 44 °C, t(max) ca. 240 min). Temperature change induced by the oxygen initiated reaction (ExoSl(45)) was almost double those initiated by water (over 4h), but lidocaine diffusion was approximately 4 times higher for the latter (ExoRap(50), 555.61 ± 22.04 μg/cm(2)/h; ExoRap(60), 663.1 ± 50.95 μg/cm(2)/h; compared to ExoSl(45), 159.36 ± 29.44 μg/cm(2)/h). The large influence of temperature change kinetics on lidocaine diffusion suggested that transport was heavily dependent on temperature induced structural changes of the barrier. CMC, like many polymers adsorbs more water when exposed to moderate increases in temperature and this appeared to be a critical determinant of lidocaine barrier diffusion rate.

  15. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  16. Elasticity of cross-linked semiflexible biopolymers under tension.

    PubMed

    von der Heydt, Alice; Wilkin, Daniel; Benetatos, Panayotis; Zippelius, Annette

    2013-09-01

    Aiming at the mechanical properties of cross-linked biopolymers, we set up and analyze a model of two weakly bending wormlike chains subjected to a tensile force, with regularly spaced inter-chain bonds (cross-links) represented by harmonic springs. Within this model, we compute the force-extension curve and the differential stiffness exactly and discuss several limiting cases. Cross-links effectively stiffen the chain pair by reducing thermal fluctuations transverse to the force and alignment direction. The extra alignment due to cross-links increases both with growing number and with growing strength of the cross-links, and is most prominent for small force f. For large f, the additional, cross-link-induced extension is subdominant except for the case of linking the chains rigidly and continuously along their contour. In this combined limit, we recover asymptotically the elasticity of a weakly bending wormlike chain without constraints, stiffened by a factor of 4. The increase in differential stiffness can be as large as 100% for small f or large numbers of cross-links.

  17. Effect of the cross-linking density on the thermoresponsive behavior of hollow PNIPAM microgels.

    PubMed

    Contreras-Cáceres, Rafael; Schellkopf, Leonard; Fernández-López, Cristina; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge; Stamm, Manfred

    2015-01-27

    We report on the fabrication of thermally responsive hollow pNIPAM particles through the oxidation of the metal core in an Au@pNIPAM system. The selective oxidation of the Au core is achieved by addition of AuCl4(-) to an aqueous dispersion of Au@pNIPAM particles in the presence of cetyltrimethylammonium bromide (CTAB). We fabricate hollow pNIPAM particles with three cross-linking densities (N,N'-methylenebis(acrylamide), BA, at 5%, 10%, and 17.5%). The study of the effect of the amount of BA within the microgel network was performed by dynamic light scattering (DLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM), showing its key role in determining the final hollow structure and thermal response. While the thermal responsiveness is largely achieved at low cross-linking densities, the hollow structure only remains at larger cross-linking densities. This was further confirmed by cryo-TEM analysis of hollow pNIPAM particles below and above the volume phase transition temperature (VPTT). Thus, it clearly shows (i) the shrinking of particle size with the temperature at low cross-linking density and (ii) the dependence of particle size on the amount of cross-linker for the final hollow pNIPAM structure. Observed differences in the hollow pNIPAM structure are attributed to different elastic contributions (Π(elas)), showing higher elasticity for microgels synthesized at lower amount of BA.

  18. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

    PubMed

    Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

    2014-03-01

    Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances.

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

    PubMed Central

    Zhang, Guandong; Liao, Yifeng; Baker, Ian

    2011-01-01

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

  20. Redox-Responsive, Core Cross-Linked Polyester Micelles

    PubMed Central

    Zhang, Zhonghai; Yin, Lichen; Tu, Chunlai; Song, Ziyuan; Zhang, Yanfeng; Xu, Yunxiang; Tong, Rong; Zhou, Qin; Ren, Jie; Cheng, Jianjun

    2013-01-01

    Monomethoxy poly(ethylene glycol)-b-poly(Tyr(alkynyl)-OCA), a biodegradable amphiphilic block copolymer, was synthesized by means of ring-opening polymerization of 5-(4-(prop-2-yn-1-yloxy)benzyl)-1,3-dioxolane-2,4-dione (Tyr(alkynyl)-OCA) and used to prepare core cross-linked polyester micelles via click chemistry. Core cross-linking not only improved the structural stability of the micelles but also allowed controlled release of cargo molecules in response to the reducing reagent. This new class of core cross-linked micelles can potentially be used in controlled release and drug delivery applications. PMID:23536920

  1. Iron Oxide as an MRI Contrast Agent for Cell Tracking

    PubMed Central

    Korchinski, Daniel J.; Taha, May; Yang, Runze; Nathoo, Nabeela; Dunn, Jeff F.

    2015-01-01

    Iron oxide contrast agents have been combined with magnetic resonance imaging for cell tracking. In this review, we discuss coating properties and provide an overview of ex vivo and in vivo labeling of different cell types, including stem cells, red blood cells, and monocytes/macrophages. Furthermore, we provide examples of applications of cell tracking with iron contrast agents in stroke, multiple sclerosis, cancer, arteriovenous malformations, and aortic and cerebral aneurysms. Attempts at quantifying iron oxide concentrations and other vascular properties are examined. We advise on designing studies using iron contrast agents including methods for validation. PMID:26483609

  2. Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

    NASA Technical Reports Server (NTRS)

    Napier, Mary E.; Stair, Peter C.

    1992-01-01

    Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

  3. Intravenous iron, inflammation, and oxidative stress: is iron a friend or an enemy of uremic patients?

    PubMed

    Garneata, Liliana

    2008-01-01

    Intravenous iron supplementation is a recognized therapy for anemia in chronic hemodialysis patients, especially in those treated with erythropoietin. The vast majority of patients with chronic kidney disease (CKD) seem to be iron-deficient, as evaluated by the usual parameters and by iron staining on bone marrow biopsy, because of multiple forms of interference with all phases of iron metabolism. The need for iron supplementation in CKD patients becomes obvious. Intravenous iron was demonstrated to be superior to oral iron in hemodialysis patients. There is also evidence for the superiority of intravenous iron in peritoneal dialysis and in nondialysis-dependent CKD patients. On the other hand, intravenous iron could promote cytotoxicity and tissue injury, and exacerbate oxidative stress and thus endothelial dysfunction, as well as inflammation and the progression of both CKD and cardiovascular disease. Nevertheless, correction of anemia is effective in reducing oxidative stress and, consequently, cardiovascular risk. The overall risk-benefit ratio favors the use of intravenous iron alone or with an erythropoietic stimulating agent in the management of renal anemia. Clinical judgment is necessary in each individual case to diagnose iron deficiency and effectively use intravenous iron.

  4. Magnetization measurements and XMCD studies on ion irradiated iron oxide and core-shell iron/iron-oxide nanomaterials

    SciTech Connect

    Kaur, Maninder; Qiang, You; Jiang, Weilin; Pearce, Carolyn; McCloy, John S.

    2014-12-02

    Magnetite (Fe3O4) and core-shell iron/iron-oxide (Fe/Fe3O4) nanomaterials prepared by a cluster deposition system were irradiated with 5.5 MeV Si2+ ions and the structures determined by x-ray diffraction as consisting of 100% magnetite and 36/64 wt% Fe/FeO, respectively. However, x-ray magnetic circular dichroism (XMCD) indicates similar surfaces in the two samples, slightly oxidized and so having more Fe3+ than the expected magnetite structure, with XMCD intensity much lower for the irradiated core-shell samples indicating weaker magnetism. X-ray absorption spectroscopy (XAS) data lack the signature for FeO, but the irradiated core-shell system consists of Fe-cores with ~13 nm of separating oxide crystallite, so it is likely that FeO exists deeper than the probe depth of the XAS (~5 nm). Exchange bias (Hex) for both samples becomes increasingly negative as temperature is lowered, but the irradiated Fe3O4 sample shows greater sensitivity of cooling field on Hex. Loop asymmetries and Hex sensitivities of the irradiated Fe3O4 sample are due to interfaces and interactions between grains which were not present in samples before irradiation as well as surface oxidation. Asymmetries in the hysteresis curves of the irradiated core/shell sample are related to the reversal mechanism of the antiferromagnetic FeO and possibly some near surface oxidation.

  5. 21 CFR 177.2420 - Polyester resins, cross-linked.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... following prescribed conditions: (a) The cross-linked polyester resins are produced by the condensation of... fiber Polyester fiber produced by the condensation of one or more of the acids listed in paragraph...

  6. Spectral Library Searching To Identify Cross-Linked Peptides.

    PubMed

    Schweppe, Devin K; Chavez, Juan D; Navare, Arti T; Wu, Xia; Ruiz, Bianca; Eng, Jimmy K; Lam, Henry; Bruce, James E

    2016-05-01

    Methods harnessing protein cross-linking and mass spectrometry (XL-MS) offer high-throughput means to identify protein-protein interactions (PPIs) and structural interfaces of protein complexes. Yet, specialized data dependent methods and search algorithms are often required to confidently assign peptide identifications to spectra. To improve the efficiency of matching high confidence spectra, we developed a spectral library based approach to search cross-linked peptide data derived from Protein Interaction Reporter (PIR) methods using the spectral library search algorithm, SpectraST. Spectral library matching of cross-linked peptide data from query spectra increased the absolute number of confident peptide relationships matched to spectra and thereby the number of PPIs identified. By matching library spectra from bona fide, previously established PIR-cross-linked peptide relationships, spectral library searching reduces the need for continued, complex mass spectrometric methods to identify peptide relationships, increases coverage of relationship identifications, and improves the accessibility of XL-MS technologies.

  7. Cross-linking of bovine and caprine caseins by microbial transglutaminase and their use as microencapsulating agents for n-3 fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bovine and caprine caseins were cross-linked with microbial transglutaminase (mTG). The mTG-cross-linked bovine or caprine casein dispersion, mixed with 14.5% maltodextrin (DE = 40), was used to prepare emulsions with 10.5% algae oil. Oxidative stability of emulsions was evaluated by peroxide valu...

  8. Large Scale Chemical Cross-linking Mass Spectrometry Perspectives.

    PubMed

    Zybailov, Boris L; Glazko, Galina V; Jaiswal, Mihir; Raney, Kevin D

    2013-02-01

    The spectacular heterogeneity of a complex protein mixture from biological samples becomes even more difficult to tackle when one's attention is shifted towards different protein complex topologies, transient interactions, or localization of PPIs. Meticulous protein-by-protein affinity pull-downs and yeast-two-hybrid screens are the two approaches currently used to decipher proteome-wide interaction networks. Another method is to employ chemical cross-linking, which gives not only identities of interactors, but could also provide information on the sites of interactions and interaction interfaces. Despite significant advances in mass spectrometry instrumentation over the last decade, mapping Protein-Protein Interactions (PPIs) using chemical cross-linking remains time consuming and requires substantial expertise, even in the simplest of systems. While robust methodologies and software exist for the analysis of binary PPIs and also for the single protein structure refinement using cross-linking-derived constraints, undertaking a proteome-wide cross-linking study is highly complex. Difficulties include i) identifying cross-linkers of the right length and selectivity that could capture interactions of interest; ii) enrichment of the cross-linked species; iii) identification and validation of the cross-linked peptides and cross-linked sites. In this review we examine existing literature aimed at the large-scale protein cross-linking and discuss possible paths for improvement. We also discuss short-length cross-linkers of broad specificity such as formaldehyde and diazirine-based photo-cross-linkers. These cross-linkers could potentially capture many types of interactions, without strict requirement for a particular amino-acid to be present at a given protein-protein interface. How these shortlength, broad specificity cross-linkers be applied to proteome-wide studies? We will suggest specific advances in methodology, instrumentation and software that are needed to make

  9. Application of novel iron core/iron oxide shell nanoparticles to sentinel lymph node identification

    NASA Astrophysics Data System (ADS)

    Cousins, Aidan; Howard, Douglas; Henning, Anna M.; Nelson, Melanie R. M.; Tilley, Richard D.; Thierry, Benjamin

    2015-12-01

    Current `gold standard' staging of breast cancer and melanoma relies on accurate in vivo identification of the sentinel lymph node. By replacing conventional tracers (dyes and radiocolloids) with magnetic nanoparticles and using a handheld magnetometer probe for in vivo identification, it is believed the accuracy of sentinel node identification in nonsuperficial cancers can be improved due to increased spatial resolution of magnetometer probes and additional anatomical information afforded by MRI road-mapping. By using novel iron core/iron oxide shell nanoparticles, the sensitivity of sentinel node mapping via MRI can be increased due to an increased magnetic saturation compared to traditional iron oxide nanoparticles. A series of in vitro magnetic phantoms (iron core vs. iron oxide nanoparticles) were prepared to simulate magnetic particle accumulation in the sentinel lymph node. A novel handheld magnetometer probe was used to measure the relative signals of each phantom, and determine if clinical application of iron core particles can improve in vivo detection of the sentinel node compared to traditional iron oxide nanoparticles. The findings indicate that novel iron core nanoparticles above a certain size possess high magnetic saturation, but can also be produced with low coercivity and high susceptibility. While some modification to the design of handheld magnetometer probes may be required for particles with large coercivity, use of iron core particles could improve MRI and magnetometer probe detection sensitivity by up to 330 %.

  10. Preparation and quality test of superparamagnetic iron oxide labeled antisense oligodeoxynucleotide probe: a preliminary study.

    PubMed

    Wen, Ming; Li, Bibo; Ouyang, Yu; Luo, Yi; Li, Shaolin

    2009-06-01

    Molecular imaging of tumor antisense gene techniques have been applied to the study of magnetic resonance (MR) gene imaging associated with malignant tumors. In this study, we designed, synthesized, and tested a novel molecular probe, in which the antisense oligodeoxynucleotide (ASODN) was labeled with superparamagnetic iron oxide (SPIO), and its efficiency was examined by in vitro MR imaging after SK-Br-3 mammary carcinoma cell lines (oncocytes) transfection. The SPIO-labeled ASODN probe was prepared through SPIO conjugated to ASODN using a chemical cross linking method. Its morphology and size were detected by atomic force microscope, size distribution were detected by laser granulometer, the conjugating rate and biological activity were determined by high performance liquid chromatography, and the stability was determined by polyacrylamide gel electrophoresis. After that, the probes were transfected into the SK-Br-3 oncocytes, cellular iron uptake was analyzed qualitatively at light and electron microscopy and was quantified at atomic absorption spectrometry, and the signal change of the transfected cells was observed and measured using MR imaging. The morphology of the SPIO-labeled ASODN probe was mostly spherical with well-distributed scattering, and the diameters were between 25 and 40 nm (95%) by atomic force microscope and laser granulometer, the conjugating rate of the probe was 99%. Moreover, this probe kept its activity under physiological conditions and could conjugate with antisense oligodeoxynucleotide. In addition, light microscopy revealed an intracellular uptake of iron oxides in the cytosol and electron microscopic studies revealed a lysosomal deposition of iron oxides in the transfected SK-Br-3 oncocytes by antisense probes, some of them gathered stacks, and the iron content of the group of transfected SK-Br-3 oncocytes by antisense probe is significantly higher (18.37 +/- 0.42 pg) than other contrast groups, the MR imaging showed that

  11. Magnetic Properties of Core/Shell Structured Iron/Iron-oxide Nanoparticles Dispersed in Polymer Matrix

    NASA Astrophysics Data System (ADS)

    Nemati Porshokouh, Zohreh; Khurshid, Hafsa; Phan, Manh-Huong; Srikanth, Hariharan

    2014-03-01

    Iron-based nanoparticles (NPs) show interesting magnetic properties for a wide range of applications; however rapid oxidation of iron limits its practical use. Protecting iron with a thin layer of iron-oxide is a possible way to prevent oxidation, forming core/shell (CS) iron/iron-oxide. Due to the different diffusivity rates of the two materials, a gap appears between the core and shell after a period of time (Kirkendall effect), degrading the magnetic properties of the sample. We minimize the Kirkendall effect while retaining good magnetic properties of ~12.5 nm CS iron/iron-oxide NPs by dispersing them into a polymer matrix. Magnetic measurements reveal that after a period of 3 months the blocking temperature (TB) of as-made CS NPs decreases from 107 K to 90 K. The change in TB marks the formation of a gap between the core and shell, which is also evident from HRTEM studies. By contrast, NPs dispersed in RP show no change in TB over the same time period. We repeated experiments with ~10.5 nm CS NPs and the results are consistent. Our study shows the importance of dispersing CS NPs in polymers to preserve desirable magnetic properties for practical applications, ranging from RF sensors and microwave devices to bioengineering.

  12. Cross-linking and the molecular packing of corneal collagen

    NASA Technical Reports Server (NTRS)

    Yamauchi, M.; Chandler, G. S.; Tanzawa, H.; Katz, E. P.

    1996-01-01

    We have quantitatively characterized, for the first time, the cross-linking in bovine cornea collagen as a function of age. The major iminium reducible cross-links were dehydro-hydroxylysinonorleucine (deH-HLNL) and dehydro-histidinohydroxymerodesmosine (deH-HHMD). The former rapidly diminished after birth; however, the latter persisted in mature animals at a level of 0.3 - 0.4 moles/mole of collagen. A nonreducible cross-link, histidinohydroxylysinonorleucine (HHL), previously found only in skin, was also found to be a major mature cross-link in cornea. The presence of HHL indicates that cornea fibrils have a molecular packing similar to skin collagen. However, like deH-HHMD, the HHL content in corneal fibrils only reaches a maximum value with time about half that of skin. These data suggest that the corneal fibrils are comprised of discrete filaments that are internally stabilized by HHL and deH-HHMD cross-links. This pattern of intermolecular cross-linking would facilitate the special collagen swelling property required for corneal transparency.

  13. Oxidative Stress and the Homeodynamics of Iron Metabolism

    PubMed Central

    Bresgen, Nikolaus; Eckl, Peter M.

    2015-01-01

    Iron and oxygen share a delicate partnership since both are indispensable for survival, but if the partnership becomes inadequate, this may rapidly terminate life. Virtually all cell components are directly or indirectly affected by cellular iron metabolism, which represents a complex, redox-based machinery that is controlled by, and essential to, metabolic requirements. Under conditions of increased oxidative stress—i.e., enhanced formation of reactive oxygen species (ROS)—however, this machinery may turn into a potential threat, the continued requirement for iron promoting adverse reactions such as the iron/H2O2-based formation of hydroxyl radicals, which exacerbate the initial pro-oxidant condition. This review will discuss the multifaceted homeodynamics of cellular iron management under normal conditions as well as in the context of oxidative stress. PMID:25970586

  14. Stabilization of soybean oil bodies by enzyme (laccase) cross-linking of adsorbed beet pectin coatings.

    PubMed

    Chen, Bingcan; McClements, David Julian; Gray, David A; Decker, Eric Andrew

    2010-08-25

    Soybean oil bodies are naturally coated by a layer of phospholipids and oleosin proteins, which protect them from in vivo environmental stresses. When oil bodies are incorporated into food products, they encounter new environmental stresses such as changes in pH, ionic strength, and temperature. Consequently, additional protection mechanisms are often needed to stabilize them. The purpose of this study was to determine whether soybean oil bodies could be stabilized by coating them with a layer of cross-linked anionic polysaccharide (beet pectin). The beet pectin layer was cross-linked via its ferulic acid groups using laccase (an enzyme that catalyzes the oxidation of phenolic groups). Oil body suspensions were prepared that contained 1 wt % oil and 0.06 wt % beet pectin at pH 7 and were then adjusted to pH 4.5 to promote electrostatic deposition of the beet pectin molecules onto the surfaces of the oil bodies. Laccase was then added to promote cross-linking of the adsorbed beet pectin layer. Cross-linked pectin-coated oil bodies had similar or better stability than uncoated oil bodies to pH changes (3 to 7), NaCl addition (0 to 500 mM), and freeze-thaw cycling (-20 °C for 22 h; +40 °C for 2 h). These pectin-coated oil bodies may provide a convenient means of incorporating soybean oil into food and other products.

  15. Aggressive wear testing of a cross-linked polyethylene in total knee arthroplasty.

    PubMed

    Muratoglu, Orhun K; Bragdon, Charles R; O'Connor, Daniel O; Perinchief, Rebecca S; Jasty, Murali; Harris, William H

    2002-11-01

    Recently, highly cross-linked polyethylenes with high wear and oxidation resistance have been developed. These materials may improve the in vivo performance of polyethylene components used in total knee arthroplasty. To date, the in vitro knee wear testing of these new polyethylenes has been done under conditions of normal gait. However, their critical assessment also must include aggressive in vitro fatigue and wear testing. In the current study, an aggressive in vitro knee wear and device fatigue model simulating a tight posterior cruciate ligament balance during stair climbing was developed and used to assess the performance of one type of highly cross-linked polyethylene tibial knee insert in comparison with conventional polyethylene. The highly cross-linked inserts and one group of conventional inserts were tested after sterilization. One additional group of conventional inserts was subjected to accelerated aging before testing. The articular surfaces of the inserts were inspected visually for surface delamination, cracking, and pitting at regular intervals during the test. The aged conventional polyethylene inserts showed extensive delamination and cracking as early as 50,000 cycles. In contrast, the unaged conventional and highly cross-linked polyethylene inserts did not show any subsurface cracking or delamination at 0.5 million cycles. The appearance and location of delamination that occurred in the aged conventional inserts tested with the current model previously have been observed in vivo with posterior cruciate-sparing design knee arthroplasties with a tight posterior cruciate ligament.

  16. Immobilisation of arsenic by iron(II)-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Kappler, A.; Hohmann, C.; Winkler, E.; Muehe, M.; Morin, G.

    2008-12-01

    Arsenic-contaminated groundwater is an environmental problem that affects about 1-2% of the world's population. As arsenic-contaminated water is also used for irrigating rice fields, the uptake of arsenic via rice is in some cases even higher than via drinking water. Arsenic is often of geogenic origin and in many cases bound to iron(III) minerals. Microbial iron(III) reduction leads to dissolution of Fe(III) minerals and thus the arsenic bound to these minerals is released to the environment. In turn, iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation followed by iron(III) mineral formation. Here, we present work on arsenic co-precipitation and immobilization by anaerobic and aerobic iron(II)-oxidizing bacteria. Co-precipitation batch experiments with pure cultures of nitrate-dependent, phototrophic, and microaerophilic Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation. Iron and arsenic speciation and redox state are determined by X- ray diffraction and synchrotron-based X-ray absorption methods (EXAFS, XANES). Microcosm experiments are set-up either with liquid media or with rice paddy soil amended with arsenic. Rice paddy soil from arsenic contaminated rice fields in China that include a natural population of Fe(II)-oxidizing microorganisms is used as inoculum. Dissolved and solid-phase arsenic and iron are quantified, Arsenic speciation is determined and the iron minerals are identified. Additionally, Arsenic uptake into the rice plant is quantified and a gene expression pattern in rice (Oryza sativa cv Gladia) is determined by microarrays as a response to the presence of Fe(II)-oxidizing bacteria.

  17. Manganese and iron oxidation by fungi isolated from building stone.

    PubMed

    de la Torre, M A; Gomez-Alarcon, G

    1994-01-01

    Acid and nonacid generating fungal strains isolated from weathered sandstone, limestone, and granite of Spanish cathedrals were assayed for their ability to oxidize iron and manganese. In general, the concentration of the different cations present in the mineral salt media directly affected Mn(IV) oxide formation, although in some cases, the addition of glucose and nitrate to the culture media was necessary. Mn(II) oxidation in acidogenic strains was greater in a medium containing the highest concentrations of glucose, nitrate, and manganese. High concentrations of Fe(II), glucose, and mineral salts were optimal for iron oxidation. Mn(IV) precipitated as oxides or hydroxides adhered to the mycelium. Most of the Fe(III) remained in solution by chelation with organic acids excreted by acidogenic strains. Other metabolites acted as Fe(III) chelators in nonacidogenic strains, although Fe(III) deposits around the mycelium were also detected. Both iron and manganese oxidation were shown to involve extracellular, hydrosoluble enzymes, with maximum specific activities during exponential growth. Strains able to oxidize manganese were also able to oxidize iron. It is concluded that iron and manganese oxidation reported in this work were biologically induced by filamentous fungi mainly by direct (enzymatic) mechanisms.

  18. Sorption of strontium onto bacteriogenic iron oxides.

    PubMed

    Langley, Sean; Gault, Andrew G; Ibrahim, Alexandre; Takahashi, Yoshio; Renaud, Rob; Fortin, Danielle; Clark, Ian D; Ferris, F Grant

    2009-02-15

    Bacteriogenic iron oxides (BIOS) were obtained from a dilute, circumneutral groundwater seep, characterized with respect to mineralogy, and examined for their ability to sorb aqueous Sr2+. BIOS were composed of microbial sheaths encrusted in 2-line ferrihydrite. Sorption experiments indicated that Sr remained completely unbound at pH < 4.5, but sorption increased with increasing pH (maximum of 95% at pH > 7.6). EXAFS analysis of Sr-loaded BIOS failed to elucidate whether Sr sorption occurred on sites specific to the mineral or microbial fraction, but indicated that sorption likely occurred by outer-sphere complexation between BIOS and hydrated Sr2+. Sorption experiments showed that at low ionic strength (I = 0.001 M), sorption followed a Langmuir isotherm (S(max) = 3.41 mol Sr (g of Fe)(1-), K(ads) = 1.26). At higher ionic strength (I = 0.1 M), there was significant inhibition of Sr sorption (S(max) = 1.06 mol Sr (g of Fe)(1-), K(ads) = 1.23), suggesting that sorption to BIOS occurs by outer-sphere complexation. The results suggest that, under dilute circumneutral conditions, BIOS deposits should efficiently sorb dissolved Sr from groundwater flow systems where such deposits exist. This finding has particular relevance to sites impacted by radioactive 90Sr groundwater contamination. PMID:19320150

  19. Sorption of strontium onto bacteriogenic iron oxides.

    PubMed

    Langley, Sean; Gault, Andrew G; Ibrahim, Alexandre; Takahashi, Yoshio; Renaud, Rob; Fortin, Danielle; Clark, Ian D; Ferris, F Grant

    2009-02-15

    Bacteriogenic iron oxides (BIOS) were obtained from a dilute, circumneutral groundwater seep, characterized with respect to mineralogy, and examined for their ability to sorb aqueous Sr2+. BIOS were composed of microbial sheaths encrusted in 2-line ferrihydrite. Sorption experiments indicated that Sr remained completely unbound at pH < 4.5, but sorption increased with increasing pH (maximum of 95% at pH > 7.6). EXAFS analysis of Sr-loaded BIOS failed to elucidate whether Sr sorption occurred on sites specific to the mineral or microbial fraction, but indicated that sorption likely occurred by outer-sphere complexation between BIOS and hydrated Sr2+. Sorption experiments showed that at low ionic strength (I = 0.001 M), sorption followed a Langmuir isotherm (S(max) = 3.41 mol Sr (g of Fe)(1-), K(ads) = 1.26). At higher ionic strength (I = 0.1 M), there was significant inhibition of Sr sorption (S(max) = 1.06 mol Sr (g of Fe)(1-), K(ads) = 1.23), suggesting that sorption to BIOS occurs by outer-sphere complexation. The results suggest that, under dilute circumneutral conditions, BIOS deposits should efficiently sorb dissolved Sr from groundwater flow systems where such deposits exist. This finding has particular relevance to sites impacted by radioactive 90Sr groundwater contamination.

  20. Stem cell tracking using iron oxide nanoparticles.

    PubMed

    Bull, Elizabeth; Madani, Seyed Yazdan; Sheth, Roosey; Seifalian, Amelia; Green, Mark; Seifalian, Alexander M

    2014-01-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) are an exciting advancement in the field of nanotechnology. They expand the possibilities of noninvasive analysis and have many useful properties, making them potential candidates for numerous novel applications. Notably, they have been shown that they can be tracked by magnetic resonance imaging (MRI) and are capable of conjugation with various cell types, including stem cells. In-depth research has been undertaken to establish these benefits, so that a deeper level of understanding of stem cell migratory pathways and differentiation, tumor migration, and improved drug delivery can be achieved. Stem cells have the ability to treat and cure many debilitating diseases with limited side effects, but a main problem that arises is in the noninvasive tracking and analysis of these stem cells. Recently, researchers have acknowledged the use of SPIONs for this purpose and have set out to establish suitable protocols for coating and attachment, so as to bring MRI tracking of SPION-labeled stem cells into common practice. This review paper explains the manner in which SPIONs are produced, conjugated, and tracked using MRI, as well as a discussion on their limitations. A concise summary of recently researched magnetic particle coatings is provided, and the effects of SPIONs on stem cells are evaluated, while animal and human studies investigating the role of SPIONs in stem cell tracking will be explored.

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

    NASA Astrophysics Data System (ADS)

    Wu, Wei; He, Quanguo; Jiang, Changzhong

    2008-10-01

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

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

    PubMed Central

    2008-01-01

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

  3. Synthesis and heating effect of iron/iron oxide composite and iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Zeng, Q.; Baker, I.; Loudis, J. A.; Liao, Y. F.; Hoopes, P. J.

    2007-02-01

    Fe/Fe oxide nanoparticles, in which the core consists of metallic Fe and the shell is composed of Fe oxides, were obtained by reduction of an aqueous solution of FeCl 3 within a NaBH 4 solution, or, using a water-in-oil micro-emulsion with CTAB as the surfactant. The reduction was performed either in an inert atmosphere or in air, and passivation with air was performed to produce the Fe/Fe 3O 4 core/shell composite. Phase identification and particle size were determined by X-ray diffraction and TEM. Thermal analysis was performed using a differential scanning calorimeter. The quasistatic magnetic properties were measured using a VSM, and the specific absorption rates (SARs) of both Fe oxide and Fe/Fe 3O 4 composite nanoparticles either dispersed in methanol or in an epoxy resin were measured by Luxtron fiber temperature sensors in an alternating magnetic field of 150 Oe at 250 kHz. It was found that the preparation conditions, including the concentrations of solutions, the mixing procedure and the heat treatment, influence the particle size, the crystal structure and consequently the magnetic properties of the particles. Compared with Fe oxides, the saturation magnetization (MS) of Fe/Fe 3O 4 particles (100-190 emu/g) can be twice as high, and the coercivity (H C) can be tunable from several Oe to several hundred Oe. Hence, the SAR of Fe/Fe 3O 4 composite nanoparticles can be much higher than that of Fe oxides, with a maximum SAR of 345 W/g. The heating behavior is related to the magnetic behavior of the nanoparticles.

  4. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section 148.275 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE... be transported on open hold all-steel barges after exposure to air for a period of at least ten days....

  5. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section 148.275 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE... be transported on open hold all-steel barges after exposure to air for a period of at least ten days....

  6. 46 CFR 148.275 - Iron oxide, spent; iron sponge, spent.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Iron oxide, spent; iron sponge, spent. 148.275 Section 148.275 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE... be transported on open hold all-steel barges after exposure to air for a period of at least ten days....

  7. The Cys-Tyr cross-link of cysteine dioxygenase changes the optimal pH of the reaction without a structural change.

    PubMed

    Davies, Casey G; Fellner, Matthias; Tchesnokov, Egor P; Wilbanks, Sigurd M; Jameson, Guy N L

    2014-12-23

    Cysteine dioxygenase (CDO) is a non-heme monoiron enzyme with an unusual posttranslational modification in the proximity of the ferrous iron active site. This modification, a cysteine to tyrosine thioether bond, cross-links two β-strands of the β-barrel. We have investigated its role in catalysis through a combined crystallographic and kinetic approach. The C93G variant lacks the cross-link and shows little change in structure from that of the wild type, suggesting that the cross-link does not stabilize an otherwise unfavorable conformation. A pH-dependent kinetic study shows that both cross-linked and un-cross-linked CDO are active but the optimal pH decreases with the presence of the cross-link. This result reflects the effect of the thioether bond on the pKa of Y157 and this residue's role in catalysis. At higher pH values, kcat is also higher for the cross-linked form, extending the pH range of activity. We therefore propose that the cross-link also increases activity by controlling deleterious interactions involving the thiol/ate of C93.

  8. Iron oxide-based nanomagnets in nanomedicine: fabrication and applications

    PubMed Central

    Meng Lin, Meng; Kim, Hyung-Hwan; Kim, Hyuck; Muhammed, Mamoun; Kyung Kim, Do

    2010-01-01

    Iron oxide-based nanomagnets have attracted a great deal of attention in nanomedicine over the past decade. Down to the nanoscale, superparamagnetic iron oxide nanoparticles can only be magnetized in the presence of an external magnetic field, which makes them capable of forming stable colloids in a physio-biological medium. Their superparamagnetic property, together with other intrinsic properties, such as low cytotoxicity, colloidal stability, and bioactive molecule conjugation capability, makes such nanomagnets ideal in both in-vitro and in-vivo biomedical applications. In this review, a chemical, physical, and biological synthetic approach to prepare iron oxide-based nanomagnets with different physicochemical properties was illustrated and compared. The growing interest in iron oxide-based nanomagnets with multifunctionalities was explored in cancer diagnostics and treatment, focusing on their combined roles in a magnetic resonance contrast agent, hyperthermia, and magnetic force assisted drug delivery. Iron oxides as magnetic carriers in gene therapy were reviewed with a focus on the sophisticated design and construction of magnetic vectors. Finally, the iron oxide-based nanomagnet also represents a very promising tool in particle/cell interfacing in controlling cellular functionalities, such as adhesion, proliferation, differentiation, and cell patterning, in stem cell therapy and tissue engineering applications. PMID:22110854

  9. Iron oxide nanoparticles in geomicrobiology: from biogeochemistry to bioremediation.

    PubMed

    Braunschweig, Juliane; Bosch, Julian; Meckenstock, Rainer U

    2013-09-25

    Iron oxides are important constituents of soils and sediments and microbial iron reduction is considered to be a significant anaerobic respiration process in the subsurface, however low microbial reduction rates of macroparticulate Fe oxides in laboratory studies led to an underestimation of the role of Fe oxides in the global Fe redox cycle. Recent studies show the high potential of nano-sized Fe oxides in the environment as, for example, electron acceptor for microbial respiration, electron shuttle between different microorganisms, and scavenger for heavy metals. Biotic and abiotic reactivity of iron macroparticles differ significantly from nano-sized Fe oxides, which are usually much more reactive. Factors such as particle size, solubility, ferrous iron, crystal structure, and organic molecules were identified to influence the reactivity. This review discusses factors influencing the microbial reactivity of Fe oxides. It highlights the differences between natural and synthetic Fe oxides especially regarding the presence of organic molecules such as humic acids and natural organic matter. Attention is given to the transport behavior of Fe oxides in laboratory systems and in the environment, because of the high affinity of different contaminants to Fe oxide surfaces and associated co-transport of pollutants. The high reactivity of Fe oxides and their potential as adsorbents for different pollutants are discussed with respect to application and development of remediation technologies.

  10. Probabilistic cross-link analysis and experiment planning for high-throughput elucidation of protein structure.

    PubMed

    Ye, Xiaoduan; O'Neil, Patrick K; Foster, Adrienne N; Gajda, Michal J; Kosinski, Jan; Kurowski, Michal A; Bujnicki, Janusz M; Friedman, Alan M; Bailey-Kellogg, Chris

    2004-12-01

    Emerging high-throughput techniques for the characterization of protein and protein-complex structures yield noisy data with sparse information content, placing a significant burden on computation to properly interpret the experimental data. One such technique uses cross-linking (chemical or by cysteine oxidation) to confirm or select among proposed structural models (e.g., from fold recognition, ab initio prediction, or docking) by testing the consistency between cross-linking data and model geometry. This paper develops a probabilistic framework for analyzing the information content in cross-linking experiments, accounting for anticipated experimental error. This framework supports a mechanism for planning experiments to optimize the information gained. We evaluate potential experiment plans using explicit trade-offs among key properties of practical importance: discriminability, coverage, balance, ambiguity, and cost. We devise a greedy algorithm that considers those properties and, from a large number of combinatorial possibilities, rapidly selects sets of experiments expected to discriminate pairs of models efficiently. In an application to residue-specific chemical cross-linking, we demonstrate the ability of our approach to plan experiments effectively involving combinations of cross-linkers and introduced mutations. We also describe an experiment plan for the bacteriophage lambda Tfa chaperone protein in which we plan dicysteine mutants for discriminating threading models by disulfide formation. Preliminary results from a subset of the planned experiments are consistent and demonstrate the practicality of planning. Our methods provide the experimenter with a valuable tool (available from the authors) for understanding and optimizing cross-linking experiments. PMID:15557270

  11. Wear measurement of highly cross-linked UHMWPE using a 7Be tracer implantation technique.

    PubMed

    Wimmer, Markus A; Laurent, Michel P; Dwiwedi, Yasha; Gallardo, Luis A; Chipps, Kelly A; Blackmon, Jeffery C; Kozub, Raymond L; Bardayan, Daniel W; Gross, Carl J; Stracener, Daniel W; Smith, Michael S; Nesaraja, Caroline D; Erikson, Luke; Patel, Nidhi; Rehm, Karl E; Ahmad, Irshad; Greene, John P; Greife, Uwe

    2013-04-01

    The very low wear rates achieved with the current highly cross-linked ultrahigh molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are therefore being explored. The purpose of this study was to perform a proof-of-concept experiment on the use of the radioactive tracer beryllium-7 ((7)Be) for the determination of in vitro wear in a highly cross-linked orthopedic UHMWPE. Three cross-linked and four conventional UHMWPE pins made from compression-molded GUR 1050, were activated with 10(9) to 10(10) (7)Be nuclei using a new implantation setup that produced a homogenous distribution of implanted nuclei up to 8.5 μm below the surface. The pins were tested for wear in a six-station pin-on-flat apparatus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and estimated to be 17 ± 3 μg per million cycles. The conventional-to-cross-linked ratio of the wear rates was 13.1 ± 0.8, in the expected range for these materials. Oxidative degradation damage from implantation was negligible; however, a weak dependence of wear on implantation dose was observed limiting the number of radioactive tracer atoms that can be introduced. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.

  12. Spectroscopic characterization of collagen cross-links in bone

    NASA Technical Reports Server (NTRS)

    Paschalis, E. P.; Verdelis, K.; Doty, S. B.; Boskey, A. L.; Mendelsohn, R.; Yamauchi, M.

    2001-01-01

    Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

  13. Collagen/elastin hydrogels cross-linked by squaric acid.

    PubMed

    Skopinska-Wisniewska, J; Kuderko, J; Bajek, A; Maj, M; Sionkowska, A; Ziegler-Borowska, M

    2016-03-01

    Hydrogels based on collagen and elastin are very valuable materials for medicine and tissue engineering. They are biocompatible; however their mechanical properties and resistance for enzymatic degradation need to be improved by cross-linking. Up to this point many reagents have been tested but more secure reactants are still sought. Squaric acid (SqAc), 3,4-dihydroxy 3-cyclobutene 1,2-dione, is a strong, cyclic acid, which reacts easily with amine groups. The properties of hydrogels based on collagen/elastin mixtures (95/5, 90/10) containing 5%, 10% and 20% of SqAc and neutralized via dialysis against deionized water were tested. Cross-linked, 3-D, transparent hydrogels were created. The cross-linked materials are stiffer and more resistant to enzymatic degradation than those that are unmodified. The pore size, swelling ability and surface polarity are reduced due to 5% and 10% of SqAc addition. At the same time, the cellular response is not significantly affected by the cross-linking. Therefore, squaric acid would be regarded as a safe, effective cross-linking agent.

  14. Iron, oxidative stress, and redox signaling in the cardiovascular system.

    PubMed

    Gudjoncik, Aurélie; Guenancia, Charles; Zeller, Marianne; Cottin, Yves; Vergely, Catherine; Rochette, Luc

    2014-08-01

    The redox state of the cell is predominantly dependent on an iron redox couple and is maintained within strict physiological limits. Iron is an essential metal for hemoglobin synthesis in erythrocytes, for oxidation-reduction reactions, and for cellular proliferation. The maintenance of stable iron concentrations requires the coordinated regulation of iron transport into plasma from dietary sources in the duodenum, from recycled senescent red cells in macrophages, and from storage in hepatocytes. The absorption of dietary iron, which is present in heme or nonheme form, is carried out by mature villus enterocytes of the duodenum and proximal jejunum. Multiple physiological processes are involved in maintaining iron homeostasis. These include its storage at the intracellular and extracellular level. Control of iron balance in the whole organism requires communication between sites of uptake, utilization, and storage. Key protein transporters and the molecules that regulate their activities have been identified. In this field, ferritins and hepcidin are the major regulator proteins. A variety of transcription factors may be activated depending on the level of oxidative stress, leading to the expression of different genes. Major preclinical and clinical trials have shown advances in iron-chelation therapy for the treatment of iron-overload disease as well as cardiovascular and chronic inflammatory diseases.

  15. Iron, oxidative stress, and redox signaling in the cardiovascular system.

    PubMed

    Gudjoncik, Aurélie; Guenancia, Charles; Zeller, Marianne; Cottin, Yves; Vergely, Catherine; Rochette, Luc

    2014-08-01

    The redox state of the cell is predominantly dependent on an iron redox couple and is maintained within strict physiological limits. Iron is an essential metal for hemoglobin synthesis in erythrocytes, for oxidation-reduction reactions, and for cellular proliferation. The maintenance of stable iron concentrations requires the coordinated regulation of iron transport into plasma from dietary sources in the duodenum, from recycled senescent red cells in macrophages, and from storage in hepatocytes. The absorption of dietary iron, which is present in heme or nonheme form, is carried out by mature villus enterocytes of the duodenum and proximal jejunum. Multiple physiological processes are involved in maintaining iron homeostasis. These include its storage at the intracellular and extracellular level. Control of iron balance in the whole organism requires communication between sites of uptake, utilization, and storage. Key protein transporters and the molecules that regulate their activities have been identified. In this field, ferritins and hepcidin are the major regulator proteins. A variety of transcription factors may be activated depending on the level of oxidative stress, leading to the expression of different genes. Major preclinical and clinical trials have shown advances in iron-chelation therapy for the treatment of iron-overload disease as well as cardiovascular and chronic inflammatory diseases. PMID:24888568

  16. Inflammatory imaging with ultrasmall superparamagnetic iron oxide.

    PubMed

    Matsushita, Taro; Kusakabe, Yoshinori; Fujii, Hitomi; Murase, Katsutoshi; Yamazaki, Youichi; Murase, Kenya

    2011-02-01

    The purpose of this study was to investigate the usefulness and feasibility of magnetic resonance imaging (MRI) with ultrasmall superparamagnetic iron oxide (USPIO) (USPIO-enhanced MRI) for imaging inflammatory tissues. First, we investigated the relationship between the apparent transverse relaxation rate (R2*) and the concentration of USPIO by phantom studies and measured the apparent transverse relaxivity (r2*) of USPIO. Second, we performed animal experiments using a total of 30 mice. The mice were divided into five groups [A (n=6), B (n=6), C (n=6), sham control (n=6), and control (n=6)]. The mice in Groups A, B, C and control were subcutaneously injected with 0.1 ml of turpentine oil on Day 0, while those in the sham control group were subcutaneously injected with 0.1 ml of saline. The mice in Groups A, B, C and sham control were intraperitoneally injected with 200 μmol Fe per kilogram body weight of USPIO (28 nm in diameter) immediately after the first MRI study on Days 3, 5, 7 and 7, respectively, and those in the control group were not injected with USPIO. The second and third MRI studies were performed at 24 and 48 h after USPIO administration, respectively. The maps of R2* were generated from the apparent transverse relaxation time (T2*)-weighted images with six different echo times. The phantom studies showed that there was a linear relationship between R2* and the concentration of USPIO (r=0.99) and the r2* value of USPIO was 105.7 mM(-1) s(-1). There was a significant increase of R2* in inflammatory tissues in Group C at 24 h after USPIO administration compared with the precontrast R2* value. Our results suggest that USPIO-enhanced MRI combined with R2* measurement is useful for detecting inflammatory tissues. PMID:20850245

  17. Iron release and oxidant damage in human myoblasts by divicine.

    PubMed

    Ninfali, P; Perini, M P; Bresolin, N; Aluigi, G; Cambiaggi, C; Ferrali, M; Pompella, A

    2000-01-01

    Divicine is an aglycone derived from vicine, a glucosidic compound contained in fava beans (Vicia faba major or broad beans). In this study, we investigated the effect of divicine on cultured human myoblasts from normal subjects, in order to see if the drug may induce signs of oxidant stress in these cells. Myoblasts incubated 24 hours in the presence of 1 mM divicine, showed an increase of carbonyl groups and 4-hydroxynonenal (4-HNE) bound to cell proteins, as well as a significant release of iron and lactate dehydrogenase in the culture medium. Desferrioxamine (DFO), an iron chelator, significantly prevented protein oxidation and formation 4-HNE adducts. Our results can be interpreted as indicating that divicine autooxidizes both at extracellular level and into myoblasts thus inducing the release of free iron, which initiates oxidation of cellular proteins and lipids. DFO protects the cells by subtracting the free iron both at intracellular and extracellular level. PMID:10794072

  18. Analysis of iron oxide precipitates in constructed mine wastewater treatments

    SciTech Connect

    Partezana, J.M.

    1996-10-01

    The purpose or this research project is to characterize iron oxide precipitates collected from abandoned mine drainage (AMD) treatment facilities in order to determine whether these precipitates have possible commercial value. The treatment facilities use constructed wetlands to raise pH levels to near neutral levels and to remove iron and other heavy metals from AMD polluted water. The main commercial value of interest is in the use of pigments in products such as paints, clay and brick. The precipitates arc characterized for composition and quality against natural and synthetic commercial pigment products. Various processing techniques were developed for sample preparation. Analysis tests include: general pigment tests, heavy metals, anions, particle size, and particle composition. Results show that the iron oxide precipitates are chemically similar to the commercial iron oxide but will require additional processing to meet pigment qualifications.

  19. Iron accumulation with age, oxidative stress and functional decline.

    PubMed

    Xu, Jinze; Knutson, Mitchell D; Carter, Christy S; Leeuwenburgh, Christiaan

    2008-01-01

    Identification of biological mediators in sarcopenia is pertinent to the development of targeted interventions to alleviate this condition. Iron is recognized as a potent pro-oxidant and a catalyst for the formation of reactive oxygen species in biological systems. It is well accepted that iron accumulates with senescence in several organs, but little is known about iron accumulation in muscle and how it may affect muscle function. In addition, it is unclear if interventions which reduced age-related loss of muscle quality, such as calorie restriction, impact iron accumulation. We investigated non-heme iron concentration, oxidative stress to nucleic acids in gastrocnemius muscle and key indices of sarcopenia (muscle mass and grip strength) in male Fischer 344 X Brown Norway rats fed ad libitum (AL) or a calorie restricted diet (60% of ad libitum food intake starting at 4 months of age) at 8, 18, 29 and 37 months of age. Total non-heme iron levels in the gastrocnemius muscle of AL rats increased progressively with age. Between 29 and 37 months of age, the non-heme iron concentration increased by approximately 200% in AL-fed rats. Most importantly, the levels of oxidized RNA in gastrocnemius muscle of AL rats were significantly increased as well. The striking age-associated increase in non-heme iron and oxidized RNA levels and decrease in sarcopenia indices were all attenuated in the calorie restriction (CR) rats. These findings strongly suggest that the age-related iron accumulation in muscle contributes to increased oxidative damage and sarcopenia, and that CR effectively attenuates these negative effects.

  20. Iron Accumulation with Age, Oxidative Stress and Functional Decline

    PubMed Central

    Xu, Jinze; Knutson, Mitchell D.; Carter, Christy S.; Leeuwenburgh, Christiaan

    2008-01-01

    Identification of biological mediators in sarcopenia is pertinent to the development of targeted interventions to alleviate this condition. Iron is recognized as a potent pro-oxidant and a catalyst for the formation of reactive oxygen species in biological systems. It is well accepted that iron accumulates with senescence in several organs, but little is known about iron accumulation in muscle and how it may affect muscle function. In addition, it is unclear if interventions which reduced age-related loss of muscle quality, such as calorie restriction, impact iron accumulation. We investigated non-heme iron concentration, oxidative stress to nucleic acids in gastrocnemius muscle and key indices of sarcopenia (muscle mass and grip strength) in male Fischer 344 X Brown Norway rats fed ad libitum (AL) or a calorie restricted diet (60% of ad libitum food intake starting at 4 months of age) at 8, 18, 29 and 37 months of age. Total non-heme iron levels in the gastrocnemius muscle of AL rats increased progressively with age. Between 29 and 37 months of age, the non-heme iron concentration increased by approximately 200% in AL-fed rats. Most importantly, the levels of oxidized RNA in gastrocnemius muscle of AL rats were significantly increased as well. The striking age-associated increase in non-heme iron and oxidized RNA levels and decrease in sarcopenia indices were all attenuated in the calorie restriction (CR) rats. These findings strongly suggest that the age-related iron accumulation in muscle contributes to increased oxidative damage and sarcopenia, and that CR effectively attenuates these negative effects. PMID:18682742

  1. Engineering of Superparamagnetic Core-Shell Iron Oxide/N-Chloramine Nanoparticles for Water Purification.

    PubMed

    Haham, Hai; Natan, Michal; Gutman, Ori; Kolitz-Domb, Michal; Banin, Ehud; Margel, Shlomo

    2016-07-20

    In this study, we describe the synthesis and characterization of superparamagnetic core-shell iron oxide (IO)/N-halamine antibacterial nanoparticles (NPs). For this purpose, superparamagnetic IO core NPs were coated with cross-linked polymethacrylamide (PMAA) by surfactant-free dispersion copolymerization of methacrylamide and N,N-methylenebis(acrylamide) in an aqueous continuous phase. The effect of the polymerization process on the chemical composition, size, shape, crystallinity, and magnetic properties of the IO/PMAA NPs was elucidated. Conversion of the core-shell IO/PMAA NPs into their N-halamine form, IO/PMAA-Cl, was accomplished using a chlorination reaction with sodium hypochlorite. The influence of chlorination on the shape, crystallinity, and magnetic properties of the IO/PMAA NPs was studied. The IO/PMAA-Cl NPs demonstrated excellent antibacterial activity against Gram-negative and Gram-positive bacteria. Finally, the chlorination recharging capabilities of the NPs and their potential for use in the purification of water containing bacteria were demonstrated with magnetic columns packed with the IO/PMAA-Cl NPs. PMID:27348740

  2. Oxidation-Induced Degradable Nanogels for Iron Chelation

    PubMed Central

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-01-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells. PMID:26868174

  3. Synthesis of carbon-encapsulated iron nanoparticles via solid state reduction of iron oxide nanoparticles

    SciTech Connect

    Bystrzejewski, M.

    2011-06-15

    The encapsulation of iron nanoparticles in protective carbon cages leads to unique hybrid core-shell nanomaterials. Recent literature reports suggest that such nanocomposites can be obtained in a relatively simple process involving the solid state carbothermal reduction of iron oxide nanoparticles. This approach is very attractive because it does not require advanced equipment and consumes less energy in comparison to widely used plasma methods. The presented more-in-depth study shows that the carbothermal approach is sensitive to temperature and the process yield strongly depends on the morphology and crystallinity of the carbon material used as a reductant. - Graphical abstract: Reduction of iron oxide nanoparticles by carbon black at 1200 deg. C yields well crystallized carbon-encapsulated iron nanoparticles. Highlights: > Carbon-encapsulated iron nanoparticles were synthesized by carbothermal reduction of iron oxide nanoparticles. > The process has the highest selectivity at 1200 C. > Lower temperatures result in iron oxide nanoparticles wrapped in carbon matrix. > The encapsulation rate of Fe at 1200 deg. C was found to be 15%.

  4. Extreme dryness and DNA-protein cross-links

    NASA Astrophysics Data System (ADS)

    Bieger-Dose, A.; Dose, K.; Meffert, R.; Mehler, M.; Risi, S.

    Exposure of fungal conidia (Aspergillus ochraceus) or spores of Bacillus subtilis to extreme dryness or vacuum induces DNA lesions, including strand breaks and the formation of DNA-protein cross-links. In wet cells only a small amount of protein is bound to DNA, but exposure to conditions of lowered water activity results in an increasing number of cross-links between DNA and proteins. In fungal conidia these cross-links are detected after selective iodination (125J) of the DNA-bound proteins followed by gel electrophoresis and subsequent autoradiography. Another approach is the labelling of DNA with 32p by means of nick translation and the detection of differences in the electrophoretic mobility of DNA before and after digestion with proteinase K of proteins bound to DNA.

  5. FTIR Spectroscopic Studies on Cross Linking of SU-8 Photoresist

    NASA Astrophysics Data System (ADS)

    Kalaiselvi, S. M. P.; Tan, T. L.; Rawat, R. S.; Lee, P.; Heussler, S. P.; Breese, M. B. H.

    2013-11-01

    The usage of chemically-amplified, negative tone SU-8 photoresist is numerous, spanning industrial, scientific and medical fields. Hence, in this study, some preliminary studies were conducted to understand the dosage and heat treatment requirements of the SU-8 photoresist essential for pattern generation using X-ray lithography. In this work, using Synchrotron as the X-ray source, SU-8 photoresist was characterized for X-ray lithography in terms of its process parameters such as X-ray exposure dose, post exposure bake (PEB) time and temperature for various photoresist thicknesses which is considered worthwhile in view of applications of SU-8 for the fabrication of very high aspect ratio micro structures. The process parameters were varied and the resultant cross linking of the molecular chains of the photoresist was accurately monitored using a Fourier Transform Infra-Red (FTIR) spectrometer and the results are discussed. The infrared absorption peak at 914 cm-1 in the spectrum of the SU-8 photoresist was found to be a useful indicator for the completion of cross linking in the SU-8 photoresist. Results show that the cross linking of the SU-8 photoresist is at a higher rate from 0 J/cm3 to 30 J/cm3 after which the peak almost saturates regardless of the PEB time. It is a good evidence for the validation of dosage requirement of SU-8 photoresist for effective completion of cross linking, which in turn is a requirement for efficient fabrication of micro and nano structures. An analogous behavior was also observed between the extent of cross linking and the PEB time and temperature. The rate of cross linking declines after a certain period of PEB time regardless of PEB temperature. The obtained results also show a definite relation between variation of the absorbance area of the peak at 914 cm-1 and the X-ray exposure dose.

  6. The Oxidation Of Iron In A Gel Using Consumer Chemicals

    ERIC Educational Resources Information Center

    Wright, Stephen W.; Folger, Marsha R.; Quinn, Ryan P.; Sauls, Frederick C.; Krone, Diane

    2005-01-01

    An experiment is conducted for the oxidation of iron in a gel using consumer chemicals, which is pertinent to the students' understanding of redox chemistry and of the relative oxidation potentials of various metals. The experiment can be carried out with consumer chemicals that might be purchased at a supermarket and commonly found in the home.

  7. Synthesis of phase pure praseodymium barium copper iron oxide.

    PubMed

    Konne, Joshua L; Davis, Sean A; Glatzel, Stefan; Hall, Simon R

    2013-06-18

    The control of crystallization of praseodymium barium copper iron oxide, an intermediate temperature solid oxide fuel cell cathode material, has been demonstrated for the first time using a biotemplated sol-gel synthesis technique. The results obtained showed significant improvement in purity, synthesis time, surface area and simplicity over that previously reported.

  8. Photochemical Activation of Chlorine by Iron and Iron Oxide Aerosol

    NASA Astrophysics Data System (ADS)

    Wittmer, J.; Zetzsch, C.

    2015-12-01

    The photochemical activation of chlorine by dissolved iron in sea-salt aerosol droplets and by highly dispersed Fe2O3 aerosol particles (mainly hematite, specific surface > 100 m2/g), exposed to gaseous HCl, was investigated in humidified air in a Teflon simulation chamber. Employing the radical-clock technique, we quantified the production of gaseous atomic Cl. When the artificial sea salt aerosols contained suspended Fe2O3 alone at pH 6, no significant Cl production could be observed, even if the dissolution of iron was forced by "weathering" (repeatedly freezing and thawing for five times). Adjusting the pH in the stock suspension to 2.6, 2.2, and 1.9 and equilibrating for one week resulted in a quantifiable amount of dissolved iron (0.03, 0.2, and 0.6 mmol/L, respectively) and in gaseous Cl production rates of ~1.6, 6, and 8 × 1021 atoms cm-2 h-1, respectively. Exposing the pure Fe2O3 aerosol in the absence of salt to various gaseous HCl concentrations resulted in rates ranging from 8 × 1020 Cl atoms cm-2 h-1 (at ~4 ppb HCl) to 5 × 1022 Cl atoms cm-2 h-1 (at ~350 ppb HCl) and confirmed the uptake and conversion of HCl to atomic Cl (at HCl to Cl conversion yields of 2-5 % mol/mol, depending on the relative humidity). The relevance for environmental processes in the atmosphere will be discussed.

  9. Photo-induced cross-linking of unmodified proteins (PICUP) applied to amyloidogenic peptides.

    PubMed

    Rahimi, Farid; Maiti, Panchanan; Bitan, Gal

    2009-01-01

    The assembly of amyloidogenic proteins into toxic oligomers is a seminal event in the pathogenesis of protein misfolding diseases, including Alzheimer's, Parkinson's, and Huntington's diseases, hereditary amyotrophic lateral sclerosis, and type 2 diabetes. Owing to the metastable nature of these protein assemblies, it is difficult to assess their oligomer size distribution quantitatively using classical methods, such as electrophoresis, chromatography, fluorescence, or dynamic light scattering. Oligomers of amyloidogenic proteins exist as metastable mixtures, in which the oligomers dissociate into monomers and associate into larger assemblies simultaneously. PICUP stabilizes oligomer populations by covalent cross-linking and when combined with fractionation methods, such as sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) or size-exclusion chromatography (SEC), PICUP provides snapshots of the oligomer size distributions that existed before cross-linking. Hence, PICUP enables visualization and quantitative analysis of metastable protein populations and can be used to monitor assembly and decipher relationships between sequence modifications and oligomerization(1). Mechanistically, PICUP involves photo-oxidation of Ru(2+) in a tris(bipyridyl)Ru(II) complex (RuBpy) to Ru(3+) by irradiation with visible light in the presence of an electron acceptor. Ru(3+) is a strong one-electron oxidizer capable of abstracting an electron from a neighboring protein molecule, generating a protein radical(1,2). Radicals are unstable, highly-reactive species and therefore disappear rapidly through a variety of intra- and intermolecular reactions. A radical may utilize the high energy of an unpaired electron to react with another protein monomer forming a dimeric radical, which subsequently loses a hydrogen atom and forms a stable, covalently-linked dimer. The dimer may then react further through a similar mechanism with monomers or other dimers to form higher

  10. Oegylated and cross-linking carbazole dendrons and dendrimers: Synthesis, characterization, assembly and thin film fabrication

    NASA Astrophysics Data System (ADS)

    Felipe, Mary Jane Legaspi

    2011-12-01

    Dendrimers and dendrons (fractional dendrimers) are macromolecular structures that have well-defined molecular weights and precise number of functional groups. Tailoring these structures has provided designer molecules that can be used for various applications including drug delivery, sensors, and anti-biofouling surfaces. Overall, this dissertation provides novel protocols for the understanding of molecular design, synthesis, and structure-property relationship of OEGylated and conjugated carbazole dendrons and dendrimers. In this design, the use of oligo(ethylene glycol) (OEG) allows for the fabrication of biocompatible materials and imparts hydrophilicity on the structure while the carbazole functionality allows the cross-linking of these designer molecules. Such fine-tuning of macromolecular structures leading to the fabrication of anti-biofouling thin films, nanostructuring at the air-water interface, and assembly into supramolecular superstructures are considered in this dissertation. Chapter 2 details the synthesis, characterization, and electrochemical cross-linking of OEGylated linear dendrons and "Janus-type" dendrimers. Cross-linking the carbazole moieties enables the deposition of these films on Au, indium tin oxide-coated glass, and doped silicon through cyclic voltammetry and provides films with secondary level of organization imparted by the inter- and intra-molecular interaction among the carbazole units. Chapter 3 describes the fabrication of nonspecific protein adsorption resistant surfaces through electrochemical grafting of three different dendrons on SAM carbazole-coated gold substrates. The predictable shape of each dendron and the ability to cross-link the carbazole units have enabled parametrization of OEG conformation and density on these interfaces. Chapter 4 demonstrates the fundamental architectural requirements for obtaining stable films with OEGylated linear dendron molecules providing a new architectural design of nanostructuring

  11. Swelling of cross-linked polystyrene spheres in toluene vapor

    SciTech Connect

    Zhang, R.; Graf, K.; Berger, R.

    2006-11-27

    The swelling behavior of individual micron-sized polystyrene (PS) spheres in toluene vapor was studied via mass loading by means of micromechanical cantilever sensors. For 4%-8% cross-linked PS a mass increase of 180% in saturated toluene vapor was measured. The mass of the swollen PS sphere decreases with increasing exposure time to ultraviolet light. In addition, the swelling response is significantly different between the first and the second exposure to toluene vapor. This is attributed to the formation of a cross-linked shell at the surface of the PS spheres. Shape persistent parts were observed for locally irradiated PS spheres.

  12. Cross-Linked Nanotube Materials with Variable Stiffness Tethers

    NASA Technical Reports Server (NTRS)

    Frankland, Sarah-Jane V.; Odegard, Gregory M.; Herzog, Matthew N.; Gates, Thomas S.; Fay, Catherine C.

    2004-01-01

    The constitutive properties of a cross-linked single-walled carbon nanotube material are predicted with a multi-scale model. The material is modeled as a transversely isotropic solid using concepts from equivalent-continuum modeling. The elastic constants are determined using molecular dynamics simulation. Some parameters of the molecular force field are determined specifically for the cross-linker from ab initio calculations. A demonstration of how the cross-linked nanotubes may affect the properties of a nanotube/polyimide composite is included using a micromechanical analysis.

  13. Potassium promotion of iron oxide dehydrogenation catalysts supported on magnesium oxide: 1. Preparation and characterization

    SciTech Connect

    Stobbe, D.E.; Buren, F.R. van ); Dillen, A.J. van; Geus, J.W. )

    1992-06-01

    Catalysts of iron oxide supported on magnesium oxide and promoted with potassium were prepared by incipient wetness impregnation of preshaped magnesium oxide support pellets with a solution of an iron complex, either ammonium iron (III) citrate or ammonium iron (III) EDTA and potassium carbonate. Iron and potassium were applied wither simultaneously or consecutively. As determined using X-ray diffraction, thermogravimetric analysis, and magnetic measurements, calcination above 923 K results in the formation of a mixed oxide of iron and potassium, viz., KFeO[sub 2]. After calcination at 973 K the average crystallite size of the KFeO[sub 2] phase is about 300 [angstrom]. The formation of KFeO[sub 2] appeared to have a strong retarding effect on the reduction of the iron oxide phase to metallic iron. It was found that the KFeO[sub 2] phase is unstable in atomspheric air due to reaction with carbon dioxide and moisture to form potassium (hydrogen) carbonate and (hydrated) iron oxide.

  14. Deoxyribonucleic acid-protein and deoxyribonucleic acid interstrand cross-links induced in isolated chromatin by hydrogen peroxide and ferrous ethylenediaminetetraacetate chelates

    SciTech Connect

    Lesko, S.A.; Drocourt, J.; Yang, S.

    1982-01-01

    DNA-protein and DNA interstrand cross-links were induced in isolated chromatin after treatment with H/sub 2/O/sub 2/ and ferrous ethylenediaminetetraacetate (EDTA). Retention of DNA on membrane filters after heating of chromatin in a dissociating solvent indicated the presence of a stable linkage between DNA and protein. Treatment of protein-free DNA with H/sub 2/O/sub 2//Fe/sup 2 +/-EDTA did not result in enhanced filter retention. Incubation of cross-linked chromatin with proteinase K completely eliminated filter retention. Resistance to S/sub 1/ nuclease after a denaturation-renaturation cycle was used to detect DNA interstrand cross-links. Heating the treated chromatin at 45/sup 0/C for 16 h and NaBH/sub 4/ reduction enhanced the extent of interstrand cross-linking. The following data are consistent with, but do not totally prove, the hypothesis that cross-links are induced by hydroxyl radicals generated in Fenton-type reactions: (1) cross-linking was inhibited by hydroxyl radical scavengers; (2) the degree of inhibition of DNA interstrand cross-links correlated very closely with the rate constants of the scavengers for reaction with hydroxyl radicals; (3) cross-linking was eliminated or greatly reduced by catalase; (4) the extent of cross-linking was directly related to the concentration of Fe/sup 2 +/-EDTA. Partial inhibition of cross-linking by superoxide dismutase indicates that super-oxide-driven Fenton chemistry is involved. The data indicate that DNA cross-linking may play a role in the manifestation of the biological activity of agents of systems that generate reactive hydroxyl radicals.

  15. Biogeochemistry of Iron Oxidation in a Circumneutral Freshwater Habitat

    NASA Astrophysics Data System (ADS)

    Duckworth, O.; Homstrom, S.; Pena, J.; Zacharias, E.; Sposito, G.

    2007-12-01

    Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, may be biologically- mediated when it occurs in iron-rich redox gradients. West Berry Creek, a small circumneutral tributary flowing through a mixed coniferous forest in Big Basin State Park, California, contains localized iron (hydr)oxide precipitates at points along its course where anoxic groundwater meets oxygenated creek water. These mixing zones establish redox gradients and iron-rich microbial mats that may create microenvironments that promote active biogeochemical cycling of Fe. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography-mass spectrometry detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the iron precipitates to be amorphous minerals, such as ferrihydrite. Microbial biofilm communities are associated with the iron (hydr)oxide deposits. Clone libraries developed from 16s rDNA sequences revealed the presence of microorganisms related to the neutrophilic iron- oxidizing bacteria Gallionella and Siderooxidans; in addition, micrographs suggest the widespread presence of sheath-forming bacteria (e.g., Leptothrix). Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera Pseudomonas, Sphingomonas, and Nitrospira. These geosymbiotic systems appear to be significant not only for the biogeochemical cycling of iron in the creek, but also for the cycling of organic species, inorganic nutrients, and trace metals.

  16. Self-cross-linking biopolymers as injectable in situ forming biodegradable scaffolds.

    PubMed

    Balakrishnan, Biji; Jayakrishnan, A

    2005-06-01

    The injectable polymer scaffolds which are biocompatible and biodegradable are important biomaterials for tissue engineering and drug delivery. Hydrogels derived from natural proteins and polysaccharides are ideal scaffolds for tissue engineering since they resemble the extracellular matrices of the tissue comprised of various amino acids and sugar-based macromolecules. Here, we report a new class of hydrogels derived from oxidized alginate and gelatin. We show that periodate-oxidized sodium alginate having appropriate molecular weight and degree of oxidation rapidly cross-links proteins such as gelatin in the presence of small concentrations of sodium tetraborate (borax) to give injectable systems for tissue engineering, drug delivery and other medical applications. The rapid gelation in the presence of borax is attributed to the slightly alkaline pH of the medium as well as the ability of borax to complex with hydroxyl groups of polysaccharides. The effect of degree of oxidation and concentration of alginate dialdehyde, gelatin and borax on the speed of gelation was examined. As a general rule, the gelling time decreased with increase in concentration of oxidized alginate, gelatin and borax and increase in the degree of oxidation of alginate. Cross-linking parameters of the gel matrix were studied by swelling measurements and trinitrobenzene sulphonic acid (TNBS) assay. In general, the degree of cross-linking was found to increase with increase in the degree of oxidation of alginate, whereas the swelling ratio and the degree of swelling decreased. The gel was found to be biocompatible and biodegradable. The potential of the system as an injectable drug delivery vehicle and as a tissue-engineering scaffold is demonstrated by using primaquine as a model drug and by encapsulation of hepatocytes inside the gel matrix, respectively.

  17. Does vitamin E-stabilized ultrahigh-molecular-weight polyethylene address concerns of cross-linked polyethylene in total knee arthroplasty?

    PubMed

    Haider, Hani; Weisenburger, Joel N; Kurtz, Steven M; Rimnac, Clare M; Freedman, Jordan; Schroeder, David W; Garvin, Kevin L

    2012-03-01

    Concerns about reduced strength, fatigue resistance, and oxidative stability of highly cross-linked and remelted ultrahigh-molecular-weight polyethylene (UHMWPE) have limited its clinical acceptance for total knee arthroplasty. We hypothesized that a highly cross-linked UHMWPE stabilized with vitamin E would have less oxidation and loss of mechanical properties. We compared the oxidation, in vitro strength, fatigue-crack propagation resistance, and wear of highly cross-linked UHMWPE doped with vitamin E to γ-inert-sterilized direct compression-molded UHMWPE (control). After accelerated aging, the control material showed elevated oxidation, loss of small-punch mechanical properties, and loss of fatigue-crack propagation resistance. In contrast, the vitamin E-stabilized material had minimal changes and exhibited 73% to 86% reduction in wear for both cruciate-retaining and posterior-stabilized total knee arthroplasty designs. Highly cross-linked vitamin E-stabilized UHMWPE performed well in vitro.

  18. Inhibition of tau aggregation by a rosamine derivative that blocks tau intermolecular disulfide cross-linking.

    PubMed

    Haque, Md Mamunul; Kim, Dohee; Yu, Young Hyun; Lim, Sungsu; Kim, Dong Jin; Chang, Young-Tae; Ha, Hyung-Ho; Kim, Yun Kyung

    2014-09-01

    Abnormal tau aggregates are presumed to be neurotoxic and are an important therapeutic target for multiple neurodegenerative disorders including Alzheimer's disease. Growing evidence has shown that tau intermolecular disulfide cross-linking is critical in generating tau oligomers that serve as a building block for higher-order aggregates. Here we report that a small molecule inhibitor prevents tau aggregation by blocking the generation of disulfide cross-linked tau oligomers. Among the compounds tested, a rosamine derivative bearing mild thiol reactivity selectively labeled tau and effectively inhibited oligomerization and fibrillization processes in vitro. Our data suggest that controlling tau oxidation status could be a new therapeutic strategy for prevention of abnormal tau aggregation. PMID:24919397

  19. Transmembrane Signaling Characterized in Bacterial Chemoreceptors by Using Sulfhydryl Cross-Linking in vivo

    NASA Astrophysics Data System (ADS)

    Lee, Geoffrey F.; Lebert, Michael R.; Lilly, Angela A.; Hazelbauer, Gerald L.

    1995-04-01

    Transmembrane signaling by bacterial chemoreceptors is thought to involve conformational changes within a stable homodimer. We investigated the functional consequences of constraining movement between pairs of helices in the four-helix structure of the transmembrane domain of chemoreceptor Trg. Using a family of cysteine-containing receptors, we identified oxidation treatments for intact cells that catalyzed essentially complete sulfhydryl cross-linking at selected positions and yet left flagellar and sensory functions largely unperturbed. Constraining movement by cross-links between subunits had little effect on tactic response, but constraining movement between transmembrane segments of the monomer drastically reduced function. We deduce that transmembrane signaling requires substantial movement between transmembrane helices of a monomer but not between interacting helices across the interface between subunits.

  20. Iron and oxidative stress in cardiomyopathy in thalassemia.

    PubMed

    Berdoukas, Vasilios; Coates, Thomas D; Cabantchik, Zvi Ioav

    2015-11-01

    With repeated blood transfusions, patients with thalassemia major rapidly become loaded with iron, often surpassing hepatic metal accumulation capacity within ferritin shells and infiltrating heart and endocrine organs. That pathological scenario contrasts with the physiological one, which is characterized by an efficient maintenance of all plasma iron bound to circulating transferrin, due to a tight control of iron ingress into plasma by the hormone hepcidin. Within cells, most of the acquired iron becomes protein-associated, as once released from endocytosed transferrin, it is used within mitochondria for the synthesis of protein prosthetic groups or it is incorporated into enzyme active centers or alternatively sequestered within ferritin shells. A few cell types also express the iron extrusion transporter ferroportin, which is under the negative control of circulating hepcidin. However, that system only backs up the major cell regulated iron uptake/storage machinery that is poised to maintain a basal level of labile cellular iron for metabolic purposes without incurring potentially toxic scenarios. In thalassemia and other transfusion iron-loading conditions, once transferrin saturation exceeds about 70%, labile forms of iron enter the circulation and can gain access to various types of cells via resident transporters or channels. Within cells, they can attain levels that exceed their ability to chemically cope with labile iron, which has a propensity for generating reactive oxygen species (ROS), thereby inducing oxidative damage. This scenario occurs in the heart of hypertransfused thalassemia major patients who do not receive adequate iron-chelation therapy. Iron that accumulates in cardiomyocytes forms agglomerates that are detected by T2* MRI. The labile forms of iron infiltrate the mitochondria and damage cells by inducing noxious ROS formation, resulting in heart failure. The very rapid relief of cardiac dysfunction seen after intensive iron

  1. Quantification of Iron Oxides and Hydroxides in Desert Aeolian Particles

    NASA Astrophysics Data System (ADS)

    Lafon, S.; Rajot, J.; Alfaro, S.; Gaudichet, A.

    2002-12-01

    Long range transport of desert dust over oceans constitute a source of iron for the surface water. Assessing the iron cycle and its biogeochemical implications in oceanic areas requires determination and quantification of the iron status in aeolian particles. Indeed, in such aerosols, the iron is either trapped in the silicate structure or present under the form of oxides and hydroxides (free iron). We propose a method to apportion iron between free and entrapped forms in mineral aerosols. It consists in the adaptation of a well known method used for soil characterization to the treatment of aerosol samples, which represent less than 1 mg of material collected by air filtration on polycarbonate filters. The iron oxides and hydroxides are extracted selectively using the combined action of reductive and complexant agents in a buffered solution. The iron content is measured before and after this chemical extraction using X ray fluorescence spectrometry. We attempt to give some values for three main desert source areas using aerosol samples collected near Niamey (Niger) either during Harmattan events or during local erosion events, and samples collected downwind of the Gobi desert in China. Results emphasize firstly that iron trapped in the structure of silicate minerals represents an important part of total iron content. This suggests that, regarding dissolution processes in sea water, total elemental iron content of aeolian dust can not be used directly to calculate the flux of iron available. Secondly, our results show that the free iron content vary according to the origin of dusts. Niger samples have contents in free iron of 4.4 % (SD = 0.8) for local erosion and 2.8 % (SD = 1.0) for Harmattan. Chinese samples contain 3.7 % (SD = 0.5) of free iron. These differences could be linked to the parent soil mineralogical composition that varies with geographical location, but for some of our samples it also could be linked to a size fractionation process occurring first

  2. A chameleon catalyst for nonheme iron-promoted olefin oxidation.

    PubMed

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

    2014-11-18

    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  3. Iron oxide and gold nanoparticles in cancer therapy

    NASA Astrophysics Data System (ADS)

    Gotman, Irena; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.; Gutmanas, Elazar Y.

    2016-08-01

    Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

  4. Targeted iron oxide nanoparticles for the enhancement of radiation therapy.

    PubMed

    Hauser, Anastasia K; Mitov, Mihail I; Daley, Emily F; McGarry, Ronald C; Anderson, Kimberly W; Hilt, J Zach

    2016-10-01

    To increase the efficacy of radiation, iron oxide nanoparticles can be utilized for their ability to produce reactive oxygen species (ROS). Radiation therapy promotes leakage of electrons from the electron transport chain and leads to an increase in mitochondrial production of the superoxide anion which is converted to hydrogen peroxide by superoxide dismutase. Iron oxide nanoparticles can then catalyze the reaction from hydrogen peroxide to the highly reactive hydroxyl radical. Therefore, the overall aim of this project was to utilize iron oxide nanoparticles conjugated to a cell penetrating peptide, TAT, to escape lysosomal encapsulation after internalization by cancer cells and catalyze hydroxyl radical formation. It was determined that TAT functionalized iron oxide nanoparticles and uncoated iron oxide nanoparticles resulted in permeabilization of the lysosomal membranes. Additionally, mitochondrial integrity was compromised when A549 cells were treated with both TAT-functionalized nanoparticles and radiation. Pre-treatment with TAT-functionalized nanoparticles also significantly increased the ROS generation associated with radiation. A long term viability study showed that TAT-functionalized nanoparticles combined with radiation resulted in a synergistic combination treatment. This is likely due to the TAT-functionalized nanoparticles sensitizing the cells to subsequent radiation therapy, because the nanoparticles alone did not result in significant toxicities. PMID:27521615

  5. Magnetic composites based on hybrid spheres of aluminum oxide and superparamagnetic nanoparticles of iron oxides

    NASA Astrophysics Data System (ADS)

    Braga, Tiago P.; Vasconcelos, Igor F.; Sasaki, José M.; Fabris, J. D.; de Oliveira, Diana Q. L.; Valentini, Antoninho

    2010-03-01

    Materials containing hybrid spheres of aluminum oxide and superparamagnetic nanoparticles of iron oxides were obtained from a chemical precursor prepared by admixing chitosan and iron and aluminum hydroxides. The oxides were first characterized with scanning electron microscopy, X-ray diffraction, and Mössbauer spectroscopy. Scanning electron microscopy micrographs showed the size distribution of the resulting spheres to be highly homogeneous. The occurrence of nano-composites containing aluminum oxides and iron oxides was confirmed from powder X-ray diffraction patterns; except for the sample with no aluminum, the superparamagnetic relaxation due to iron oxide particles were observed from Mössbauer spectra obtained at 298 and 110 K; the onset six line-spectrum collected at 20 K indicates a magnetic ordering related to the blocking relaxation effect for significant portion of small spheres in the sample with a molar ratio Al:Fe of 2:1.

  6. Characterization of a novel cross-linked lipase: impact of cross-linking on solubility and release from drug product.

    PubMed

    Hetrick, Evan M; Sperry, David C; Nguyen, Hung K; Strege, Mark A

    2014-04-01

    Liprotamase is a novel non-porcine pancreatic enzyme replacement therapy containing purified biotechnology-derived lipase, protease, and amylase together with excipients in a capsule formulation. To preserve the structural integrity and biological activity of lipase (the primary drug substance) through exposure of the drug product to the low-pH gastric environment, the enzyme was processed through the use of cross-linked enzyme crystal (CLEC) technology, making the lipase-CLEC drug substance insoluble under acidic conditions but fully soluble at neutral pH and in alkaline environments. In this report we characterize the degree of cross-linking for lipase-CLEC and demonstrate its impact on lipase-CLEC solubility and release from the drug product under relevant physiological pH conditions. Cross-linked lipase-CLEC was characterized via size exclusion chromatography (SEC) and capillary electrophoresis sodium dodecyl sulfate polyacrylamide gel electrophoresis (CE-SDS-PAGE). A combination of methodologies was developed to understand the impact of cross-linking on drug product release. Dissolution evaluation using USP Apparatus 2 at pH 5.0 with an enzyme activity-based end point demonstrated solubility discrimination based on degree of cross-linking, while full release was demonstrated at pH 6.5. The dissolution of the drug product was also evaluated using a dual-stage test employing a USP Apparatus 4 flow-through system to mimic the changing pH environments experienced in the stomach and intestine to understand the impact of cross-linking on drug product performance. Use of USP Apparatus 4 to characterize the pH-dependent release of lipase-CLEC represents a novel approach compared to the Apparatus 1 test employing an acid-challenge stage outlined in the USP for delayed-release pancrelipase, and the advantages of this approach may prove useful for understanding the pH-dependence of release for other drug products. Collectively, these studies confirmed that degree of

  7. Development and use of iron oxide nanoparticles (Part 1): Synthesis of iron oxide nanoparticles for MRI

    PubMed Central

    Lodhia, J; Mandarano, G; Ferris, NJ; Eu, P; Cowell, SF

    2010-01-01

    Contrast agents, such as iron oxide, enhance MR images by altering the relaxation times of tissues in which the agent is present. They can also be used to label targeted molecular imaging probes. Unfortunately, no molecular imaging probe is currently available on the clinical MRI market. A promising platform for MRI contrast agent development is nanotechnology, where superparamagnetic iron oxide nanoparticles (SPIONS) are tailored for MR contrast enhancement, and/or for molecular imaging. SPIONs can be produced using a range of methods and the choice of method will be influenced by the characteristics most important for a particular application. In addition, the ability to attach molecular markers to SPIONS heralds their application in molecular imaging. There are many reviews on SPION synthesis for MRI; however, these tend to be targeted to a chemistry audience. The development of MRI contrast agents attracts experienced researchers from many fields including some researchers with little knowledge of medical imaging or MRI. This situation presents medical radiation practitioners with opportunities for involvement, collaboration or leadership in research depending on their level of commitment and their ability to learn. Medical radiation practitioners already possess a large portion of the understanding, knowledge and skills necessary for involvement in MRI development and molecular imaging. Their expertise in imaging technology, patient care and radiation safety provides them with skills that are directly applicable to research on the development and application of SPIONs and MRI. In this paper we argue that MRI SPIONs, currently limited to major research centres, will have widespread clinical use in the future. We believe that knowledge about this growing area of research provides an opportunity for medical radiation practitioners to enhance their specialised expertise to ensure best practice in a truly multi-disciplinary environment. This review outlines how and

  8. Haem-assisted dityrosine-cross-linking of fibrinogen under non-thermal plasma exposure: one important mechanism of facilitated blood coagulation

    PubMed Central

    Ke, Zhigang; Huang, Qing

    2016-01-01

    Although blood coagulation facilitated by non-thermal plasma has been reported several years ago, the insight to the involved mechanisms is still rather limited. In this work, we report our discovery of a new mechanism for the haem-promoted blood-coagulation caused by non-thermal plasma treatment. The reason for the haem role is due to that its oxidized form, namely, hematin, can promote the dityrosine cross-linking of fibrinogen, the most important coagulation protein, to form a membrane-like layer on the surface of the treated blood with plasma exposure. Both haem and non-thermal-plasma generated hydrogen peroxide are requisite for the cross-linking process. We confirmed that fibrinogen can coordinate with the haem iron to form a protein-haem complex which shows pseudo-peroxidase activity, and in the presence of hydrogen peroxide, the complex can induce the dityrosine formation between fibrinogen molecules, leading to the fibrin network necessary for the blood coagulation. Understanding of such an underlying mechanism can be useful to guide more efficient application of non-thermal plasma in the management of hemostasis, thrombosis and etc. PMID:27229173

  9. Potential Effects of Corneal Cross-Linking upon the Limbus

    PubMed Central

    2016-01-01

    Corneal cross-linking is nowadays the most used strategy for the treatment of keratoconus and recently it has been exploited for an increasing number of different corneal pathologies, from other ectatic disorders to keratitis. The safety of this technique has been widely assessed, but clinical complications still occur. The potential effects of cross-linking treatment upon the limbus are incompletely understood; it is important therefore to investigate the effect of UV exposure upon the limbal niche, particularly as UV is known to be mutagenic to cellular DNA and the limbus is where ocular surface tumors can develop. The risk of early induction of ocular surface cancer is undoubtedly rare and has to date not been published other than in one case after cross-linking. Nevertheless it is important to further assess, understand, and reduce where possible any potential risk. The aim of this review is to summarize all the reported cases of a pathological consequence for the limbal cells, possibly induced by cross-linking UV exposure, the studies done in vitro or ex vivo, the theoretical bases for the risks due to UV exposure, and which aspects of the clinical treatment may produce higher risk, along with what possible mechanisms could be utilized to protect the limbus and the delicate stem cells present within it. PMID:27689081

  10. Cross-linking of dithiols by mitomycin C.

    PubMed

    Paz, Manuel M

    2010-08-16

    Upon reduction, the antitumor drug mitomycin C undergoes a cascade of reactions to give a bis-electrophile that alkylates cellular nucleophiles. We recently reported that dithiols activate mitomycin C by reduction, and we report here that dithiols, after executing the reductive activation of mitomycin C, are bis-alkylated by the activated drug to form S,S'-cross-links as the predominant end products. The diastereomeric pair of adducts formed by 1,3-propanedithiol has been fully characterized by UV, HRMS, CD, and NMR experiments. Racemic dithiol (+/-)-dithiothreitol gave four diastereomeric cross-links, and (+/-)-dihydrolipoic acid gave eight cross-links (two regioisomers with four diastereomers each) that were partially characterized by UV and MS. The observed dependence of cross-link formation on dithiol concentration indicated the requirement of a second reduction step by dithiol, prior to the alkylation of the second arm of the dithiol. The existence of unidentified reaction pathways was manifested by the formation of unexpected intermediates during the course of the reaction of mitomycin C with dithiols and by the formation of unsoluble mitosene derivatives in the reaction between equimolar amounts of dithiol and mitomycin C. Mechanistic details of the reaction are addressed in light of these results. Finally, we discuss the potential relevance of our findings for the interaction of mitomycin C with dithiol-containing proteins.

  11. Porous Cross-Linked Polyimide-Urea Networks

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Nguyen, Baochau N. (Inventor)

    2015-01-01

    Porous cross-linked polyimide-urea networks are provided. The networks comprise a subunit comprising two anhydride end-capped polyamic acid oligomers in direct connection via a urea linkage. The oligomers (a) each comprise a repeating unit of a dianhydride and a diamine and a terminal anhydride group and (b) are formulated with 2 to 15 of the repeating units. The subunit was formed by reaction of the diamine and a diisocyanate to form a diamine-urea linkage-diamine group, followed by reaction of the diamine-urea linkage-diamine group with the dianhydride and the diamine to form the subunit. The subunit has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups. The subunit has been chemically imidized to yield the porous cross-linked polyimide-urea network. Also provided are wet gels, aerogels, and thin films comprising the networks, and methods of making the networks.

  12. Femtosecond laser collagen cross-linking without traditional photosensitizers

    NASA Astrophysics Data System (ADS)

    Guo, Yizang; Wang, Chao; Celi, Nicola; Vukelic, Sinisa

    2015-03-01

    Collagen cross-linking in cornea has the capability of enhancing its mechanical properties and thereby providing an alternative treatment for eye diseases such as keratoconus. Currently, riboflavin assisted UVA light irradiation is a method of choice for cross-link induction in eyes. However, ultrafast pulsed laser interactions may be a powerful alternative enabling in-depth treatment while simultaneously diminishing harmful side effects such as, keratocyte apoptosis. In this study, femtosecond laser is utilized for treatment of bovine cornea slices. It is hypothesized that nonlinear absorption of femtosecond laser pulses plays a major role in the maturation of immature cross-links and the promotion of their growth. Targeted irradiation with tightly focused laser pulses allows for the absence of a photosensitizing agent. Inflation test was conducted on half treated porcine cornea to identify the changes of mechanical properties due to laser treatment. Raman spectroscopy was utilized to study subtle changes in the chemical composition of treated cornea. The effects of treatment are analyzed by observing shifts in Amide I and Amide III bands, which suggest deformation of the collagen structure in cornea due to presence of newly formed cross-links.

  13. Citric-acid-derived photo-cross-linked biodegradable elastomers.

    PubMed

    Gyawali, Dipendra; Tran, Richard T; Guleserian, Kristine J; Tang, Liping; Yang, Jian

    2010-01-01

    Citric-acid-derived thermally cross-linked biodegradable elastomers (CABEs) have recently received significant attention in various biomedical applications, including tissue-engineering orthopedic devices, bioimaging and implant coatings. However, citric-acid-derived photo-cross-linked biodegradable elastomers are rarely reported. Herein, we report a novel photo-cross-linked biodegradable elastomer, referred to as poly(octamethylene maleate citrate) (POMC), which preserves pendant hydroxyl and carboxylic functionalities after cross-linking for the potential conjugation of biologically active molecules. Pre-POMC is a low-molecular-mass pre-polymer with an average molecular mass between 701 and 1291 Da. POMC networks are soft and elastic with an initial modulus of 0.07 to 1.3 MPa and an elongation-at-break between 38 and 382%. FT-IR-ATR results confirmed the successful surface immobilization of type-I collagen onto POMC films, which enhanced in vitro cellular attachment and proliferation. Photo-polymerized POMC films implanted subcutaneously into Sprague-Dawley rats demonstrated minimal in vivo inflammatory responses. The development of POMC enriches the family of citric-acid-derived biodegradable elastomers and expands the available biodegradable polymers for versatile needs in biomedical applications.

  14. Citric-Acid-Derived Photo-cross-Linked Biodegradable Elastomers

    PubMed Central

    Gyawali, Dipendra; Tran, Richard T.; Guleserian, Kristine J.; Tang, Liping; Yang, Jian

    2010-01-01

    Citric-acid-derived thermally cross-linked biodegradable elastomers (CABEs) have recently received significant attention in various biomedical applications, including tissue-engineering orthopedic devices, bioimaging and implant coatings. However, citric-acid-derived photo-cross-linked biodegradable elastomers are rarely reported. Herein, we report a novel photo-cross-linked biodegradable elastomer, referred to as poly(octamethylene maleate citrate) (POMC), which preserves pendant hydroxyl and carboxylic functionalities after cross-linking for the potential conjugation of biologically active molecules. POMC is a low-molecular-mass pre-polymer with a molecular mass average between 701 and 1291 Da. POMC networks are soft and elastic with an initial modulus of 0.07 to 1.3 MPa and an elongation at break between 38 and 382%. FT-IR–ATR results confirmed the successful surface immobilization of type-I collagen onto POMC films, which enhanced in vitro cellular attachment and proliferation. Photo-polymerized POMC films implanted subcutaneously into Sprague–Dawley rats demonstrated minimal in vivo inflammatory responses. The development of POMC enriches the family of citric-acid-derived biodegradable elastomers and expands the available biodegradable polymers for versatile needs in biomedical applications. PMID:20557687

  15. Potential Effects of Corneal Cross-Linking upon the Limbus

    PubMed Central

    2016-01-01

    Corneal cross-linking is nowadays the most used strategy for the treatment of keratoconus and recently it has been exploited for an increasing number of different corneal pathologies, from other ectatic disorders to keratitis. The safety of this technique has been widely assessed, but clinical complications still occur. The potential effects of cross-linking treatment upon the limbus are incompletely understood; it is important therefore to investigate the effect of UV exposure upon the limbal niche, particularly as UV is known to be mutagenic to cellular DNA and the limbus is where ocular surface tumors can develop. The risk of early induction of ocular surface cancer is undoubtedly rare and has to date not been published other than in one case after cross-linking. Nevertheless it is important to further assess, understand, and reduce where possible any potential risk. The aim of this review is to summarize all the reported cases of a pathological consequence for the limbal cells, possibly induced by cross-linking UV exposure, the studies done in vitro or ex vivo, the theoretical bases for the risks due to UV exposure, and which aspects of the clinical treatment may produce higher risk, along with what possible mechanisms could be utilized to protect the limbus and the delicate stem cells present within it.

  16. Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor)

    2016-01-01

    A method for creating a three dimensional cross-linked polyimide structure includes dissolving a diamine, a dianhydride, and a triamine in a solvent, imidizing a polyamic acid gel by heating the gel, extracting the gel in a second solvent, supercritically drying the gel, and removing the solvent to create a polyimide aerogel.

  17. A pentanuclear iron catalyst designed for water oxidation

    NASA Astrophysics Data System (ADS)

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K. K.; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-01

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth’s crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between FeII5 and FeIII5; the FeIII5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

  18. Bacterial oxidation of ferrous iron at low temperatures.

    PubMed

    Kupka, Daniel; Rzhepishevska, Olena I; Dopson, Mark; Lindström, E Börje; Karnachuk, Olia V; Tuovinen, Olli H

    2007-08-15

    This study comprises the first report of ferrous iron oxidation by psychrotolerant, acidophilic iron-oxidizing bacteria capable of growing at 5 degrees C. Samples of mine drainage-impacted surface soils and sediments from the Norilsk mining region (Taimyr, Siberia) and Kristineberg (Skellefte district, Sweden) were inoculated into acidic ferrous sulfate media and incubated at 5 degrees C. Iron oxidation was preceded by an approximately 3-month lag period that was reduced in subsequent cultures. Three enrichment cultures were chosen for further work and one culture designated as isolate SS3 was purified by colony isolation from a Norilsk enrichment culture for determining the kinetics of iron oxidation. The 16S rRNA based phylogeny of SS3 and two other psychrotolerant cultures, SS5 from Norilsk and SK5 from Northern Sweden, was determined. Comparative analysis of amplified 16S rRNA gene sequences showed that the psychrotolerant cultures aligned within Acidithiobacillus ferrooxidans. The rate constant of iron oxidation by growing cultures of SS3 was in the range of 0.0162-0.0104 h(-1) depending on the initial pH. The oxidation kinetics followed an exponential pattern, consistent with a first order rate expression. Parallel iron oxidation by a mesophilic reference culture of Acidithiobacillus ferrooxidans was extremely slow and linear. Precipitates harvested from the 5 degrees C culture were identified by X-ray diffraction as mixtures of schwertmannite (ideal formula Fe(8)O(8)(OH)(6)SO(4)) and jarosite (KFe(3)(SO(4))(2)(OH)(6)). Jarosite was much more dominant in precipitates produced at 30 degrees C. PMID:17304566

  19. Evidence of cell surface iron speciation of acidophilic iron-oxidizing microorganisms in indirect bioleaching process.

    PubMed

    Nie, Zhen-yuan; Liu, Hong-chang; Xia, Jin-lan; Yang, Yi; Zhen, Xiang-jun; Zhang, Li-Juan; Qiu, Guan-zhou

    2016-02-01

    While indirect model has been widely accepted in bioleaching, but the evidence of cell surface iron speciation has not been reported. In the present work the iron speciation on the cell surfaces of four typically acidophilic iron-oxidizing microorganism (mesophilic Acidithiobacillus ferrooxidans ATCC 23270, moderately thermophilic Leptospirillum ferriphilum YSK and Sulfobacillus thermosulfidooxidans St, and extremely thermophilic Acidianus manzaensis YN25) grown on different energy substrates (chalcopyrite, pyrite, ferrous sulfate and elemental sulfur (S(0))) were studied in situ firstly by using synchrotron-based micro- X-ray fluorescence analysis and X-ray absorption near-edge structure spectroscopy. Results showed that the cells grown on iron-containing substrates had apparently higher surface iron content than the cells grown on S(0). Both ferrous iron and ferric iron were detected on the cell surface of all tested AIOMs, and the Fe(II)/Fe(III) ratios of the same microorganism were affected by different energy substrates. The iron distribution and bonding state of single cell of A. manzaensis were then studied in situ by scanning transmission soft X-ray microscopy based on dual-energy contrast analysis and stack analysis. Results showed that the iron species distributed evenly on the cell surface and bonded with amino, carboxyl and hydroxyl groups.

  20. Synthesis of Surface-Modified Iron Oxides for the Solvent-Free Recovery of Bacterial Bioactive Compound Prodigiosin and Its Algicidal Activity.

    PubMed

    Arivizhivendhan, K V; Mahesh, M; Boopathy, R; Patchaimurugan, K; Maharaja, P; Swarnalatha, S; Regina Mary, R; Sekaran, G

    2016-09-15

    Prodigiosin (PG) is a bioactive compound produced by several bacterial species. Currently, many technologies are being developed for the production of PG by fermentation processes. However, new challenges are being faced with regard to the production of PG in terms of the recovery and purification steps, owing to the labile nature of PG molecules and the cost of the purification steps. Conventional methods have limitations due to high cost, low reusability, and health hazards. Hence, the present investigation was focused on the development of surface-functionalized magnetic iron oxide ([Fe3O4]F) for solvent-free extraction of bioactive PG from the bacterial fermented medium. Fe3O4 was functionalized with diethanolamine and characterized by FT-IR, diffuse reflectance spectroscopy, thermogravimetric analysis, scanning electron microscopy, and confocal microscopy. The various process parameters, such as contact time, temperature, pH, and mass of Fe3O4, were optimized for the extraction of PG using functionalized Fe3O4. Instrumental analyses confirmed that the PG molecules were cross-linked with functional groups on [Fe3O4]F through van der Waals forces of attraction. PG extracted through Fe3O4 or [Fe3O4]F was separated from the fermentation medium by applying an external electromagnetic field and regenerated for successive reuse cycles. The purity of the extracted PG was characterized by high-performance liquid chromatography, FT-IR, and UV-visible spectroscopy. The iron oxide-diethanolamine-PG cross-linked ([Fe3O4]F-PG) composite matrix effectively deactivates harmful fouling by cyanobacterial growth in water-treatment plants. The present investigation provides the possibility of solvent-free extraction of bacterial bioactive PG from a fermented medium using functionalized magnetic iron oxide. PMID:27487290

  1. Synthesis of Surface-Modified Iron Oxides for the Solvent-Free Recovery of Bacterial Bioactive Compound Prodigiosin and Its Algicidal Activity.

    PubMed

    Arivizhivendhan, K V; Mahesh, M; Boopathy, R; Patchaimurugan, K; Maharaja, P; Swarnalatha, S; Regina Mary, R; Sekaran, G

    2016-09-15

    Prodigiosin (PG) is a bioactive compound produced by several bacterial species. Currently, many technologies are being developed for the production of PG by fermentation processes. However, new challenges are being faced with regard to the production of PG in terms of the recovery and purification steps, owing to the labile nature of PG molecules and the cost of the purification steps. Conventional methods have limitations due to high cost, low reusability, and health hazards. Hence, the present investigation was focused on the development of surface-functionalized magnetic iron oxide ([Fe3O4]F) for solvent-free extraction of bioactive PG from the bacterial fermented medium. Fe3O4 was functionalized with diethanolamine and characterized by FT-IR, diffuse reflectance spectroscopy, thermogravimetric analysis, scanning electron microscopy, and confocal microscopy. The various process parameters, such as contact time, temperature, pH, and mass of Fe3O4, were optimized for the extraction of PG using functionalized Fe3O4. Instrumental analyses confirmed that the PG molecules were cross-linked with functional groups on [Fe3O4]F through van der Waals forces of attraction. PG extracted through Fe3O4 or [Fe3O4]F was separated from the fermentation medium by applying an external electromagnetic field and regenerated for successive reuse cycles. The purity of the extracted PG was characterized by high-performance liquid chromatography, FT-IR, and UV-visible spectroscopy. The iron oxide-diethanolamine-PG cross-linked ([Fe3O4]F-PG) composite matrix effectively deactivates harmful fouling by cyanobacterial growth in water-treatment plants. The present investigation provides the possibility of solvent-free extraction of bacterial bioactive PG from a fermented medium using functionalized magnetic iron oxide.

  2. Purification of Lysosomes Using Supraparamagnetic Iron Oxide Nanoparticles (SPIONs).

    PubMed

    Rofe, Adam P; Pryor, Paul R

    2016-04-01

    Lysosomes can be rapidly isolated from tissue culture cells using supraparamagnetic iron oxide particles (SPIONs). In this protocol, colloidal iron dextran (FeDex) particles, a type of SPION, are taken up by cultured mouse macrophage cells via the endocytic pathway. The SPIONs accumulate in lysosomes, the end point of the endocytic pathway, permitting the lysosomes to be isolated magnetically. The purified lysosomes are suitable for in vitro fusion assays or for proteomic analysis. PMID:27037068

  3. Purification of Lysosomes Using Supraparamagnetic Iron Oxide Nanoparticles (SPIONs).

    PubMed

    Rofe, Adam P; Pryor, Paul R

    2016-04-01

    Lysosomes can be rapidly isolated from tissue culture cells using supraparamagnetic iron oxide particles (SPIONs). In this protocol, colloidal iron dextran (FeDex) particles, a type of SPION, are taken up by cultured mouse macrophage cells via the endocytic pathway. The SPIONs accumulate in lysosomes, the end point of the endocytic pathway, permitting the lysosomes to be isolated magnetically. The purified lysosomes are suitable for in vitro fusion assays or for proteomic analysis.

  4. Safety assessment of chronic oral exposure to iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Chamorro, Susana; Gutiérrez, Lucía; Vaquero, María Pilar; Verdoy, Dolores; Salas, Gorka; Luengo, Yurena; Brenes, Agustín; José Teran, Francisco

    2015-05-01

    Iron oxide nanoparticles with engineered physical and biochemical properties are finding a rapidly increasing number of biomedical applications. However, a wide variety of safety concerns, especially those related to oral exposure, still need to be addressed for iron oxide nanoparticles in order to reach clinical practice. Here, we report on the effects of chronic oral exposure to low doses of γ-Fe2O3 nanoparticles in growing chickens. Animal observation, weight, and diet intake reveal no adverse signs, symptoms, or mortality. No nanoparticle accumulation was observed in liver, spleen, and duodenum, with feces as the main excretion route. Liver iron level and duodenal villi morphology reflect the bioavailability of the iron released from the partial transformation of γ-Fe2O3 nanoparticles in the acid gastric environment. Duodenal gene expression studies related to the absorption of iron from γ-Fe2O3 nanoparticles indicate the enhancement of a ferric over ferrous pathway supporting the role of mucins. Our findings reveal that oral administration of iron oxide nanoparticles is a safe route for drug delivery at low nanoparticle doses.

  5. Virus-Templated Near-Amorphous Iron Oxide Nanotubes.

    PubMed

    Shah, Sachin N; Khan, Abid A; Espinosa, Ana; Garcia, Miguel A; Nuansing, Wiwat; Ungureanu, Mariana; Heddle, Jonathan G; Chuvilin, Andrey L; Wege, Christina; Bittner, Alexander M

    2016-06-14

    We present a simple synthesis of iron oxide nanotubes, grown under very mild conditions from a solution containing Fe(II) and Fe(III), on rod-shaped tobacco mosaic virus templates. Their well-defined shape and surface chemistry suggest that these robust bionanoparticles are a versatile platform for synthesis of small, thin mineral tubes, which was achieved efficiently. Various characterization tools were used to explore the iron oxide in detail: Electron microscopy (SEM, TEM), magnetometry (SQUID-VSM), diffraction (XRD, TEM-SAED), electron spectroscopies (EELS, EDX, XPS), and X-ray absorption (XANES with EXAFS analysis). They allowed determination of the structure, crystallinity, magnetic properties, and composition of the tubes. The protein surface of the viral templates was crucial to nucleate iron oxide, exhibiting analogies to biomineralization in natural compartments such as ferritin cages. PMID:27181278

  6. Virus-Templated Near-Amorphous Iron Oxide Nanotubes.

    PubMed

    Shah, Sachin N; Khan, Abid A; Espinosa, Ana; Garcia, Miguel A; Nuansing, Wiwat; Ungureanu, Mariana; Heddle, Jonathan G; Chuvilin, Andrey L; Wege, Christina; Bittner, Alexander M

    2016-06-14

    We present a simple synthesis of iron oxide nanotubes, grown under very mild conditions from a solution containing Fe(II) and Fe(III), on rod-shaped tobacco mosaic virus templates. Their well-defined shape and surface chemistry suggest that these robust bionanoparticles are a versatile platform for synthesis of small, thin mineral tubes, which was achieved efficiently. Various characterization tools were used to explore the iron oxide in detail: Electron microscopy (SEM, TEM), magnetometry (SQUID-VSM), diffraction (XRD, TEM-SAED), electron spectroscopies (EELS, EDX, XPS), and X-ray absorption (XANES with EXAFS analysis). They allowed determination of the structure, crystallinity, magnetic properties, and composition of the tubes. The protein surface of the viral templates was crucial to nucleate iron oxide, exhibiting analogies to biomineralization in natural compartments such as ferritin cages.

  7. Eyelid allergic contact dermatitis to black iron oxide.

    PubMed

    Saxena, M; Warshaw, E; Ahmed, D D

    2001-03-01

    Eye cosmetics are a common cause of eyelid dermatitis. These products contain pigments, fragrances, resins, preservatives and vehicles. Mascara might cause either irritant or allergic contact dermatitis (ACD) of the eyelids. We present the case of a 44-year-old woman with a 10-month history of periorbital and eyelid dermatitis. Epicutaneous patch testing using the TRUE Test, cosmetic series, steroid series, and her personal products yielded a strong reaction to her mascara. Subsequent patch testing to the mascara components provided by the manufacturer revealed a severe reaction only to 5% black iron oxide. This black iron oxide was further tested in 10 normal controls with no reactions produced. There is only one previous report of eyelid ACD secondary to iron oxide that represents a rare cause of eyelid ACD.

  8. Development of Novel Biopolymer/Synthetic-Polymer/Iron Oxide Nanocomposites

    NASA Astrophysics Data System (ADS)

    Mena Montoya, Marleth; Carranza, Sugeheidy; Hinojosa, Moisés; González, Virgilio

    2009-03-01

    In this work we report the successful development of a family of magnetic nanocomposites based on chitosan or/and polyamide 6 matrix with dispersed iron oxide nanoparticles synthesized by chemical co-precipitation. The iron oxide contents varied from 5 up to 23 wt%, the nanocomposites were studied by FTIR, UV-vis, TGA, XRD, TEM and magnetometry. The FTIR analysis demonstrates an interaction between the amide group of the polyamide 6 and the ceramic material. In formic acid, the nanocomposites absorb in the UV-Vis range, and the magnitude of the band gap (optical), calculated using the band of higher wavelength, is between 2.16 and 2.19 eV. In nanocomposites with chitosan/polyamide 6 matrix the developed morphologies are spherulites of polyamide 6 surrounded by chitosan, with the iron oxide particles presumably in the form of ferrihidryte. The measured magnetic properties revealed a superparamagnetic character on the studied specimens.

  9. Imaging circulating cells and lymphoid tissues with iron oxide nanoparticles.

    PubMed

    Elias, Andrew; Tsourkas, Andrew

    2009-01-01

    The use of nanometer-sized iron oxide nanoparticles and micron-sized iron oxide particles as magnetic resonance (MR) contrast agents has garnered a high degree of interest in diverse areas of biology and medicine. Applications such as cell tracking, molecular imaging, gene detection, and lymphography are being explored to provide insight into disease mechanisms, monitor therapeutic efficacy, and facilitate diagnostic imaging. What makes iron oxide so appealing is a number of favorable properties including high detectability by MR, biodegradability and low toxicity. Here we describe the recent progress on the use of magnetic nanoparticles in imaging circulating cells and lymphoid tissues. The study of the lymph system and the biodistribution of various circulating immune cells is important in the diagnosis, prognosis, and treatment of a wide range of diseases and is expected to have a profound effect on patient outcome.

  10. Visualization study on sedimentation of micron iron oxide particles.

    PubMed

    Chen, Jin-Fang; Luo, Ye; Xu, Jun-Hui; Chen, Qi-Ming; Guo, Jia

    2006-09-15

    In this paper, a novel technique combined light-electronic microscopy and computer imaging trace was used for visualization of the sedimentation of micron iron oxide particles in a customized micro-reactor. Micron iron oxide particles were recovered from the cinder of sulfuric acid production by sedimentation separating and hydraulic rating. Effects of particle size, shape and surface roughness on the sedimentation velocity were investigated. For irregular-shape particles, the sedimentation velocity and the geometric parameters of the particles were measured by the imaging trace technique. A correction coefficient (c) was used to modify the Stokes equation. In this study, the relationship between the correction coefficient and the equivalent diameter (d(p)) was found to be linear: c=0.6272-0.0298d(p), for iron oxide particles with equivalent diameter 4-22 microm.

  11. The effect of an additional phosphite stabilizer on the properties of radiation cross-linked vitamin E blends of UHMWPE.

    PubMed

    Oral, Ebru; Neils, Andrew; Yabannavar, Pooja; Muratoglu, Orhun K

    2014-06-01

    Antioxidant stabilization of radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) has been introduced to improve the oxidative stability of total joint implant bearing surfaces. Blending of an antioxidant with UHMWPE resin powder followed by consolidation and radiation cross-linking has been cleared by the FDA for use in both total hips and total knees for designs incorporating two antioxidants, namely vitamin E and Covernox™ (a medical grade version of Irganox™ 1010). The antioxidants in the polymer are expected to protect the polymer during consolidation, during radiation cross-linking, on the shelf before implantation, and in vivo after implantation. To maximize the protection of the polymer afforded by the antioxidant in vivo, a novel approach may be the use of multiple antioxidants, especially to protect the primary antioxidant for a longer period of time. We hypothesized that the addition of a phosphite stabilizer (Irgafos 168™) commonly used in conjunction with hindered phenolic antioxidants in polymer processing could improve the oxidative stability of radiation cross-linked blends of vitamin E. To test our hypothesis, we prepared UHMWPE blends with 0.05 wt% Irgafos and 0.05 wt% vitamin E and compared its cross-link density, wear resistance, tensile properties, and impact strength to control blends containing only vitamin E. Our hypothesis was not supported; the cross-link density of UHMWPE was significantly decreased by the additive without additional benefit to oxidative stability. To our knowledge, this was the first attempt at using multiple stabilizers in medical grade UHMWPE.

  12. The role of iron in prostaglandin synthesis: ferrous iron mediated oxidation of arachidonic acid.

    PubMed

    Rao, G H; Gerrard, J M; Eaton, J W; White, J G

    1978-07-01

    Arachidonic acid (AA) is the essential substrate for production of platelet endoperoxides and thromboxanes. Iron or heme is an essential cofactor for the peroxidase, lipoxygenase and cyclo-oxygenase enzymes involved in formation of these products. The present study has examined the direct interactions between iron and arachidonic acid. Iron caused the oxidation of AA into more polar products which could be detected by UV absorbtion at 232 nM or the thiobarbituric acid (TBA) reaction. High pressure liquid chromatography, chem-ionization and electron-impact mass spectrometry and nuclear magnetic resonance spectroscopy suggest that the major product was a hydroperoxide of AA. Ferrous iron (Fe++) and oxygen were absolute requirements. Fe++ was converted to the ferric iron (Fe+++) state during oxidation of AA, but Fe+++ could not substitute for Fe++. No other enzymes, cofactors or ions were involved. Conversion of AA to a hydroperoxide by Fe++ was inhibited by the antioxidant, 2, (3)-Tert-butyl-4-hydroxyanisole, the radical scavenger, nitroblue tetrazolium, and iron chelating agents, including EDTA, imidazole and dihydroxybenzoic acid. The reaction was not affected by superoxide dismutase, catalase or aspirin. These findings and preliminary studies of the Fe++ induced oxidation product of AA as a substrate for prostaglandin synthesis and inhibitor of prostacyclin production indicate the critical role of Fe++ in AA activation.

  13. A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui

    A novel poly(ether ether ketone) (PEEK) containing pendant carboxyl groups has been synthesized by a nucleophilic polycondensation reaction. Sulfonated polymers (SPEEKs) with different ion exchange capacity are then obtained by post-sulfonation process. The structures of PEEK and SPEEKs are characterized by both FT-IR and 1H NMR. The properties of SPEEKs as candidates for proton exchange membranes are studied. The cross-linking reaction is performed at 140 °C using poly(vinyl alcohol) (PVA) as the cross-linker. In comparison with the non-cross-linked membranes, some properties of the cross-linked membranes are significantly improved, such as water uptake, methanol resistance, mechanical and oxidative stabilities, while the proton conductivity decreases. The effect of PVA content on proton conductivity, water uptake, swelling ratio, and methanol permeability is also investigated. Among all the membranes, SPEEK-C-8 shows the highest selectivity of 50.5 × 10 4 S s cm -3, which indicates that it is a suitable candidate for applications in direct methanol fuel cells.

  14. Chitosan nanogels by template chemical cross-linking in polyion complex micelle nanoreactors.

    PubMed

    Maggi, Flavia; Ciccarelli, Serena; Diociaiuti, Marco; Casciardi, Stefano; Masci, Giancarlo

    2011-10-10

    Chitosan covalent nanogels cross-linked with genipin were prepared by template chemical cross-linking of chitosan in polyion complex micelle (PIC) nanoreactors. By using this method, we were able to prepare chitosan nanogels using only biocompatible materials without organic solvents. PIC were prepared by interaction between chitosan (X(n) = 23, 44, and 130) and block copolymer poly(ethylene oxide)-block-poly[sodium 2-(acrylamido)-2-methylpropanesulfonate] (PEO-b-PAMPS) synthesized by single-electron transfer-living radical polymerization (SET-LRP). PIC with small size (diameter about 50 nm) and low polydispersity were obtained up to 5 mg/mL. After cross-linking of chitosan with genipin, the nanoreactors were dissociated by adding NaCl. The dissociation of the nanoreactors and the formation of the nanogels were confirmed by (1)H NMR, DLS, and TEM. The size of the smallest nanogels was about 50 nm in the swollen state and 20 nm in the dry state. The amount of genipin used during reticulation was an important parameter to modulate the size of the nanogels in solution. PMID:21866922

  15. Cross-linked polystyrene sulfonic acid and polyethylene glycol as a low-fouling material.

    PubMed

    Alghunaim, Abdullah; Zhang Newby, Bi-min

    2016-04-01

    A negatively charged hydrophilic low fouling film was prepared by thermally cross-linking a blend consisting of polystyrene sulfonic acid (PSS) and polyethylene glycol (PEG). The film was found to be stable by dip-washing. The fouling resistance of this material toward bacterial (Escherichia coli) and colloidal (polystyrene particles) attachment, non-specific protein (fibronectin) adsorption and cell (3T3 NIH) adhesion was evaluated and was compared with glass slides modified with polyethylene glycol (PEG) brushes, oxidized 3-mercaptopropyltrimethoxysilane (sulfonic acid, SA), and n-octadecyltrichlorosilane (OTS). The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and thermodynamic models based on surface energy were used to explain the interaction behaviors of E. coli/polystyrene particles-substrate and protein-substrate interactions, respectively. The cross-linked PSS-PEG film was found to be slightly better than SA and PEG toward resisting non-specific protein adsorption, and showed comparable low attachment results as those of PEG toward particle, bacterial and NIH-3T3 cells adhesion. The low-fouling performance of PSS-PEG, a cross-linked film by a simple thermal curing process, could allow this material to be used for applications in aqueous environments, where most low fouling hydrophilic polymers, such as PSS or PEG, could not be easily retained.

  16. Hyaluronic acid and alginate covalent nanogels by template cross-linking in polyion complex micelle nanoreactors.

    PubMed

    De Santis, Serena; Diociaiuti, Marco; Cametti, Cesare; Masci, Giancarlo

    2014-01-30

    Hyaluronic acid (HA) and alginate (AL) covalent nanogels cross-linked with l-lysine ethyl ester were prepared by template chemical cross-linking of the polysaccharide in polyion complex micelle (PIC) nanoreactors. By using this method we were able to prepare HA and AL nanogels without organic solvents. PICs were prepared by using poly(ethylene oxide)-block-poly[(3-acrylamidopropyl)-trimethylammonium chloride] (PEO-b-PAMPTMA) or poly[(N-isopropylacrylamide)-block-PAMPTMA] (PNIPAAM-b-PAMPTMA). Only PNIPAAM-b-PAMPTMA block copolymers allowed to prepare PIC with small and controlled size. Short polysaccharide chains (Xn=50 and 63 for AL and HA, respectively, where Xn is the number of monosaccharidic units present in the polysaccharide) where used to optimize PIC formation. The remarkable difference in charge density and rigidity of HA and AL did not have a significant influence on the formation of PICs. PICs with small size (diameter of about 50-80 nm) and low polydispersity were obtained up to 5mg/mL of polymer. After cross-linking with l-lysine ethyl ester, the nanoreactors were dissociated by adding NaCl. The nanogels were easily purified and isolated by dialysis. The dissociation of the nanoreactors and the formation of the nanogels were confirmed by (1)H NMR, DLS, TEM and ζ-potential measurements. The size of the smallest nanogels in solution in the swollen state was 50-70 nm in presence of salt and 80-100 nm in water.

  17. Ozone-induced formation of O,O'-dityrosine cross-linked in proteins.

    PubMed

    Verweij, H; Christianse, K; Van Steveninck, J

    1982-02-18

    Treatment of spectrin, insulin, glucagon and ribonuclease with ozone results in covalent cross-linking of these proteins. This cross-linking is not reversed by treatment with dithiothreitol and thus can not be ascribed to -S-S- bond formation. A concomitant O,O'-dityrosine formation is observed by spectrofluorometric analysis of the protein and by amino acid analysis and thin-layer chromatography of hydrolyzed protein samples. It is highly probable that the observed protein cross-linking should be attributed to interpeptide O,O'-dityrosine bonds. Several authors have shown before that oxidation of proteins with horseradish peroxidase and H2O2 also leads to O,O'-dityrosine formation. Peroxidase-induced O,O'-dityrosine formation in galactose oxidase (d-galactose:oxygen 6-oxidoreductase, EC 1.1.3.9) causes a strong increase of enzyme activity. In accordance with these observations ozone treatment of galactose oxidase also leads to O,O'-dityrosine formation with a concomitant 8-fold increase of enzyme activity.

  18. Structural Analysis and Mechanical Characterization of Hyaluronic Acid-Based Doubly Cross-Linked Networks

    PubMed Central

    Jha, Amit K.; Hule, Rohan A.; Jiao, Tong; Teller, Sean S.; Clifton, Rodney J.; Duncan, Randall L.; Pochan, Darrin J.; Jia, Xinqiao

    2009-01-01

    We have created a new class of hyaluronic acid (HA)-based hydrogel materials with HA hydrogel particles (HGPs) embedded in and covalently cross-linked to a secondary network. HA HGPs with an average diameter of ∼900 nm and narrow particle size distribution were synthesized using a refined reverse micelle polymerization technique. The average mesh size of the HGPs was estimated to be approximately 5.5 to 7.0 nm by a protein uptake experiment. Sodium periodate oxidation not only introduced aldehyde groups to the particles but also reduced the average particle size. The aldehyde groups generated were used as reactive handles for subsequent cross-linking with an HA derivative containing hydrazide groups. The resulting macroscopic gels contain two distinct hierarchical networks (doubly cross-linked networks, DXNs): one within individual particles and another among different particles. Bulk gels (BGs) formed by direct mixing of HA derivatives with mutually reactive groups were included for comparison. The hydrogel microstructures were collectively characterized by microscopy and neutron scattering techniques. Their viscoelasticity was quantified at low frequencies (0.1−10 Hz) using a controlled stress rheometer and at high frequencies (up to 200 Hz) with a home-built torsional wave apparatus. Both BGs and DXNs are stable elastic gels that become stiffer at higher frequencies. The HA-based DXN offers unique structural hierarchy and mechanical properties that are suitable for soft tissue regeneration. PMID:20046226

  19. Electrolytic photodissociation of chemical compounds by iron oxide photochemical diodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1985-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor photochemical diode having visible light as its sole source of energy. The photochemical diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  20. Multifunctional Iron Oxide Nanoparticles for Diagnostics, Therapy and Macromolecule Delivery

    PubMed Central

    Yen, Swee Kuan; Padmanabhan, Parasuraman; Selvan, Subramanian Tamil

    2013-01-01

    In recent years, multifunctional nanoparticles (NPs) consisting of either metal (e.g. Au), or magnetic NP (e.g. iron oxide) with other fluorescent components such as quantum dots (QDs) or organic dyes have been emerging as versatile candidate systems for cancer diagnosis, therapy, and macromolecule delivery such as micro ribonucleic acid (microRNA). This review intends to highlight the recent advances in the synthesis and application of multifunctional NPs (mainly iron oxide) in theranostics, an area used to combine therapeutics and diagnostics. The recent applications of NPs in miRNA delivery are also reviewed. PMID:24396508

  1. Electrolytic photodissociation of chemical compounds by iron oxide electrodes

    DOEpatents

    Somorjai, Gabor A.; Leygraf, Christofer H.

    1984-01-01

    Chemical compounds can be dissociated by contacting the same with a p/n type semi-conductor diode having visible light as its sole source of energy. The diode consists of low cost, readily available materials, specifically polycrystalline iron oxide doped with silicon in the case of the n-type semi-conductor electrode, and polycrystalline iron oxide doped with magnesium in the case of the p-type electrode. So long as the light source has an energy greater than 2.2 electron volts, no added energy source is needed to achieve dissociation.

  2. Recovery of iron oxide from coal fly ash

    DOEpatents

    Dobbins, Michael S.; Murtha, Marlyn J.

    1983-05-31

    A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

  3. Corneal Cross-Linking: Evaluating the Potential for a Lower Power, Shorter Duration Treatment

    PubMed Central

    Caruso, Ciro; Barbaro, Gaetano; Tronino, Diana; Ostacolo, Carmine; Sacchi, Antonia; Pacente, Luigi; Del Prete, Antonio; Sala, Marina; Troisi, Salvatore

    2016-01-01

    Purpose: To determine the cross-linking effect of a riboflavin ultraviolet-A (UV-A) corneal cross-linking treatment that is both shorter and has lower energy than the Dresden protocol. Methods: In a first experiment, 12 human corneas were presoaked with riboflavin and then irradiated with UV-A at 3 mW/cm2 after clearing the surface of riboflavin, with no added riboflavin during irradiation. Percent UV-A transmission through the corneas was measured at intervals up to 30 minutes. A second experiment involved 24 porcine corneas. Eight were de-epithelialized, presoaked in riboflavin for 30 minutes, and irradiated at 1.5 mW/cm2 for 10 minutes. An additional 8 were riboflavin treated and similarly irradiated, but with epithelium intact and a final 8 corneas were not treated. Young modulus was measured in all 24 corneas at the end of the experiment. Results: The first experiment showed essentially complete riboflavin oxidation after only 10 minutes. Based on these results, a shortened UV-A exposure cross-linking experiment was designed using a reduced UV-A fluence of 1.5 mW/cm2, an endothelial exposure within safety limits in humans. With this protocol Young modulus was the same in the irradiated porcine corneas but with epithelium intact as in the untreated corneas. In contrast, Young modulus increased by a factor of 1.99 in the UV-A cross-linked corneas at 1.5 mW/cm2 for 10 minutes with the epithelium removed. Conclusions: A shorter, lower energy protocol than the Dresden protocol seems to provide a significant increase in Young modulus, similar to published results with higher energy, longer exposure protocols. PMID:26989958

  4. Size-dependent magnetic properties of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Patsula, Vitalii; Moskvin, Maksym; Dutz, Silvio; Horák, Daniel

    2016-01-01

    Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.

  5. Growth Kinetics of Attached Iron-Oxidizing Bacteria

    PubMed Central

    Wichlacz, Paul L.; Unz, Richard F.

    1985-01-01

    A model of growth and substrate utilization for ferrous-iron-oxidizing bacteria attached to the disks of a rotating biological contactor was developed and tested. The model describes attached bacterial growth as a saturation function in which the rate of substrate utilization is determined by a maximum substrate oxidation rate constant (P), a half-saturation constant (Ks), and the concentration of substrate within the rotating biological contactor (S1). The maximum oxidation rate constant was proportional to flow rate, and the substrate concentration in the reactor varied with influent substrate concentration (S0). The model allowed the prediction of metabolic constants and included terms for both constant and growth-rate-dependent maintenance energies. Estimates for metabolic constants of the attached population of acidophilic, chemolithotrophic, iron-oxidizing bacteria limited by ferrous iron were: maximum specific growth rate (μmax), 1.14 h−1; half-saturation constant (Ks) for ferrous iron, 54.9 mg/liter; constant maintenance energy coefficient (m1), 0.154 h−1; growth-rate-dependent maintenance energy coefficient (m′), 0.07 h−1; maximum yield (Yg), 0.063 mg of organic nitrogen per mg of Fe(II) oxidized. PMID:16346863

  6. Enhanced rates of electrolytic styrene epoxidation catalyzed by cross-linked myoglobin-poly(L-lysine) films in bicontinuous microemulsions.

    PubMed

    Vaze, Abhay; Parizo, Michael; Rusling, James F

    2004-12-01

    Redox proteins attached to surfaces designed for biocatalysis hold promise for future clean synthetic routes. It is advantageous for these biocatalysts to operate in low-toxicity fluids with a high capacity to dissolve reactants. Here we report cross-linked films of myoglobin (Mb) and poly(L-lysine) (PLL) chemically attached to oxidized carbon cloth cathodes that in microemulsions feature the protein in a water-rich film environment with reactant in an oil-rich environment. These cross-linked Mb/PLL films were the most stable in microemuslions and had the largest turnover rates for epoxidation of styrene compared to lightly cross-linked or uncross-linked Mb/poly(styrene sulfonate) films. Up to 40-fold larger turnover rates were found in bicontinuous microemulsions compared to oil-in-water microemulsions and micelles. Enhanced turnover rates are correlated with up to 10-fold faster mass transport of solutes in the oil phases of the bicontinuous fluids.

  7. Cross-linked polyelectrolyte for direct methanol fuel cells applications based on a novel sulfonated cross-linker

    NASA Astrophysics Data System (ADS)

    Li, Mingyu; Zhang, Gang; Xu, Shuai; Zhao, Chengji; Han, Miaomiao; Zhang, Liyuan; Jiang, Hao; Liu, Zhongguo; Na, Hui

    2014-06-01

    A novel type of cross-linked proton exchange membrane of lower methanol permeation and high proton conductivity is prepared, based on a newly synthesized sulfonated cross-linker: carboxyl terminated benzimidazole trimer bearing sulfonic acid groups (s-BI). Compared to membranes cross-linked with non-sulfonated cross-linker (BI), SPEEK/s-BI-n membranes show higher IEC values and proton conductivities. Meanwhile, oxidative stability and mechanical property of SPEEK/s-BI-n membranes are obviously improved. Among SPEEK/s-BI-n membranes, SPEEK/s-BI-2 exhibits high proton conductivity, low swelling ratio (0.122 S cm-1 and 15.2% at 60 °C, respectively) and low methanol permeability coefficient. These results imply that the cross-linked membranes prepared with the newly sulfonated cross-linker are promising for the direct methanol fuel cells (DMFCs) application.

  8. Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

    2015-06-01

    A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

  9. Deposition rates of oxidized iron on Mars

    NASA Technical Reports Server (NTRS)

    Burns, R. G.

    1993-01-01

    The reddened oxidized surface of Mars is indicative of temporal interactions between the Martian atmosphere and its surface. During the evolution of the Martian regolith, primary ferromagnesian silicate and sulfide minerals in basaltic rocks apparently have been oxidized to secondary ferric-bearing assemblages. To evaluate how and when such oxidized deposits were formed on Mars, information about the mechanisms and rates of chemical weathering of Fe(2+)-bearing minerals has been determined. In this paper, mechanisms and rates of deposition of ferric oxide phases on the Martian surface are discussed.

  10. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    EPA Science Inventory

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  11. Iron oxides, dissolved silica, and regulation of marine phosphate concentration

    NASA Astrophysics Data System (ADS)

    Planavsky, N.; Reinhard, C.; Lyons, T.

    2008-12-01

    Phosphorous concentrations in iron oxide-rich sediments reflect orthophosphate levels in the water column from which iron oxides precipitated. Sediment P/Fe ratios are also strongly influenced by the concentrations of dissolved species that inhibit orthophosphate-to-ferrihydrite sorption, most notably silica. It may, therefore, be possible to use P/Fe ratios in iron oxide-rich sediments to estimate past dissolved P concentrations, if one considers the evolution of the silica cycle. A compilation of Fe and P data in iron oxide-rich sediments through time reveals an increase in P/Fe ratios after the Jurassic. We propose that this trend indicates evolution of the iron-oxide phosphate removal mechanism caused by decreasing levels of sorption inhibition by dissolved silica. The large difference in P/Fe ratios in Cenozoic versus older iron-oxide rich sediments can be linked with Si drawdown caused by the proliferation of siliceous plankton in the Cretaceous. There is also a late Mesozoic or Cenozoic increase in V/Fe ratios, which provides additional evidence for lower ferrihydrite anion sorption efficiency prior to diatom radiation. P/Fe ratios in iron oxide-rich sediments from the early and middle Phanerozoic are comparable to the ratios in iron formations previously presented as evidence for an early Precambrian phosphate crisis (Bjerrum and Canfield, 2002, Nature, 417:159-162). Given the compelling evidence for higher Si concentrations in the Precambrian compared to the Phanerozoic and dissolved P concentrations comparable to modern levels throughout the Phanerozoic, the presented trend of P/Fe ratios suggests dissolved P concentrations were higher in Precambrian than Phanerozoic oceans. High dissolved P levels in the Precambrian may have been linked to inhibited carbonate fluorapatite (CFA) formation as a result of persistently high levels of carbonate supersaturation. Carbonate ion substitution into CFA scales with the ambient carbonate ion activity and increases

  12. Magnetic resonance imaging contrast of iron oxide nanoparticles developed for hyperthermia is dominated by iron content

    PubMed Central

    Wabler, Michele; Zhu, Wenlian; Hedayati, Mohammad; Attaluri, Anilchandra; Zhou, Haoming; Mihalic, Jana; Geyh, Alison; DeWeese, Theodore L.; Ivkov, Robert; Artemov, Dmitri

    2015-01-01

    Purpose Magnetic iron oxide nanoparticles (MNPs) are used as contrast agents for magnetic resonance imaging (MRI) and hyperthermia for cancer treatment. The relationship between MRI signal intensity and cellular iron concentration for many new formulations, particularly MNPs having magnetic properties designed for heating in hyperthermia, is lacking. In this study, we examine the correlation between MRI T2 relaxation time and iron content in cancer cells loaded with various MNP formulations. Materials and methods Human prostate carcinoma DU-145 cells were loaded with starch-coated bionised nanoferrite (BNF), iron oxide (Nanomag® D-SPIO), Feridex™, and dextran-coated Johns Hopkins University (JHU) particles at a target concentration of 50 pg Fe/cell using poly-D-lysine transfection reagent. T2-weighted MRI of serial dilutions of these labelled cells was performed at 9.4 T and iron content quantification was performed using inductively coupled plasma mass spectrometry (ICP-MS). Clonogenic assay was used to characterise cytotoxicity. Results No cytotoxicity was observed at twice the target intracellular iron concentration (~100 pg Fe/cell). ICP-MS revealed highest iron uptake efficiency with BNF and JHU particles, followed by Feridex and Nanomag-D-SPIO, respectively. Imaging data showed a linear correlation between increased intracellular iron concentration and decreased T2 times, with no apparent correlation among MNP magnetic properties. Conclusions This study demonstrates that for the range of nanoparticle concentrations internalised by cancer cells the signal intensity of T2-weighted MRI correlates closely with absolute iron concentration associated with the cells. This correlation may benefit applications for cell-based cancer imaging and therapy including nanoparticle-mediated drug delivery and hyperthermia. PMID:24773041

  13. DETERMINATION OF THE RATES AND PRODUCTS OF FERROUS IRON OXIDATION IN ARSENIC-CONTAMINATED POND WATER.

    EPA Science Inventory

    Dissolved ferrous iron and arsenic in the presence of insufficient oxygenated ground water is released into a pond. When the mixing of ferrous iron and oxygenated water within the pond occurs, the ferrous iron is oxidized and precipitated as an iron oxide. Groups of experiments...

  14. Synthesis, characterization, applications, and challenges of iron oxide nanoparticles.

    PubMed

    Ali, Attarad; Zafar, Hira; Zia, Muhammad; Ul Haq, Ihsan; Phull, Abdul Rehman; Ali, Joham Sarfraz; Hussain, Altaf

    2016-01-01

    Recently, iron oxide nanoparticles (NPs) have attracted much consideration due to their unique properties, such as superparamagnetism, surface-to-volume ratio, greater surface area, and easy separation methodology. Various physical, chemical, and biological methods have been adopted to synthesize magnetic NPs with suitable surface chemistry. This review summarizes the methods for the preparation of iron oxide NPs, size and morphology control, and magnetic properties with recent bioengineering, commercial, and industrial applications. Iron oxides exhibit great potential in the fields of life sciences such as biomedicine, agriculture, and environment. Nontoxic conduct and biocompatible applications of magnetic NPs can be enriched further by special surface coating with organic or inorganic molecules, including surfactants, drugs, proteins, starches, enzymes, antibodies, nucleotides, nonionic detergents, and polyelectrolytes. Magnetic NPs can also be directed to an organ, tissue, or tumor using an external magnetic field for hyperthermic treatment of patients. Keeping in mind the current interest in iron NPs, this review is designed to report recent information from synthesis to characterization, and applications of iron NPs. PMID:27578966

  15. Synthesis, characterization, applications, and challenges of iron oxide nanoparticles

    PubMed Central

    Ali, Attarad; Zafar, Hira; Zia, Muhammad; ul Haq, Ihsan; Phull, Abdul Rehman; Ali, Joham Sarfraz; Hussain, Altaf

    2016-01-01

    Recently, iron oxide nanoparticles (NPs) have attracted much consideration due to their unique properties, such as superparamagnetism, surface-to-volume ratio, greater surface area, and easy separation methodology. Various physical, chemical, and biological methods have been adopted to synthesize magnetic NPs with suitable surface chemistry. This review summarizes the methods for the preparation of iron oxide NPs, size and morphology control, and magnetic properties with recent bioengineering, commercial, and industrial applications. Iron oxides exhibit great potential in the fields of life sciences such as biomedicine, agriculture, and environment. Nontoxic conduct and biocompatible applications of magnetic NPs can be enriched further by special surface coating with organic or inorganic molecules, including surfactants, drugs, proteins, starches, enzymes, antibodies, nucleotides, nonionic detergents, and polyelectrolytes. Magnetic NPs can also be directed to an organ, tissue, or tumor using an external magnetic field for hyperthermic treatment of patients. Keeping in mind the current interest in iron NPs, this review is designed to report recent information from synthesis to characterization, and applications of iron NPs. PMID:27578966

  16. The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

    PubMed

    Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

    2016-05-01

    Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases.

  17. Model selection for athermal cross-linked fiber networks.

    PubMed

    Shahsavari, A; Picu, R C

    2012-07-01

    Athermal random fiber networks are usually modeled by representing each fiber as a truss, a Euler-Bernoulli or a Timoshenko beam, and, in the case of cross-linked networks, each cross-link as a pinned, rotating, or welded joint. In this work we study the effect of these various modeling options on the dependence of the overall network stiffness on system parameters. We conclude that Timoshenko beams can be used for the entire range of density and beam stiffness parameters, while the Euler-Bernoulli model can be used only at relatively low network densities. In the high density-high bending stiffness range, strain energy is stored predominantly in the axial and shear deformation modes, while in the other extreme range of parameters, the energy is stored in the bending mode. The effect of the model size on the network stiffness is also discussed. PMID:23005468

  18. [Cross-linking and intrastromal corneal ring segment].

    PubMed

    Renesto, Adimara da Candelaria; Sartori, Marta; Campos, Mauro

    2011-01-01

    Corneal cross-linking is a procedure used for stabilizing the cornea in patients with progressive keratoconus by increasing corneal rigidity, and it is also used in corneal inflammatory melting process. The intrastromal corneal ring segments act by flattening the center of the cornea. Originally designed for the correction of mild myopia, the segments are now being used for reduction of keratoconus in order to improve the uncorrected visual acuity, the best spectacle corrected visual acuity, to allow good tolerance to the use of contact lenses and delay the need for corneal grafting procedures. The present text presents a review of corneal cross-linking and insertion of intrastromal corneal ring segments, emphasizing their indications, results and complications related until now. PMID:21670914

  19. Collagen cross-linking: Strengthening the unstable cornea

    PubMed Central

    Tomkins, Oren; Garzozi, Hanna J

    2008-01-01

    Corneal ectasia, a weakening of corneal integrity, occurs both due to acquired and congenital conditions such as keratoconus. It is a progressing condition that affects both visual acuity, and corneal stability. Various methods exist for correcting this impairment, however none address the inherit pathology, an increase laxity of the corneal stroma. Collagen cross-linking, a new, minimally invasive method, aims to strengthen the stroma by inducing cross links between neighboring collagen fibers. This method results in an increase in corneal tensile strength, with no medium term adverse effects on its normal architecture. Clinically, treated patients display improvement in both visual acuity and keratometric readings. This method may provide clinicians with easily accessible tools to stop the progression, and even correct visual deterioration due to corneal ectasia. Here we review the current information regarding this new method, as well as discuss its potential benefits and downfalls. PMID:19668440

  20. Cytokines and growth factors cross-link heparan sulfate

    PubMed Central

    Migliorini, Elisa; Thakar, Dhruv; Kühnle, Jens; Sadir, Rabia; Dyer, Douglas P.; Li, Yong; Sun, Changye; Volkman, Brian F.; Handel, Tracy M.; Coche-Guerente, Liliane; Fernig, David G.; Lortat-Jacob, Hugues; Richter, Ralf P.

    2015-01-01

    The glycosaminoglycan heparan sulfate (HS), present at the surface of most cells and ubiquitous in extracellular matrix, binds many soluble extracellular signalling molecules such as chemokines and growth factors, and regulates their transport and effector functions. It is, however, unknown whether upon binding HS these proteins can affect the long-range structure of HS. To test this idea, we interrogated a supramolecular model system, in which HS chains grafted to streptavidin-functionalized oligoethylene glycol monolayers or supported lipid bilayers mimic the HS-rich pericellular or extracellular matrix, with the biophysical techniques quartz crystal microbalance (QCM-D) and fluorescence recovery after photobleaching (FRAP). We were able to control and characterize the supramolecular presentation of HS chains—their local density, orientation, conformation and lateral mobility—and their interaction with proteins. The chemokine CXCL12α (or SDF-1α) rigidified the HS film, and this effect was due to protein-mediated cross-linking of HS chains. Complementary measurements with CXCL12α mutants and the CXCL12γ isoform provided insight into the molecular mechanism underlying cross-linking. Fibroblast growth factor 2 (FGF-2), which has three HS binding sites, was also found to cross-link HS, but FGF-9, which has just one binding site, did not. Based on these data, we propose that the ability to cross-link HS is a generic feature of many cytokines and growth factors, which depends on the architecture of their HS binding sites. The ability to change matrix organization and physico-chemical properties (e.g. permeability and rigidification) implies that the functions of cytokines and growth factors may not simply be confined to the activation of cognate cellular receptors. PMID:26269427

  1. Estimating the Degree of Cross-Linking in Rubber

    NASA Technical Reports Server (NTRS)

    Fedors, R. F.

    1983-01-01

    Degree of cross-linking or network chain concentration of rubber estimated with aid of new method. Quantity is needed in studies of mechanical behavior of rubber. New method is based on finding rubber follows different stress/ strain relationships in extension and retraction. When rubber specimen is stretched to given extension ration and released. Stress-vs-strain curve follows two paths: one for extension and other for retraction.

  2. Optimized Fragmentation Regime for Diazirine Photo-Cross-Linked Peptides

    PubMed Central

    2016-01-01

    Cross-linking/mass spectrometry has evolved into a robust technology that reveals structural insights into proteins and protein complexes. We leverage a new tribrid instrument with improved fragmentation capacities in a systematic comparison to identify which fragmentation method would be best for the identification of cross-linked peptides. Specifically, we explored three fragmentation methods and two combinations: collision-induced dissociation (CID), beam-type CID (HCD), electron-transfer dissociation (ETD), ETciD, and EThcD. Trypsin-digested, SDA-cross-linked human serum albumin (HSA) served as a test sample, yielding over all methods and in triplicate analysis in total 2602 matched PSMs and 1390 linked residue pairs at 5% false discovery rate, as confirmed by the crystal structure. HCD wins in number of matched peptide-spectrum-matches (958 PSMs) and identified links (446). CID is most complementary, increasing the number of identified links by 13% (58 links). HCD wins together with EThcD in cross-link site calling precision, with approximately 62% of sites having adjacent backbone cleavages that unambiguously locate the link in both peptides, without assuming any cross-linker preference for amino acids. Overall quality of spectra, as judged by sequence coverage of both peptides, is best for EThcD for the majority of peptides. Sequence coverage might be of particular importance for complex samples, for which we propose a data dependent decision tree, else HCD is the method of choice. The mass spectrometric raw data has been deposited in PRIDE (PXD003737). PMID:27454319

  3. Newer protocols and future in collagen cross-linking.

    PubMed

    Cummings, Arthur B; McQuaid, Rebecca; Mrochen, Michael

    2013-08-01

    Corneal Cross-Linking (CXL) is an established surgical procedure for the treatment of corneal disorders such as corneal ectasia and keratoconus. This method of treatment stabilises the corneal structure and increases rigidity, reducing the requirement for corneal transplantation. Since its development, many scientific studies have been conducted to investigate ways of improving the procedure. Biomechanical stability of the cornea after exposure to UV-A light, and the effect of shortening procedure time has been some of the many topics explored.

  4. Optimized Fragmentation Regime for Diazirine Photo-Cross-Linked Peptides.

    PubMed

    Giese, Sven H; Belsom, Adam; Rappsilber, Juri

    2016-08-16

    Cross-linking/mass spectrometry has evolved into a robust technology that reveals structural insights into proteins and protein complexes. We leverage a new tribrid instrument with improved fragmentation capacities in a systematic comparison to identify which fragmentation method would be best for the identification of cross-linked peptides. Specifically, we explored three fragmentation methods and two combinations: collision-induced dissociation (CID), beam-type CID (HCD), electron-transfer dissociation (ETD), ETciD, and EThcD. Trypsin-digested, SDA-cross-linked human serum albumin (HSA) served as a test sample, yielding over all methods and in triplicate analysis in total 2602 matched PSMs and 1390 linked residue pairs at 5% false discovery rate, as confirmed by the crystal structure. HCD wins in number of matched peptide-spectrum-matches (958 PSMs) and identified links (446). CID is most complementary, increasing the number of identified links by 13% (58 links). HCD wins together with EThcD in cross-link site calling precision, with approximately 62% of sites having adjacent backbone cleavages that unambiguously locate the link in both peptides, without assuming any cross-linker preference for amino acids. Overall quality of spectra, as judged by sequence coverage of both peptides, is best for EThcD for the majority of peptides. Sequence coverage might be of particular importance for complex samples, for which we propose a data dependent decision tree, else HCD is the method of choice. The mass spectrometric raw data has been deposited in PRIDE (PXD003737). PMID:27454319

  5. Reversible PH Lability of Cross-Linked Vault Nanocapsules

    SciTech Connect

    Yu, M.; Ng, B.C.; Rome, L.H.; Tolbert, S.H.; Monbouquette, H.G.

    2009-05-28

    Vaults are ubiquitous, self-assembled protein nanocapsules with dimension in the sub-100 nm range that are conserved across diverse phyla from worms to humans. Their normal presence in humans at a copy number of over 10 000/cell makes them attractive as potential drug delivery vehicles. Toward this goal, bifunctional amine-reactive reagents are shown to be useful for the reversible cross-linking of recombinant vaults such that they may be closed and opened in a controllable manner.

  6. Electrochemical Characterization of Ultrathin Cross-Linked Metal Nanoparticle Films.

    PubMed

    Han, Chu; Percival, Stephen J; Zhang, Bo

    2016-09-01

    Here we report the preparation, characterization, and electrochemical study of conductive, ultrathin films of cross-linked metal nanoparticles (NPs). Nanoporous films ranging from 40 to 200 nm in thickness composed of gold and platinum NPs of ∼5 nm were fabricated via a powerful layer-by-layer spin coating process. This process allows preparation of uniform NP films as large as 2 × 2 cm(2) with precise control over thickness, structure, and electrochemical and electrocatalytic properties. Gold, platinum, and bimetallic NP films were fabricated and characterized using cyclic voltammetry, scanning electron microscopy, and conductance measurements. Their electrocatalytic activity toward the oxygen reduction reaction (ORR) was investigated. Our results show that the electrochemical activity of such NP films is initially hindered by the presence of dense thiolate cross-linking ligands. Both electrochemical cycling and oxygen plasma cleaning are effective means in restoring their electrochemical activity. Gold NP films have higher electric conductivity than platinum possibly due to more uniform film structure and closer particle-particle distance. The electrochemical and electrocatalytic performance of platinum NP films can be greatly enhanced by the incorporation of gold NPs. This work focuses on electrochemical characterization of cross-linked NP films and demonstrates several unique properties. These include quick and easy preparation, ultrathin and uniform film thickness, tunable structure and composition, and transferability to many other substrates.

  7. Magnetic macromolecular cross linked enzyme aggregates (CLEAs) of glucoamylase.

    PubMed

    Nadar, Shamraja S; Rathod, Virendra K

    2016-02-01

    This work illustrates the preparation of magnetic macromolecular glucoamylase CLEAs using dialdehydic pectin, as a cross linker instead of traditional glutaraldehyde. The effect of precipitators type and amount, cross linker concentration, cross linking time and amount of amino functionalized magnetic nanoparticles (AFMNs) on glucoamylase activity was studied. Glucoamylase magnetic macromolecular CLEAs prepared by precipitation in presence of AFMNs by ammonium sulfate were subsequently cross linked by dialdehydic pectin. After cross-linked by pectin, 95.4% activity recovery was achieved in magnetic macromolecular CLEAs, whereas in case of glutaraldehyde cross linker, 85.3% activity recovery was achieved. Magnetic macromolecular CLEAs showed 2.91 and 1.27 folds higher thermal stability as compared to free and magnetic glutaraldehyde CLEAs. In kinetics study, magnetic macromolecular CLEAs retained same Km values, whereas magnetic glutaraldehyde CLEAs showed higher Km value than free enzyme. The porous structure of magnetic macromolecular CLEAs was not only enhanced mass transfer toward macromolecular substrates, but also showed compression resistance for 5 consecutive cycles which was checked in terms of effectiveness factor. At the end, in reusability study; magnetic macromolecular CLEAs were retained 84% activity after 10(th) cycle without leaching of enzyme which is 22% higher than traditional magnetic CLEAs.

  8. Ion exchange selectivity for cross-linked polyacrylic acid

    NASA Technical Reports Server (NTRS)

    May, C. E.; Philipp, W. H.

    1983-01-01

    The ion separation factors for 21 common metal ions with cross-linked polyacrylic acid were determined as a function of pH and the percent of the cross-linked polyacrylic acid neutralized. The calcium ion was used as a reference. At a pH of 5 the decreasing order of affinity of the ions for the cross-linked polyacrylic acid was found to be: Hg++, Fe+++, Pb++, Cr+++, Cu++, Cd++, Al+++, Ag+, Zn++, Ni++, Mn++, Co++, Ca++, Sr++, Ba++, Mg++, K+, Rb+, Cs+, Na+, and Li+. Members of a chemical family exhibited similar selectivities. The Hg++ ion appeared to be about a million times more strongly bound than the alkali metal ions. The relative binding of most of the metal ions varied with pH; the very tightly and very weakly bound ions showed the largest variations with pH. The calcium ion-hydrogen ion equilibrium was perturbed very little by the presence of the other ions. The separation factors and selectivity coefficients are discussed in terms of equilibrium and thermodynamic significance.

  9. Homogeneous UVA system for corneal cross-linking treatment

    NASA Astrophysics Data System (ADS)

    Ayres Pereira, Fernando R.; Stefani, Mario A.; Otoboni, José A.; Richter, Eduardo H.; Ventura, Liliane

    2010-02-01

    The treatment of keratoconus and corneal ulcers by collagen cross-linking using ultraviolet type A irradiation, combined with photo-sensitizer Riboflavin (vitamin B2), is a promising technique. The standard protocol suggests instilling Riboflavin in the pre-scratched cornea every 5min for 30min, during the UVA irradiation of the cornea at 3mW/cm2 for 30 min. This process leads to an increase of the biomechanical strength of the cornea, stopping the progression, or sometimes, even reversing Keratoconus. The collagen cross-linking can be achieved by many methods, but the utilization of UVA light, for this purpose, is ideal because of its possibility of a homogeneous treatment leading to an equal result along the treated area. We have developed a system, to be clinically used for treatment of unhealthy corneas using the cross-linking technique, which consists of an UVA emitting delivery device controlled by a closed loop system with high homogeneity. The system is tunable and delivers 3-5 mW/cm2, at 365nm, for three spots (6mm, 8mm and 10mm in diameter). The electronics close loop presents 1% of precision, leading to an overall error, after the calibration, of less than 10% and approximately 96% of homogeneity.

  10. Fiber optic immunosensor for cross-linked fibrin concentration

    NASA Astrophysics Data System (ADS)

    Moskowitz, Samuel E.

    2000-08-01

    Working with calcium ions in the blood, platelets produce thromboplastin which transforms prothrombin into thrombin. Removing peptides, thrombin changes fibrinogen into fibrin. Cross-linked insoluble fibrin polymers are solubilized by enzyme plasmin found in blood plasma. Resulting D-dimers are elevated in patients with intravascular coagulation, deep venous thrombosis, pulmonary embolism, myocardial infarction, multiple trauma, cancer, impaired renal and liver functions, and sepsis. Consisting principally of a NIR 780 nm GaAlAs laser diode and a 800 nm avalanche photodiode (APD), the fiber-optic immunosensor can determined D-dimer concentration to levels <0.1 ng/ml. A capture monoclonal antibody to the antigen soluble cross-linked fibrin is employed. Immobilized at the tip of an optical fiber by avidin-biotin, the captured antigen is detected by a second antibody which is labeled with NN 382 fluorescent dye. An evanescent wave traveling on an excitation optical fiber excites the antibody-antigen fluorophore complex. Concentration of cross-linked fibrin is directly proportional to the APD measured intensity of fluorescence. NIR fluorescence has advantages of low background interference, short fluorescence lifetime, and large difference between excitation and emission peaks. Competitive ELISA test for D-dimer concentration requires trained personnel performing a time consuming operation.

  11. Induction and repair of DNA cross-links induced by sulfur mustard in the A-549 cell line followed by a comet assay.

    PubMed

    Jost, Petr; Svobodova, Hana; Stetina, Rudolf

    2015-07-25

    Sulfur mustard is a highly toxic chemical warfare agent with devastating impact on intoxicated tissues. DNA cross-links are probably the most toxic DNA lesions induced in the cell by sulfur mustard. The comet assay is a very sensitive method for measuring DNA damage. In the present study using the A-549 lung cell line, the comet assay protocol was optimized for indirect detection of DNA cross-links induced by sulfur mustard. The method is based on the additional treatment of the assayed cells containing cross-links with the chemical mutagen, styrene oxide. Alkali-labile adducts of styrene oxide cause DNA breaks leading to the formation of comets. A significant dose-dependent reduction of DNA migration of the comet's tail was found after exposing cells to sulfur mustard, indicative of the amount of sulfur mustard induced cross-links. The remarkable decrease of % tail DNA could be observed as early as 5min following exposure to sulfur mustard and the maximal effect was found after 30min, when DNA migration was reduced to the minimum. Sulfur mustard preincubated in culture medium without cells lost its ability to induce cross-links and had a half-life of about 15min. Pre-incubation longer than 30min does not lead to a significant increase in cross-links when applied to cells. However, the amount of cross-links is decreased during further incubation due to repair. The current modification of the comet assay provides a useful tool for detecting DNA cross-links induced by sulfur mustard and could be used for detection of other DNA cross-linking agents such as chemotherapeutic drugs. PMID:25986970

  12. Induction and repair of DNA cross-links induced by sulfur mustard in the A-549 cell line followed by a comet assay.

    PubMed

    Jost, Petr; Svobodova, Hana; Stetina, Rudolf

    2015-07-25

    Sulfur mustard is a highly toxic chemical warfare agent with devastating impact on intoxicated tissues. DNA cross-links are probably the most toxic DNA lesions induced in the cell by sulfur mustard. The comet assay is a very sensitive method for measuring DNA damage. In the present study using the A-549 lung cell line, the comet assay protocol was optimized for indirect detection of DNA cross-links induced by sulfur mustard. The method is based on the additional treatment of the assayed cells containing cross-links with the chemical mutagen, styrene oxide. Alkali-labile adducts of styrene oxide cause DNA breaks leading to the formation of comets. A significant dose-dependent reduction of DNA migration of the comet's tail was found after exposing cells to sulfur mustard, indicative of the amount of sulfur mustard induced cross-links. The remarkable decrease of % tail DNA could be observed as early as 5min following exposure to sulfur mustard and the maximal effect was found after 30min, when DNA migration was reduced to the minimum. Sulfur mustard preincubated in culture medium without cells lost its ability to induce cross-links and had a half-life of about 15min. Pre-incubation longer than 30min does not lead to a significant increase in cross-links when applied to cells. However, the amount of cross-links is decreased during further incubation due to repair. The current modification of the comet assay provides a useful tool for detecting DNA cross-links induced by sulfur mustard and could be used for detection of other DNA cross-linking agents such as chemotherapeutic drugs.

  13. Nitric oxide initiates iron binding to neocuproine.

    PubMed

    Vanin, A F; Serezhenkov, V A; Malenkova, I V

    2001-04-01

    It was demonstrated that two species of paramagnetic dinitrosyl iron complex (DNIC) with neocuproine form under the following conditions: in addition of neocuproine to a solution of DNIC with phosphate; in gaseous NO treatment of a mixture of Fe(2+) + neocuproine aqueous solutions at pH 6.5-8; and in addition of Fe(2+)--citrate complex + neocuproine to a S-nitrosocysteine (cys-NO) solution. The first form of DNIC with neocuproine is characterized by an EPR signal with g-factor values of 2.087, 2.055, and 2.025, when it is recorded at 77K. At room temperature, the complex displays a symmetric singlet at g = 2.05. The second form of DNIC with neocuproine gives an EPR signal with g-factor values of 2.042, 2.02, and 2.003, which can be recorded at a low temperature only.The revealed complexes are close to DNIC with cysteine in their stability. The ability of neocuproine to bind Fe(2+) in the presence of NO with formation of paramagnetic DNICs warrants critical reevaluation of the statement that neocuproine is only able to bind Cu(+) ions. It was suggested that the observed affinity of neocuproine to iron was due to transition of Fe(2+) in DNIC with neocuproine to Fe(+). In experiments on cys-NO, it was shown that the stabilizing effect of neocuproine on this compound could be due to neocuproine binding to the iron catalyzing decomposition of cys-NO.

  14. Nitric oxide initiates iron binding to neocuproine.

    PubMed

    Vanin, A F; Serezhenkov, V A; Malenkova, I V

    2001-04-01

    It was demonstrated that two species of paramagnetic dinitrosyl iron complex (DNIC) with neocuproine form under the following conditions: in addition of neocuproine to a solution of DNIC with phosphate; in gaseous NO treatment of a mixture of Fe(2+) + neocuproine aqueous solutions at pH 6.5-8; and in addition of Fe(2+)--citrate complex + neocuproine to a S-nitrosocysteine (cys-NO) solution. The first form of DNIC with neocuproine is characterized by an EPR signal with g-factor values of 2.087, 2.055, and 2.025, when it is recorded at 77K. At room temperature, the complex displays a symmetric singlet at g = 2.05. The second form of DNIC with neocuproine gives an EPR signal with g-factor values of 2.042, 2.02, and 2.003, which can be recorded at a low temperature only.The revealed complexes are close to DNIC with cysteine in their stability. The ability of neocuproine to bind Fe(2+) in the presence of NO with formation of paramagnetic DNICs warrants critical reevaluation of the statement that neocuproine is only able to bind Cu(+) ions. It was suggested that the observed affinity of neocuproine to iron was due to transition of Fe(2+) in DNIC with neocuproine to Fe(+). In experiments on cys-NO, it was shown that the stabilizing effect of neocuproine on this compound could be due to neocuproine binding to the iron catalyzing decomposition of cys-NO. PMID:11292366

  15. Iron Kinetics and Evolution of Microbial Populations in Low-pH, Ferrous Iron-Oxidizing Bioreactors.

    PubMed

    Jones, Rose M; Johnson, D Barrie

    2016-08-01

    Iron-rich, acidic wastewaters are commonplace pollutants associated with metal and coal mining. Continuous-flow bioreactors were commissioned and tested for their capacities to oxidize ferrous iron in synthetic and actual acid mine drainage waters using (initially) pure cultures of the recently described acidophilic, iron-oxidizing heterotrophic bacterium Acidithrix ferrooxidans grown in the presence of glucose and yeast extract. The bioreactors became rapidly colonized by this bacterium, which formed macroscopic streamer growths in the flowing waters. Over 97% of ferrous iron in pH 2.0-2.2 synthetic mine water was oxidized (at up to 225 mg L(-1) h(-1)) at dilution rates (D) of 0.6 h(-1). Rates of iron oxidation decreased with pH but were still significant, with influent liquors as low as pH 1.37. When fed with actual mine water, >90% of ferrous iron was oxidized at D values of 0.4 h(-1), and microbial communities within the bioreactors changed over time, with Atx. ferrooxidans becoming increasingly displaced by the autotrophic iron-oxidizing acidophiles Ferrovum myxofaciens, Acidithiobacillus ferrivorans, and Leptospirillum ferrooxidans (which were all indigenous to the mine water), although this did not have a negative impact on net ferrous-iron oxidation. The results confirmed the potential of using a heterotrophic acidophile to facilitate the rapid commissioning of iron-oxidizing bioreactors and illustrated how microbial communities within them can evolve without compromising the performances of the bioreactors. PMID:27377871

  16. Cross linking molecular systems to form ultrathin dielectric layers

    NASA Astrophysics Data System (ADS)

    Feng, Danqin

    Dehydrogenation leads to cross linking of polymer or polymer like formation in very different systems: self-assembled monolayers and in closo -carboranes leading to the formation of semiconducting and dielectric boron carbide. We find evidence of intermolecular interactions for a self-assembled monolayer (SAM) formed from a large molecular adsorbate, [1,1';4',1"-terphenyl]-4,4"-dimethanethiol, from the dispersion of the molecular orbitals with changing the wave vector k and from the changes with temperature. With the formation self assembled molecular (SAM) layer, the molecular orbitals hybridize to electronic bands, with indications of significant band dispersion of the unoccupied molecular orbitals. Although organic adsorbates and thin films are generally regarded as "soft" materials, the effective Debye temperature, indicative of the dynamic motion of the lattice normal to the surface, can be very high, e.g. in the multilayer film formed from [1,1'-biphenyl]-4,4'-dimethanethiol (BPDMT). Depending on molecular orientation, the effective Debye temperature can be comparable to that of graphite due to the 'stiffness' of the benzene rings, but follows the expected Debye-Waller behavior for the core level photoemission intensities with temperature. This is not always the case. We find that a monomolecular film formed from [1,1';4',1"-terphenyl]-4,4"-dimethanethiol deviates from Debye-Waller temperature behavior and is likely caused by temperature dependent changes in molecular orientation. We also find evidence for the increase in dielectric character with polymerization (cross-linking) in spite of the decrease in the HOMO-LUMO gap upon irradiation of TPDMT. The changes in the HOMO-LUMO gap, with cross-linking, are roughly consistent with the band dispersion. The decomposition and cross-linking processes are also accompanied by changes in molecular orientation. The energetics of the three isomeric carborane cage compounds [ closo-1,2-orthocarborane, closo-1

  17. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...

  18. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...

  19. Iron oxidation state in hydrous rhyolites

    NASA Astrophysics Data System (ADS)

    Humphreys, M.; Brooker, R.; Fraser, D.; Smith, V. C.

    2012-12-01

    Recent studies have suggested that the Earth's mantle at subduction zones is oxidized relative to that at mid-ocean ridges. One possible origin of the oxidation is thought to be hydrous fluids, which are released into the mantle from the down-going slab during subduction. However, this is controversial; other studies have concluded that there is no intrinsic difference in oxidation state. One potential problem in determining primary oxidation states is that magmas produced by partial melting of the sub-arc mantle undergo significant degassing and crystallisation near the earth's surface, which may overprint the oxidation state of the primary melt. H2O contents of melt inclusions may be affected by partial re-equilibration. The effect of H2O on Fe oxidation state is unclear, although theoretical arguments typically predict increasing Fe3+/ΣFe during shallow degassing as a result of preferential diffusion of H2 out of the melt: FeO (m) + H2O (m) = Fe2O3 (m) + H2 (g) [1] We used XANES to measure Fe3+/Fe2+ in cylinders of rhyolitic obsidian that had been hydrated in gold capsules in cold-seal apparatus. Runs were performed at 850-900 °C under H2O-saturated conditions for short run times (20-80 minutes). Surprisingly, we find a positive correlation between Fe3+/ΣFe and H2O content of the glass. This is inconsistent with the effects of reaction [1], but can be explained by considering the acid-base properties of the hydrous melt. In particular, basic behaviour of FeO but amphoteric behaviour of Fe2O3, and changes in melt basicity relating to dissolution of H2O, can explain increasing Fe3+/Fe2+ with increasing H2O. We discuss the implications of these results for using melt compositions to infer the oxidation state of the earth's mantle.

  20. Iron oxide nanotubes synthesized via template-based electrodeposition

    NASA Astrophysics Data System (ADS)

    Lim, Jin-Hee; Min, Seong-Gi; Malkinski, Leszek; Wiley, John B.

    2014-04-01

    Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, magnetization curves show ferromagnetism with weak coercivity at room temperature, while FC-ZFC curves exhibit the Verwey transition at 125 K.Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition

  1. Integrated reactive ion etching to pattern cross-linked hydrophilic polymer structures for protein immobilization

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Parijat; Strickland, Aaron D.; Kim, Il; Malliaras, George G.; Batt, Carl A.

    2007-04-01

    Patterning of cross-linked hydrophilic polymer features using reactive ion etching (RIE) capable of covalently immobilizing proteins has been achieved. Projection photolithography was used to pattern photoresist to create micromolds. Vapor phase molecular self-assembly of polymerizable monolayer in molds allowed covalent binding of hydrogel on surface during free-radical polymerization. Excess hydrogel blanket film was consumed with oxygen RIE resulting into hydrogel pattern of 1μm size aligned to prefabricated silicon oxide structures. Proteins were finally coupled through their primary amine groups selectively to acid functionalized hydrogel features through stable amide linkages using 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride and N-hydroxysulfosuccinimide.

  2. Simultaneous reductive dissolution of iron oxide and oxidation of iodide in ice.

    NASA Astrophysics Data System (ADS)

    Kim, Kitae; Choi, Wonyong

    2015-04-01

    Iron is an important trace element controlling the metabolism and growth of all kinds of living species. Especially, the bio-availability of iron has been regarded as the limiting factor for primary productivity in HNLC (High Nutrients Low Chlorophyll) regions including Southern ocean. The dissolution of iron oxide provides enhanced the bio-availability of iron for phytoplankton growth. The halogen chemistry in polar regions is related to various important environmental processes such as Antarctic Ozone Depletion Event(ODE), mercury depletion, oxidative processes in atmosphere, and the formation of CCN (Cloud Condensation Nuclei). In this study, we investigated the reductive dissolution of iron oxide particles to produce Fe(II)aq and simultaneous oxidation of I- (iodide) to I3- (tri-iodide) in ice phase under UV irradiation or dark condition. The reductive generation of Fe(II)aq from iron oxides and oxidation of iodide to I3- were negligible in water but significantly accelerated in frozen solution both in the presence and absence of light. The enhanced reductive generation of Fe(II)aq and oxidative formation of I3- in ice were observed regardless of the various types of iron oxides [hematite (α-Fe2O3) maghemite (γ- Fe2O3), goethite (α-FeOOH), lepidocrocite (γ-FeOOH) and, magnetite (Fe3O4)]. We explained that the enhanced redox production of Fe(II)aq and I3- in ice is contributed to the freeze concentration of iodides, protons, and dissolved oxygen in the unfrozen solution. When the concentration of both iodides and protons were raised by 10-fold each, the formation of Fe(II)aq in water under UV irradiation was approached to those in ice. The outdoor experiments were carried out under ambient solar radiation in winter season of mid-latitude (Pohang, Korea: 36°N latitude) and also confirmed that the production of Fe(II)aq via reductive dissolution of iron oxide and I3- generation via I- oxidation were enhanced in frozen solution. These results suggest that iron

  3. Selective stabilization of aliphatic organic carbon by iron oxide

    PubMed Central

    Adhikari, Dinesh; Yang, Yu

    2015-01-01

    Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter. PMID:26061259

  4. Selective stabilization of aliphatic organic carbon by iron oxide.

    PubMed

    Adhikari, Dinesh; Yang, Yu

    2015-01-01

    Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter. PMID:26061259

  5. Oxidation, carburization and/or sulfidation resistant iron aluminide alloy

    DOEpatents

    Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

    2003-08-19

    The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or Zro.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B. .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

  6. The Molecular Mechanism of Iron(III) Oxide Nucleation.

    PubMed

    Scheck, Johanna; Wu, Baohu; Drechsler, Markus; Rosenberg, Rose; Van Driessche, Alexander E S; Stawski, Tomasz M; Gebauer, Denis

    2016-08-18

    A molecular understanding of the formation of solid phases from solution would be beneficial for various scientific fields. However, nucleation pathways are still not fully understood, whereby the case of iron (oxyhydr)oxides poses a prime example. We show that in the prenucleation regime, thermodynamically stable solute species up to a few nanometers in size are observed, which meet the definition of prenucleation clusters. Nucleation then is not governed by a critical size, but rather by the dynamics of the clusters that are forming at the distinct nucleation stages, based on the chemistry of the linkages within the clusters. This resolves a longstanding debate in the field of iron oxide nucleation, and the results may generally apply to oxides forming via hydrolysis and condensation. The (molecular) understanding of the chemical basis of phase separation is paramount for, e.g., tailoring size, shape and structure of novel nanocrystalline materials.

  7. The Molecular Mechanism of Iron(III) Oxide Nucleation.

    PubMed

    Scheck, Johanna; Wu, Baohu; Drechsler, Markus; Rosenberg, Rose; Van Driessche, Alexander E S; Stawski, Tomasz M; Gebauer, Denis

    2016-08-18

    A molecular understanding of the formation of solid phases from solution would be beneficial for various scientific fields. However, nucleation pathways are still not fully understood, whereby the case of iron (oxyhydr)oxides poses a prime example. We show that in the prenucleation regime, thermodynamically stable solute species up to a few nanometers in size are observed, which meet the definition of prenucleation clusters. Nucleation then is not governed by a critical size, but rather by the dynamics of the clusters that are forming at the distinct nucleation stages, based on the chemistry of the linkages within the clusters. This resolves a longstanding debate in the field of iron oxide nucleation, and the results may generally apply to oxides forming via hydrolysis and condensation. The (molecular) understanding of the chemical basis of phase separation is paramount for, e.g., tailoring size, shape and structure of novel nanocrystalline materials. PMID:27466739

  8. Missing Iron-Oxidizing Acidophiles Highly Sensitive to Organic Compounds

    PubMed Central

    Ueoka, Nagayoshi; Kouzuma, Atsushi; Watanabe, Kazuya

    2016-01-01

    The genus Acidithiobacillus includes iron-oxidizing lithoautotrophs that thrive in acidic mine environments. Acidithiobacillus ferrooxidans is a representative species and has been extensively studied for its application to the bioleaching of precious metals. In our attempts to cultivate the type strain of A. ferrooxidans (ATCC 23270T), repeated transfers to fresh inorganic media resulted in the emergence of cultures with improved growth traits. Strains were isolated from the resultant culture by forming colonies on inorganic silica-gel plates. A representative isolate (strain NU-1) was unable to form colonies on agarose plates and was more sensitive to organics, such as glucose, than the type strain of A. ferrooxidans. Strain NU-1 exhibited superior growth traits in inorganic iron media to those of other iron-oxidizing acidithiobacilli, suggesting its potential for industrial applications. A draft genome of NU-1 uncovered unique features in catabolic enzymes, indicating that this strain is not a mutant of the A. ferrooxidans type strain. Our results indicate that the use of inorganic silica-gel plates facilitates the isolation of as-yet-unexamined iron-oxidizing acidithiobacilli from environmental samples and enrichment cultures. PMID:27356527

  9. Oxide Dispersion Strengthened Iron Aluminide by CVD Coated Powders

    SciTech Connect

    Asit Biswas Andrew J. Sherman

    2006-09-25

    This I &I Category2 program developed chemical vapor deposition (CVD) of iron, aluminum and aluminum oxide coated iron powders and the availability of high temperature oxidation, corrosion and erosion resistant coating for future power generation equipment and can be used for retrofitting existing fossil-fired power plant equipment. This coating will provide enhanced life and performance of Coal-Fired Boilers components such as fire side corrosion on the outer diameter (OD) of the water wall and superheater tubing as well as on the inner diameter (ID) and OD of larger diameter headers. The program also developed a manufacturing route for readily available thermal spray powders for iron aluminide coating and fabrication of net shape component by powder metallurgy route using this CVD coated powders. This coating can also be applid on jet engine compressor blade and housing, industrial heat treating furnace fixtures, magnetic electronic parts, heating element, piping and tubing for fossil energy application and automotive application, chemical processing equipment , heat exchanger, and structural member of aircraft. The program also resulted in developing a new fabrication route of thermal spray coating and oxide dispersion strengthened (ODS) iron aluminide composites enabling more precise control over material microstructures.

  10. In vivo biodistribution of iron oxide nanoparticles: an overview

    NASA Astrophysics Data System (ADS)

    Tate, Jennifer A.; Petryk, Alicia A.; Giustini, Andrew J.; Hoopes, P. Jack

    2011-03-01

    Iron oxide nanoparticles present a promising alternative to conventional energy deposition-based tissue therapies. The success of such nanoparticles as a therapeutic for diseases like cancer, however, depends heavily on the particles' ability to localize to tumor tissue as well as provide minimal toxicity to surrounding tissues and key organs such as those involved in the reticuloendothelial system (RES). We present here the results of a long term clearance study where mice injected intravenously with 2 mg Fe of 100 nm dextran-coated iron oxide nanoparticles were sacrificed at 14 and 580 days post injection. Histological analysis showed accumulation of the nanoparticles in some RES organs by the 14 day time point and clearance of the nanoparticles by the 580 day time point with no obvious toxicity to organs. An additional study reported herein employs 20 nm and 110 nm starch-coated iron oxide nanoparticles at 80 mg Fe/kg mouse in a size/biodistribution study with endpoints at 4, 24 and 72 hours. Preliminary results show nanoparticle accumulation in the liver and spleen with some elevated iron accumulation in tumoral tissues with differences between the 20 nm and the 110 nm nanoparticle depositions.

  11. Covalent Immobilization of Catalase onto Regenerated Silk Fibroins via Tyrosinase-Catalyzed Cross-Linking.

    PubMed

    Wang, Ping; Qi, Chenglong; Yu, Yuanyuan; Yuan, Jiugang; Cui, Li; Tang, Gengtie; Wang, Qiang; Fan, Xuerong

    2015-09-01

    Regenerated silk fibroins could be used as medical scaffolds and carrier materials for enzyme immobilization. In the present work, tyrosinase enzyme was used for enzymatic oxidation of silk fibroins, followed by immobilization of catalase onto the fibroin surfaces through physical adsorption and covalent cross-linking as well. Spectrophotometry, SDS-PAGE, and Fourier transform infrared spectroscopy (FTIR) were used to examine the efficiency of enzymatic oxidation and catalase immobilization, respectively. The results indicate that tyrosine residues in silk fibroins could be oxidized and converted to the active o-quinones. Incubating silk fibroins with catalase and tyrosinase led to a noticeable change of molecular weight distribution, indicating the occurrence of the cross-links between silk fibroins and catalase molecules. Two different pathways were proposed for the catalase immobilizations, and the method based on grafting of catalase onto the freeze-dried fibroin membrane is more acceptable. The residual enzyme activity for the immobilized catalase exhibited higher than that of the control after repeated washing cycles. Meanwhile, the thermal stability and alkali resistance were also slightly improved as compared to free catalase. The mechanisms of enzymatic immobilization are also concerned.

  12. The oxidation behavior of ODS iron aluminides

    SciTech Connect

    Pint, B.A.; Tortorelli, P.F.; Wright, I.G.

    1996-05-01

    Oxide-dispersed Fe-28at.%Al-2%Cr alloys were produced by a powder metallurgy technique followed by hot extrusion. A variety of stable oxides were added to the base alloy to assess the effect of these dopants on the oxidation behavior at 1200{degrees}C in air and O{sub 2}. An Al{sub 2}O{sub 3} dispersion flattened the {alpha}-Al{sub 2}O{sub 3} scale, but produced none of the other reactive element effects and had an adverse influence on the long-term oxidation behavior. A Y{sub 2}O{sub 3} dispersion improved the alumina scale adhesion relative to a Zr alloy addition at 1200{degrees} and 1300{degrees}C. However, the Y{sub 2}O{sub 3} dispersion was not as effective in improving scale adhesion in Fe{sub 3}Al as it is in FeCrAl. This inferior performance is attributed to a larger amount of interfacial void formation on ODS Fe{sub 3}Al.

  13. Composition, nucleation, and growth of iron oxide concretions

    NASA Astrophysics Data System (ADS)

    Parry, W. T.

    Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions. Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite-smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions. Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection. Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on

  14. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    NASA Astrophysics Data System (ADS)

    Sohn, I.; Fruehan, R. J.

    2006-04-01

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H2O generated from the reduction of Fe2O3 by H2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.

  15. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2006-04-15

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900{sup o}C to 1000{sup o}C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 degrees C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H{sub 2O generated from the reduction of Fe{sub 2}O{sub 3} by H-2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50% reduction of the iron oxide.

  16. RGDS-functionalized polyethylene glycol hydrogel-coated magnetic iron oxide nanoparticles enhance specific intracellular uptake by HeLa cells

    PubMed Central

    Nazli, Caner; Ergenc, Tugba Ipek; Yar, Yasemin; Acar, Havva Yagci; Kizilel, Seda

    2012-01-01

    The objective of this study was to develop thin, biocompatible, and biofunctional hydrogel-coated small-sized nanoparticles that exhibit favorable stability, viability, and specific cellular uptake. This article reports the coating of magnetic iron oxide nanoparticles (MIONPs) with covalently cross-linked biofunctional polyethylene glycol (PEG) hydrogel. Silanized MIONPs were derivatized with eosin Y, and the covalently cross-linked biofunctional PEG hydrogel coating was achieved via surface-initiated photopolymerization of PEG diacrylate in aqueous solution. The thickness of the PEG hydrogel coating, between 23 and 126 nm, was tuned with laser exposure time. PEG hydrogel-coated MIONPs were further functionalized with the fibronectin-derived arginine-glycine-aspartic acid-serine (RGDS) sequence, in order to achieve a biofunctional PEG hydrogel layer around the nanoparticles. RGDS-bound PEG hydrogel-coated MIONPs showed a 17-fold higher uptake by the human cervical cancer HeLa cell line than that of amine-coated MIONPs. This novel method allows for the coating of MIONPs with nano-thin biofunctional hydrogel layers that may prevent undesirable cell and protein adhesion and may allow for cellular uptake in target tissues in a specific manner. These findings indicate that the further biofunctional PEG hydrogel coating of MIONPs is a promising platform for enhanced specific cell targeting in biomedical imaging and cancer therapy. PMID:22619531

  17. A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

    NASA Astrophysics Data System (ADS)

    Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

    2007-09-01

    Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

  18. Intratumoral iron oxide nanoparticle hyperthermia and radiation cancer treatment

    NASA Astrophysics Data System (ADS)

    Hoopes, P. J.; Strawbridge, R. R.; Gibson, U. J.; Zeng, Q.; Pierce, Z. E.; Savellano, M.; Tate, J. A.; Ogden, J. A.; Baker, I.; Ivkov, R.; Foreman, A. R.

    2007-02-01

    The potential synergism and benefit of combined hyperthermia and radiation for cancer treatment is well established, but has yet to be optimized clinically. Specifically, the delivery of heat via external arrays /applicators or interstitial antennas has not demonstrated the spatial precision or specificity necessary to achieve appropriate a highly positive therapeutic ratio. Recently, antibody directed and possibly even non-antibody directed iron oxide nanoparticle hyperthermia has shown significant promise as a tumor treatment modality. Our studies are designed to determine the effects (safety and efficacy) of iron oxide nanoparticle hyperthermia and external beam radiation in a murine breast cancer model. Methods: MTG-B murine breast cancer cells (1 x 106) were implanted subcutaneous in 7 week-old female C3H/HeJ mice and grown to a treatment size of 150 mm3 +/- 50 mm3. Tumors were then injected locally with iron oxide nanoparticles and heated via an alternating magnetic field (AMF) generator operated at approximately 160 kHz and 400 - 550 Oe. Tumor growth was monitored daily using standard 3-D caliper measurement technique and formula. specific Mouse tumors were heated using a cooled, 36 mm diameter square copper tube induction coil which provided optimal heating in a 1 cm wide region in the center of the coil. Double dextran coated 80 nm iron oxide nanoparticles (Triton Biosystems) were used in all studies. Intra-tumor, peri-tumor and rectal (core body) temperatures were continually measured throughout the treatment period. Results: Preliminary in vivo nanoparticle-AMF hyperthermia (167 KHz and 400 or 550 Oe) studies demonstrated dose responsive cytotoxicity which enhanced the effects of external beam radiation. AMF associated eddy currents resulted in nonspecific temperature increases in exposed tissues which did not contain nanoparticles, however these effects were minor and not injurious to the mice. These studies also suggest that iron oxide nanoparticle

  19. Autoclavable highly cross-linked polyurethane networks in ophthalmology.

    PubMed

    Bruin, P; Meeuwsen, E A; van Andel, M V; Worst, J G; Pennings, A J

    1993-11-01

    Highly cross-linked aliphatic polyurethane networks have been prepared by the bulk step reaction of low molecular weight polyols and hexamethylenediisocyanate (HDI). These polyurethane networks are optically transparent, colourless and autoclavable amorphous glassy thermosets, which are suited for use in ophthalmic applications such as intraocular lenses and keratoprostheses. The properties of these glassy polyurethanes, obtained from the reaction of the low molecular weight polyols triisopropanolamine (TIPA) or tetrakis (2-hydroxypropyl)ethylenediamine (Quadrol) and HDI in stoichiometric proportions, have been investigated in more detail. The glassy Quadrol/HDI-based polyurethane exhibits a reduction in ultimate glass transition temperature from 85 to 48 degrees C by uptake of 1% of water, and good ultimate mechanical properties (tensile strength 80-85 MPa, elongation at break ca 15%, modulus ca 1.5 GPa). IR spectra of these hydrophobic polyurethane networks revealed the absence of an isocyanate absorption, indicating that all isocyanates, apparently, had reacted during the cross-linking reaction. The biocompatibility could be increased by grafting tethered polyacrylamide chains onto the surface during network formation. These transparent cross-linked polyurethanes did not transmit UV light up to 400 nm, by incorporation of a small amount of the UV absorbing chromophore Coumarin 102, and could be sterilized simply by autoclaving. They were implanted in rabbit eyes, either in the form of small circular disks or in the form of a keratoprosthesis (artificial cornea). It was shown that the material was well tolerated by the rabbit eyes. Serious opacification of the cornea, a direct result of an adverse reaction to the implant, was never seen. Even 1 yr after implantation of a polyurethane keratoprosthesis the eye was still 'quiet'. PMID:7508760

  20. Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

    NASA Technical Reports Server (NTRS)

    Panek, John

    2010-01-01

    Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.

  1. Cross-linking of Newcastle disease virus (NDV) proteins.

    PubMed

    Nagai, Y; Yoshida, T; Hamaguchi, M; Iinuma, M; Maeno, K; Matsumoto, T

    1978-01-01

    The proxomity and spatial relationships of the structural proteins of Newcastle disease virus (NDV) were studied by chemical cross-linking with a series of imidoesters. When the virions were reacted by the cross-linker with a distance 6.1A or longer between the functional groups and analyzed by polyacrylamide gel electrophoresis, remarkable changes were observed in the migration patterns of the viral proteins. The most striking one was the extensive decrease in the intensity of the M protein band, and although not so strikingly, glycoprotein and nucleocapsid protein bands were reduced significantly. Instead, several protein complexes appeared at and near the top of the gels. The protein complexes formed by a reversible cross-linker, dimethyl-3,3'-dithiobispropionimidate (DTBP), were analyzed by two dimensional electrophoresis; the complexes on the first-dimension cylindrical gels were cleaved by reduction with 2-mercaptoethanol and electrophoresed laterally on the second-dimension slab gels. The results indicated that homodimers of glycoprotein, nucleocapsid protein and M protein were generated under the condition of the most gentle cross-linking employed. At the same time, however, trimer and higher homopolymers of M protein were already detectable. Under the more extensive conditions, the bulk of M protein was cross-linked to form a large protein complex with very high molecular weight. Further, small but significant amounts of glycoprotein and nucleocapsid protein were always detected in this complex. These results suggest that M protein may be present in the virion in close enough proximity to interact with each other and may further have some interactions with glycoprotein and nucleocapsid protein. On the basis of these findings possible roles of M protein in virus assembly were discussed.

  2. Newer protocols and future in collagen cross-linking

    PubMed Central

    Cummings, Arthur B; McQuaid, Rebecca; Mrochen, Michael

    2013-01-01

    Corneal Cross-Linking (CXL) is an established surgical procedure for the treatment of corneal disorders such as corneal ectasia and keratoconus. This method of treatment stabilises the corneal structure and increases rigidity, reducing the requirement for corneal transplantation. Since its development, many scientific studies have been conducted to investigate ways of improving the procedure. Biomechanical stability of the cornea after exposure to UV-A light, and the effect of shortening procedure time has been some of the many topics explored PMID:23925329

  3. LET dependence of DNA-protein cross-links

    SciTech Connect

    Blakely, E.A.; Chang, P.Y.; Bjornstad, K.A.

    1995-08-01

    We have preliminary data indicating a fluence-dependent yield of particle-induced protein cross-links (DPC`s) with a dependency on LET and particle residual energy. Our data indicate that the DPC yield for hamster fibroblasts in vitro irradiated at 32 keV/{mu}m is similar to that reported for hamster cells irradiated with cobalt-60 gamma rays. At 100-120 keV/{mu}m there is some evidence for an enhanced DPC yield with increasing particle fluence, but there are differences in the yields that are dependent on particle track structure.

  4. Curcumin Attenuates Iron Accumulation and Oxidative Stress in the Liver and Spleen of Chronic Iron-Overloaded Rats

    PubMed Central

    Badria, Farid A.; Ibrahim, Ahmed S.; Badria, Adel F.; Elmarakby, Ahmed A.

    2015-01-01

    Objectives Iron overload is now recognized as a health problem in industrialized countries, as excessive iron is highly toxic for liver and spleen. The potential use of curcumin as an iron chelator has not been clearly identified experimentally in iron overload condition. Here, we evaluate the efficacy of curcumin to alleviate iron overload-induced hepatic and splenic abnormalities and to gain insight into the underlying mechanisms. Design and Methods Three groups of male adult rats were treated as follows: control rats, rats treated with iron in a drinking water for 2 months followed by either vehicle or curcumin treatment for 2 more months. Thereafter, we studied the effects of curcumin on iron overload-induced lipid peroxidation and anti-oxidant depletion. Results Treatment of iron-overloaded rats with curcumin resulted in marked decreases in iron accumulation within liver and spleen. Iron-overloaded rats had significant increases in malonyldialdehyde (MDA), a marker of lipid peroxidation and nitric oxide (NO) in liver and spleen when compared to control group. The effects of iron overload on lipid peroxidation and NO levels were significantly reduced by the intervention treatment with curcumin (P<0.05). Furthermore, the endogenous anti-oxidant activities/levels in liver and spleen were also significantly decreased in chronic iron overload and administration of curcumin restored the decrease in the hepatic and splenic antioxidant activities/levels. Conclusion Our study suggests that curcumin may represent a new horizon in managing iron overload-induced toxicity as well as in pathological diseases characterized by hepatic iron accumulation such as thalassemia, sickle cell anemia, and myelodysplastic syndromes possibly via iron chelation, reduced oxidative stress derived lipid peroxidation and improving the body endogenous antioxidant defense mechanism. PMID:26230491

  5. Radiation induced chemical activity at iron and copper oxide surfaces

    NASA Astrophysics Data System (ADS)

    Reiff, Sarah C.

    The radiolysis of three iron oxides, two copper oxides, and aluminum oxide with varying amounts of water were performed using gamma-rays and 5 MeV 4He ions. The adsorbed water on the surfaces was characterized using temperature programmed desorption and diffuse reflectance infrared spectroscopy, which indicated that all of the oxides had chemisorbed water on the surface. Physisorbed water was observed on the Fe2O 3 and Al2O3 surfaces as well. Molecular hydrogen was produced from adsorbed water only on Fe2O3 and Al 2O3, while the other compounds did not show any hydrogen production due to the low amounts of water on the surfaces. Slurries of varying amounts of water were also examined for hydrogen production, and they showed yields that were greater than the yield for bulk water. However, the yields of hydrogen from the copper compounds were much lower than those of the iron suggesting that the copper oxides are relatively inert to radiation induced damage to nearby water. X-ray diffraction measurements did not show any indication of changes to the bulk crystal structure due to radiolysis for any of the oxides. The surfaces of the oxides were analyzed using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). For the iron samples, FeO and Fe3O4, Raman spectroscopy revealed areas of Fe2O3 had formed following irradiation with He ions. XPS indicated the formation of a new oxygen species on the iron oxide surfaces. Raman spectroscopy of the copper oxides did not reveal any changes in the surface composition, however, XPS measurements showed a decrease in the amount of OH groups on the surface of Cu2O, while for the CuO samples the amount of OH groups were found to increase following radiolysis. Pristine Al2O3 showed the presence of a surface oxyhydroxide layer which was observed to decrease following radiolysis, consistent with the formation of molecular hydrogen.

  6. Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

    PubMed

    Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

    2015-01-01

    Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

  7. Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; May, C. E.

    1983-01-01

    The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

  8. Iron aluminide alloy container for solid oxide fuel cells

    DOEpatents

    Judkins, Roddie Reagan; Singh, Prabhakar; Sikka, Vinod Kumar

    2000-01-01

    A container for fuel cells is made from an iron aluminide alloy. The container alloy preferably includes from about 13 to about 22 weight percent Al, from about 2 to about 8 weight percent Cr, from about 0.1 to about 4 weight percent M selected from Zr and Hf, from about 0.005 to about 0.5 weight percent B or from about 0.001 to about 1 weight percent C, and the balance Fe and incidental impurities. The iron aluminide container alloy is extremely resistant to corrosion and metal loss when exposed to dual reducing and oxidizing atmospheres at elevated temperatures. The alloy is particularly useful for containment vessels for solid oxide fuel cells, as a replacement for stainless steel alloys which are currently used.

  9. Promising iron oxide-based magnetic nanoparticles in biomedical engineering.

    PubMed

    Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Vo, Toi Van; Lee, Beom-Jin

    2012-12-01

    For the past few decades biomedical engineering has imprinted its significant impact on the map of science through its wide applications on many other fields. An important example obviously proving this fact is the versatile application of magnetic nanoparticles in theranostics. Due to preferable properties such as biocompatibility, non-toxicity compared to other metal derivations, iron oxide-based magnetic nanoparticles was chosen to be addressed in this review. Aim of this review is to give the readers a whole working window of these magnetic nanoparticles in the current context of science. Thus, preparation of magnetic iron oxide nanoparticles with the so-far techniques, methods of characterizing the nanoparticles as well as their most recent biomedical applications will be stated.

  10. Dendronized iron oxide colloids for imaging the sentinel lymph node

    NASA Astrophysics Data System (ADS)

    Jouhannaud, J.; Garofalo, A.; Felder-Flesch, D.; Pourroy, G.

    2015-03-01

    Various methods have been used in medicine for more than one century to explore the lymphatic system. Radioactive colloids (RuS labelled with 99mTc) or/and Vital Blue dye are injected around the primary tumour and detected by means of nuclear probe or visual colour inspection respectively. The simultaneous clinical use of both markers (dye and radionuclide) improves the sensitivity of detection close to 100%. Superparamagnetic iron oxides (SPIOs) are currently receiving much attention as strong T2 weighted magnetic resonance imaging contrast agents that can be potentially used for preoperative localization of sentinel nodes, but also for peroperative detection of sentinel node using hand-held probes. In that context, we present the elaboration of dendronized iron oxide nanoparticles elaborated at the Institute of Physics and Chemistry of Materials of Strasbourg.

  11. Identification of iron oxide and hydroxide in soil clays

    NASA Astrophysics Data System (ADS)

    Taneja, S. P.; Raj, D.

    1993-04-01

    Clay fractions of soils collected at different depths from the foothills of Karbi Anglong, Assam (India), have been analysed by Mössbauer spectroscopy. Mössbauer data, recorded at room and liquid nitrogen temperatures, show the presence of iron oxide (α-Fe 2O 3, hematite) and iron oxyhydroxide (α-FeOOH, goethite) in the form of fine particles/Al-substituted. All samples exhibited strong superparamagnetism, characteristic of the fine size of the oxide particles and the effect of aluminum substitution. Both hematite and goethite are present in the lower horizon while only goethite occurs in the upper horizon. In addition, silicate clay minerals e.g. kaolinite and illite are also identified.

  12. Reflection spectra and magnetochemistry of iron oxides and natural surfaces

    NASA Technical Reports Server (NTRS)

    Wasilewski, P.

    1978-01-01

    The magnetic properties and spectral characteristics of iron oxides are distinctive. Diagnostic features in reflectance spectra (0.5 to 2.4 micron) for alpha Fe2O3, gamma Fe2O3, and FeOOH include location of Fe3(+) absorption features, intensity ratios at various wavelengths, and the curve shape between 1.2 micron and 2.4 micron. The reflection spectrum of natural rock surfaces are seldom those of the bulk rock because of weathering effects. Coatings are found to be dominated by iron oxides and clay. A simple macroscopic model of rock spectra (based on concepts of stains and coatings) is considered adequate for interpretation of LANDSAT data. The magnetic properties of materials associated with specific spectral types and systematic changes in both spectra and magnetic properties are considered.

  13. Biosynthesis of nitric oxide activates iron regulatory factor in macrophages.

    PubMed

    Drapier, J C; Hirling, H; Wietzerbin, J; Kaldy, P; Kühn, L C

    1993-09-01

    Biosynthesis of nitric oxide (NO) from L-arginine modulates activity of iron-dependent enzymes, including mitochondrial acontiase, an [Fe-S] protein. We examined the effect of NO on the activity of iron regulatory factor (IRF), a cytoplasmic protein which modulates both ferritin mRNA translation and transferrin receptor mRNA stability by binding to specific mRNA sequences called iron responsive elements (IREs). Murine macrophages were activated with interferon-gamma and lipopolysaccharide to induce NO synthase activity and cultured in the presence or absence of NG-substituted analogues of L-arginine which served as selective inhibitors of NO synthesis. Measurement of the nitrite concentration in the culture medium was taken as an index of NO production. Mitochondria-free cytosols were then prepared and aconitase activity as well as IRE binding activity and induction of IRE binding activity were correlated and depended on NO synthesis after IFN-gamma and/or LPS stimulation. Authentic NO gas as well as the NO-generating compound 3-morpholinosydnonimine (SIN-1) also conversely modulated aconitase and IRE binding activities of purified recombinant IRF. These results provide evidence that endogenously produced NO may modulate the post-transcriptional regulation of genes involved in iron homeostasis and support the hypothesis that the [Fe-S] cluster of IRF mediates iron-dependent regulation. PMID:7504626

  14. One-step electrospinning of cross-linked chitosan fibers.

    PubMed

    Schiffman, Jessica D; Schauer, Caroline L

    2007-09-01

    Chitin is a nitrogen-rich polysaccharide that is abundant in crustaceans, mollusks, insects, and fungi and is the second most abundant organic material found in nature next to cellulose. Chitosan, the N-deacetylated derivative of chitin, is environmentally friendly, nontoxic, biodegradable, and antibacterial. Fibrous mats are typically used in industries for filter media, catalysis, and sensors. Decreasing fiber diameters within these mats causes many beneficial effects such as increased specific surface area to volume ratios. When the intrinsically beneficial effects of chitosan are combined with the enhanced properties of nanofibrous mats, applications arise in a wide range of fields, including medical, packaging, agricultural, and automotive. This is particularly important as innovative technologies that focus around bio-based materials are currently of high urgency, as they can decrease dependencies on fossil fuels. We have demonstrated that Schiff base cross-linked chitosan fibrous mats can be produced utilizing a one-step electrospinning process that is 25 times faster and, therefore, more economical than a previously reported two-step vapor-cross-linking method. These fibrous mats are insoluble in acidic, basic, and aqueous solutions for 72 h. Additionally, this improved production method results in a decreased average fiber diameter, which measures 128 +/- 40 nm. Chemical and structural analyses were conducted utilizing Fourier transform infrared spectroscopy, solubility studies, and scanning electron microscopy. PMID:17696400

  15. Collagen Cross-Linking: Current Status and Future Directions

    PubMed Central

    Hovakimyan, Marine; Guthoff, Rudolf F.; Stachs, Oliver

    2012-01-01

    Collagen cross-linking (CXL) using UVA light and riboflavin (vitamin B2) was introduced as a clinical application to stabilize the cornea by inducing cross-links within and between collagen fibers. CXL has been investigated extensively and has been shown clinically to arrest the progression of keratoconic or post-LASIK ectasia. With its minimal cost, simplicity, and proven positive clinical outcome, CXL can be regarded as a useful approach to reduce the number of penetrating keratoplasties performed. Small case series have also indicated that CXL is beneficial in corneal edema by reducing stromal swelling behavior and in keratitis by inhibiting pathogen growth. Despite these encouraging results, CXL remains a relatively new method that is potentially associated with complications. Aspects such as side effects and recurrence rates have still to be elucidated. In light of the growing interest in CXL, our paper summarizes present knowledge about this promising approach. We have intentionally endeavored to include the more relevant studies from the recent literature to provide an overview of the current status of CXL. PMID:22288005

  16. Covalently Cross-Linked Arabinoxylans Films for Debaryomyces hansenii Entrapment.

    PubMed

    González-Estrada, Ramsés; Calderón-Santoyo, Montserrat; Carvajal-Millan, Elizabeth; Ascencio Valle, Felipe de Jesús; Ragazzo-Sánchez, Juan Arturo; Brown-Bojorquez, Francisco; Rascón-Chu, Agustín

    2015-01-01

    In the present study, wheat water extractable arabinoxylans (WEAX) were isolated and characterized, and their capability to form covalently cross-linked films in presence of Debaryomyces hansenii was evaluated. WEAX presented an arabinose to xylose ratio of 0.60, a ferulic acid and diferulic acid content of 2.1 and 0.04 µg∙mg(-1) WEAX, respectively and a Fourier Transform Infra-Red (FT-IR) spectrum typical of WEAX. The intrinsic viscosity and viscosimetric molecular weight values for WEAX were 3.6 dL∙g(-1) and 440 kDa, respectively. The gelation of WEAX (1% w/v) with and without D. hansenii (1 × 10(7) CFU∙cm(-2)) was rheologically investigated by small amplitude oscillatory shear. The entrapment of D. hansenii decreased gel elasticity from 1.4 to 0.3 Pa, probably by affecting the physical interactions between WEAX chains. Covalently cross-linked WEAX films containing D. hansenii were prepared by casting. Scanning electron microscopy images show that WEAX films containing D. hansenii were porous and consisted of granular-like and fibre microstructures. Average tensile strength, elongation at break and Young's modulus values dropped when D. hansenii was present in the film. Covalently cross-lined WEAX containing D. hansenii could be a suitable as a functional entrapping film. PMID:26102070

  17. Optimization model for UV-Riboflavin corneal cross-linking

    NASA Astrophysics Data System (ADS)

    Schumacher, S.; Wernli, J.; Scherrer, S.; Bueehler, M.; Seiler, T.; Mrochen, M.

    2011-03-01

    Nowadays UV-cross-linking is an established method for the treatment of keraectasia. Currently a standardized protocol is used for the cross-linking treatment. We will now present a theoretical model which predicts the number of induced crosslinks in the corneal tissue, in dependence of the Riboflavin concentration, the radiation intensity, the pre-treatment time and the treatment time. The model is developed by merging the difussion equation, the equation for the light distribution in dependence on the absorbers in the tissue and a rate equation for the polymerization process. A higher concentration of Riboflavin solution as well as a higher irradiation intensity will increase the number of induced crosslinks. However, performed stress-strain experiments which support the model showed that higher Riboflavin concentrations (> 0.125%) do not result in a further increase in stability of the corneal tissue. This is caused by the inhomogeneous distribution of induced crosslinks throughout the cornea due to the uneven absorption of the UV-light. The new model offers the possibility to optimize the treatment individually for every patient depending on their corneal thickness in terms of efficiency, saftey and treatment time.

  18. Thermoset-cross-linked lignocellulose: a moldable plant biomass.

    PubMed

    Karumuri, Sriharsha; Hiziroglu, Salim; Kalkan, A Kaan

    2015-04-01

    The present work demonstrates a high biomass content (i.e., up to 90% by weight) and moldable material by controlled covalent cross-linking of lignocellulosic particles by a thermoset through epoxide-hydroxyl reactions. As an example for lignocellulosic biomass, Eastern redcedar was employed. Using scanning fluorescence microscopy and vibrational spectroscopy, macroscopic to molecular scale interactions of the thermoset with the lignocellulose have been revealed. Impregnation of the polymer resin into the biomass cellular network by capillary action as well as applied pressure results in a self-organizing structure in the form of thermoset microrods in a matrix of lignocellulose. We also infer permeation of the thermoset into the cell walls from the reaction of epoxides with the hydroxyls of the lignin. Compression tests reveal, at 30% thermoset content, thermoset-cross-linked lignocellulose has superior mechanical properties over a commercial wood plastic composite while comparable stiffness and strength to bulk epoxy and wood, respectively. The failure mechanism is understood to be crack propagation along the particle-thermoset interface and/or interparticle thermoset network. PMID:25734539

  19. Effects of processing conditions on the reliability of cross-linked polyethylene cable insulation. Progress report

    SciTech Connect

    Phillips, P.J.

    1981-03-01

    Crystallization and morphology were investigated in cross-linked PE. /sup 13/C NMR was used to quantify the cross-links. Production of cable is being studied. Dielectric constant and loss of cross-linked PE are being measured. (DLC)

  20. 21 CFR 177.2710 - Styrene-divinylbenzene resins, cross-linked.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Styrene-divinylbenzene resins, cross-linked. 177... resins, cross-linked. Styrene-divinylbenzene cross-linked copolymer resins may be safely used as articles... conditions: (a) The resins are produced by the copolymerization of styrene with divinylbenzene. (b)...

  1. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes.

    PubMed

    Leitner, Alexander; Joachimiak, Lukasz A; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-07-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  2. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes

    PubMed Central

    Leitner, Alexander; Joachimiak, Lukasz A.; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-01-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  3. 21 CFR 177.2710 - Styrene-divinylbenzene resins, cross-linked.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-divinylbenzene resins, cross-linked. 177... resins, cross-linked. Styrene-divinylbenzene cross-linked copolymer resins may be safely used as articles... conditions: (a) The resins are produced by the copolymerization of styrene with divinylbenzene. (b)...

  4. The role of iron redox state in the genotoxicity of ultrafine superparamagnetic iron oxide nanoparticles.

    PubMed

    Singh, Neenu; Jenkins, Gareth J S; Nelson, Bryant C; Marquis, Bryce J; Maffeis, Thierry G G; Brown, Andy P; Williams, Paul M; Wright, Chris J; Doak, Shareen H

    2012-01-01

    Ultrafine superparamagnetic iron oxide nanoparticles (USPION) hold great potential for revolutionising biomedical applications such as MRI, localised hyperthermia, and targeted drug delivery. Though evidence is increasing regarding the influence of nanoparticle physico-chemical features on toxicity, data however, is lacking that assesses a range of such characteristics in parallel. We show that iron redox state, a subtle though important physico-chemical feature of USPION, dramatically modifies the cellular uptake of these nanoparticles and influences their induction of DNA damage. Surface chemistry was also found to have an impact and evidence to support a potential mechanism of oxidative DNA damage behind the observed responses has been demonstrated. As human exposure to ferrofluids is predicted to increase through nanomedicine based therapeutics, these findings are important in guiding the fabrication of USPION to ensure they have characteristics that support biocompatibility. PMID:22027595

  5. Reducing arsenic accumulation in rice grain through iron oxide amendment.

    PubMed

    Farrow, Eric M; Wang, Jianmin; Burken, Joel G; Shi, Honglan; Yan, Wengui; Yang, John; Hua, Bin; Deng, Baolin

    2015-08-01

    Effects of soil-arsenic (As), phosphorus and iron oxide on As accumulation in rice grain were investigated. Cultivars that have significantly different sensitivity to As, straighthead-resistant Zhe 733 and straighthead-susceptible Cocodrie, were used to represent different cultivar varieties. The grain accumulation of other elements of concern, selenium (Se), molybdenum (Mo), and cadmium (Cd) was also monitored. Results demonstrated that high soil-As not only resulted in high grain-As, but could also result in high grain-Se, and Zhe 733 had significantly less grain-As than Cocodrie did. However, soil-As did not impact grain-Mo and Cd. Among all elements monitored, iron oxide amendment significantly reduced grain-As for both cultivars, while the phosphate application only reduced grain-Se for Zhe 733. Results also indicated that cultivar type significantly impacted grain accumulation of all monitored trace elements. Therefore, applying iron oxide to As-contaminated land, in addition to choosing appropriate rice cultivar, can effectively reduce the grain accumulation of As. PMID:25910688

  6. The preparation and characterization of linear and cross-linked poly(fluorenyl)

    SciTech Connect

    Hagaman, E.W.; Lee, S.K.

    1997-03-01

    Retrogressive reactions in coal processing are that class of reactions that lead to the formation of high molecular weight materials that are more intractable than those present in the coal prior to processing. This outcome almost always is regarded as deleterious. The present work focuses on the characterization of the acid-catalyzed polymerization of benzylic fluorides, and in particular the synthesis of poly(fluorenyl), as an example of the type of chemistry that may occur in the cross-linked organic matrix of coals when in contact with strong acids. Solution and solid state {sup 13}C NMR spectroscopy was used to characterize the soluble and insoluble polymers. The change in the value of the fraction of aromatic carbon that is protonated is the criterion used to monitor the extent of cross-linking in these polymer preparations. Benzylic fluorides are sensitive substances, prone to further reaction via acid catalyzed heterolytic scission of the C-F bond. The electron deficient reactive intermediate formed in this reaction undergoes electrophilic aromatic substitution. This reaction can be started with catalytic traces of acid and is self-sustaining as HF is generated in equivalent concentrations as the reaction proceeds. The relevance of this naturally non-occurring functional group in coal processing stems from the similar reaction pathway followed by both benzylic fluorides and benzylic alcohols. In the coal matrix, the operation of two exogenous processes--air oxidation and strong acid treatment of the coal (demineralization) creates a situation in which the polymerization discussed herein may occur in the coal. In addition to the polymerization reactions that produce poly(fluorenyl), the subsequent cross-linking of the linear polymer is also reported. In subsequent work, similar chemistry will be applied to soluble lignin as a model more similar to low rank coals.

  7. Electron uptake by iron-oxidizing phototrophic bacteria

    SciTech Connect

    Bose, A; Gardel, EJ; Vidoudez, C; Parra, EA; Girguis, PR

    2014-02-26

    Oxidation-reduction reactions underlie energy generation in nearly all life forms. Although most organisms use soluble oxidants and reductants, some microbes can access solid-phase materials as electron-acceptors or -donors via extracellular electron transfer. Many studies have focused on the reduction of solid-phase oxidants. Far less is known about electron uptake via microbial extracellular electron transfer, and almost nothing is known about the associated mechanisms. Here we show that the iron-oxidizing photoautotroph Rhodopseudomonas palustris TIE-1 accepts electrons from a poised electrode, with carbon dioxide as the sole carbon source/electron acceptor. Both electron uptake and ruBisCo form I expression are stimulated by light. Electron uptake also occurs in the dark, uncoupled from photosynthesis. Notably, the pioABC operon, which encodes a protein system essential for photoautotrophic growth by ferrous iron oxidation, influences electron uptake. These data reveal a previously unknown metabolic versatility of photoferrotrophs to use extracellular electron transfer for electron uptake.

  8. Iron requirement for Mn(II) oxidation by Leptothrix discophora SS-1.

    PubMed

    El Gheriany, Iman A; Bocioaga, Daniela; Hay, Anthony G; Ghiorse, William C; Shuler, Michael L; Lion, Leonard W

    2009-03-01

    A common form of biocatalysis of Mn(II) oxidation results in the formation of biogenic Mn(III, IV) oxides and is a key reaction in the geochemical cycling of Mn. In this study, we grew the model Mn(II)-oxidizing bacterium Leptothrix discophora SS-1 in media with limited iron (0.1 microM iron/5.8 mM pyruvate) and sufficient iron (0.2 microM iron/5.8 mM pyruvate). The influence of iron on the rate of extracellular Mn(II) oxidation was evaluated. Cultures in which cell growth was limited by iron exhibited reduced abilities to oxidize Mn(II) compared to cultures in medium with sufficient iron. While the extracellular Mn(II)-oxidizing factor (MOF) is thought to be a putative multicopper oxidase, Mn(II) oxidation in the presence of zero added Cu(II) was detected and the decrease in the observed Mn(II) oxidation rate in iron-limited cultures was not relieved when the medium was supplemented with Cu(II). The decline of Mn(II) oxidation under iron-limited conditions was not accompanied by siderophore production and is unlikely to be an artifact of siderophore complex formation with Mn(III). The temporal variations in mofA gene transcript levels under conditions of limited and abundant iron were similar, indicating that iron limitation did not interfere with the transcription of the mofA gene. Our quantitative PCR results provide a step forward in understanding the regulation of Mn(II) oxidation. The mechanistic role of iron in Mn(II) oxidation is uncertain; the data are consistent with a direct requirement for iron as a component of the MOF or an indirect effect of iron resulting from the limitation of one of many cellular functions requiring iron. PMID:19114505

  9. Iron Requirement for Mn(II) Oxidation by Leptothrix discophora SS-1▿

    PubMed Central

    El Gheriany, Iman A.; Bocioaga, Daniela; Hay, Anthony G.; Ghiorse, William C.; Shuler, Michael L.; Lion, Leonard W.

    2009-01-01

    A common form of biocatalysis of Mn(II) oxidation results in the formation of biogenic Mn(III, IV) oxides and is a key reaction in the geochemical cycling of Mn. In this study, we grew the model Mn(II)-oxidizing bacterium Leptothrix discophora SS-1 in media with limited iron (0.1 μM iron/5.8 mM pyruvate) and sufficient iron (0.2 μM iron/5.8 mM pyruvate). The influence of iron on the rate of extracellular Mn(II) oxidation was evaluated. Cultures in which cell growth was limited by iron exhibited reduced abilities to oxidize Mn(II) compared to cultures in medium with sufficient iron. While the extracellular Mn(II)-oxidizing factor (MOF) is thought to be a putative multicopper oxidase, Mn(II) oxidation in the presence of zero added Cu(II) was detected and the decrease in the observed Mn(II) oxidation rate in iron-limited cultures was not relieved when the medium was supplemented with Cu(II). The decline of Mn(II) oxidation under iron-limited conditions was not accompanied by siderophore production and is unlikely to be an artifact of siderophore complex formation with Mn(III). The temporal variations in mofA gene transcript levels under conditions of limited and abundant iron were similar, indicating that iron limitation did not interfere with the transcription of the mofA gene. Our quantitative PCR results provide a step forward in understanding the regulation of Mn(II) oxidation. The mechanistic role of iron in Mn(II) oxidation is uncertain; the data are consistent with a direct requirement for iron as a component of the MOF or an indirect effect of iron resulting from the limitation of one of many cellular functions requiring iron. PMID:19114505

  10. Role of nitric oxide in cellular iron metabolism.

    PubMed

    Kim, Sangwon; Ponka, Prem

    2003-03-01

    Iron regulatory proteins (IRP1 and IRP2) control the synthesis of transferrin receptors (TfR) and ferritin by binding to iron-responsive elements (IREs) which are located in the 3' untranslated region (UTR) and the 5' UTR of their respective mRNAs. Cellular iron levels affect binding of IRPs to IREs and consequently expression of TfR and ferritin. Moreover, NO*, a redox species of nitric oxide that interacts primarily with iron, can activate IRP1 RNA-binding activity resulting in an increase in TfR mRNA levels. We have shown that treatment of RAW 264.7 cells (a murine macrophage cell line) with NO+ (nitrosonium ion, which causes S-nitrosylation of thiol groups) resulted in a rapid decrease in RNA-binding of IRP2, followed by IRP2 degradation, and these changes were associated with a decrease in TfR mRNA levels. Moreover, we demonstrated that stimulation of RAW 264.7 cells with lipopolysaccharide (LPS) and interferon-gamma (IFN-gamma) increased IRP1 binding activity, whereas RNA-binding of IRP2 decreased and was followed by a degradation of this protein. Furthermore, the decrease of IRP2 binding/protein levels was associated with a decrease in TfR mRNA levels in LPS/IFN-gamma-treated cells, and these changes were prevented by inhibitors of inducible nitric oxide synthase. These results suggest that NO+-mediated degradation of IRP2 plays a major role in iron metabolism during inflammation.

  11. Evaluation of Characterization Techniques for Iron Pipe Corrosion Products and Iron Oxide Thin Films

    SciTech Connect

    Borch, Thomas; Camper, Anne K.; Biederman, Joel A.; Butterfield, Phillip; Gerlach, Robin; Amonette, James E.

    2008-10-01

    A common problem faced by drinking water studies is that of properly characterizing the corrosion products (CP) in iron pipescor synthetic Fe (hydr)oxides used to simulate the iron pipe used in municipal drinking-water systems. The present work compares the relative applicability of a suite of imaging and analytical techniques for the characterization of CPs and synthetic Fe oxide thin films and provide an overview of the type of data that each instrument can provide as well as their limitations to help researchers and consultants choose the best technique for a given task. Crushed CP from a water distribution system and synthetic Fe oxide thin films formed on glass surfaces were chosen as test samples for this evaluation. The CP and synthetic Fe oxide thin films were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray powder diffractometry (XRD), grazing incident diffractometry (GID), transmission electron microscopy (TEM), selected area electron diffraction, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared, Mössbauer spectroscopy, Brunauer-Emmett-Teller N2 adsorption and Fe concentration was determined by the ferrozine method. XRD and GID were found to be the most suitable techniques for identification of the mineralogical composition of CP and synthetic Fe oxide thin films, respectively. AFM and a combined ToF-SIMS-AFM approach proved excellent for roughness and depth profiling analysis of synthetic Fe oxide thin films, respectively. Corrosion products were difficult to study by AFM due to their surface roughness, while synthetic Fe oxide thin films resisted most spectroscopic methods due to their limited thickness (118 nm). XPS analysis is not recommended for mixtures of Fe (hydr)oxides due to their spectral similarities. SEM and TEM provided great detail on mineralogical morphology.

  12. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  13. Relationship between gravimetric wear and particle generation in hip simulators: conventional compared with cross-linked polyethylene.

    PubMed

    Ries, M D; Scott, M L; Jani, S

    2001-01-01

    Hip-simulator studies have shown reduced gravimetric wear rates for inert-gas gamma-irradiated ultra-high molecular weight polyethylene when compared with conventional ethylene-oxide-sterilized ultra-high molecular weight polyethylene. Analysis shows a greater number of particles generated from inert-gas gamma-irradiated ultra-high molecular weight polyethylene. This study was undertaken to examine particle-generation rates of polyethylene with different levels of cross-linking and to correlate them with gravimetric wear data. Particle-generation rates did not correlate with gravimetric wear rates. Particle analysis should be performed to predict the in vivo behavior of bearing surface materials. Cross-linked ultra-high molecular weight polyethylene subjected to 10 Mrad (100,000 Gy) of gamma irradiation generated significantly fewer particles than ethylene-oxide-sterilized ultra-high molecular weight polyethylene; it also demonstrated a 96% reduction in the volume of particles.

  14. New Insight into Microbial Iron Oxidation as Revealed by the Proteomic Profile of an Obligate Iron-Oxidizing Chemolithoautotroph

    PubMed Central

    Emerson, David; Sylvan, Jason B.; Orcutt, Beth N.; Jacobson Meyers, Myrna E.; Ramírez, Gustavo A.; Zhong, John D.; Edwards, Katrina J.

    2015-01-01

    Microaerophilic, neutrophilic, iron-oxidizing bacteria (FeOB) grow via the oxidation of reduced Fe(II) at or near neutral pH, in the presence of oxygen, making them relevant in numerous environments with elevated Fe(II) concentrations. However, the biochemical mechanisms for Fe(II) oxidation by these neutrophilic FeOB are unknown, and genetic markers for this process are unavailable. In the ocean, microaerophilic microorganisms in the genus Mariprofundus of the class Zetaproteobacteria are the only organisms known to chemolithoautotrophically oxidize Fe and concurrently biomineralize it in the form of twisted stalks of iron oxyhydroxides. The aim of this study was to identify highly expressed proteins associated with the electron transport chain of microaerophilic, neutrophilic FeOB. To this end, Mariprofundus ferrooxydans PV-1 was cultivated, and its proteins were extracted, assayed for redox activity, and analyzed via liquid chromatography-tandem mass spectrometry for identification of peptides. The results indicate that a cytochrome c4, cbb3-type cytochrome oxidase subunits, and an outer membrane cytochrome c were among the most highly expressed proteins and suggest an involvement in the process of aerobic, neutrophilic bacterial Fe oxidation. Proteins associated with alternative complex III, phosphate transport, carbon fixation, and biofilm formation were abundant, consistent with the lifestyle of Mariprofundus. PMID:26092463

  15. Nitric oxide-mediated modulation of iron regulatory proteins: implication for cellular iron homeostasis.

    PubMed

    Kim, Sangwon; Ponka, Prem

    2002-01-01

    Iron regulatory proteins (IRP1 and IRP2) control the synthesis of transferrin receptors (TfR) and ferritin by binding to iron-responsive elements (IREs) that are located in the 3' untranslated region (UTR) and the 5' UTR of their respective mRNAs. Cellular iron levels affect binding of IRPs to IREs and consequently expression of TfR and ferritin. Moreover, NO(.), a redox species of nitric oxide that interacts primarily with iron, can activate IRP1 RNA-binding activity resulting in an increase in TfR mRNA levels and a decrease in ferritin synthesis. We have shown that treatment of RAW 264.7 cells (a murine macrophage cell line) with NO(+) (nitrosonium ion, which causes S-nitrosylation of thiol groups) resulted in a rapid decrease in RNA-binding of IRP2, followed by IRP2 degradation, and these changes were associated with a decrease in TfR mRNA levels and a dramatic increase in ferritin synthesis. Moreover, we demonstrated that stimulation of RAW 264.7 cells with lipopolysaccharide (LPS) and interferon-gamma (IFN-gamma) increased IRP1 binding activity, whereas RNA-binding of IRP2 decreased and was followed by a degradation of this protein. Furthermore, the decrease of IRP2 binding/protein levels was associated with a decrease in TfR mRNA levels and an increase in ferritin synthesis in LPS/IFN-gamma-treated cells, and these changes were prevented by inhibitors of inducible nitric oxide synthase. These results suggest that NO(+)-mediated degradation of IRP2 plays a major role in iron metabolism during inflammation.

  16. Synthesis of superparamagnetic iron(III) oxide nanowires in double-walled carbon nanotubes.

    PubMed

    Tîlmaciu, Carmen-Mihaela; Soula, Brigitte; Galibert, Anne-Marie; Lukanov, Petar; Datas, Lucien; González, Jesús; Barquín, Luis Fernández; Rodríguez Fernández, Jesús; González-Jiménez, Fernando; Jorge, Jose; Flahaut, Emmanuel

    2009-11-21

    The synthesis and characterization of superparamagnetic iron(iii) oxide nanowires confined within double-walled carbon nanotubes by capillary filling with a melted precursor (iron iodide) followed by thermal treatment is reported for the first time.

  17. Green rust and iron oxide formation influences metolachlor dechlorination during zerovalent iron treatment.

    PubMed

    Satapanajaru, Tunlawit; Shea, Patrick J; Comfort, Steve D; Roh, Yul

    2003-11-15

    Electron transfer from zerovalent iron (Fe0) to targeted contaminants is affected by initial Fe0 composition, the oxides formed during corrosion, and surrounding electrolytes. We previously observed enhanced metolachlor destruction by Fe0 when iron or aluminum salts were present in the aqueous matrix and Eh/pH conditions favored formation of green rusts. To understand these enhanced destruction rates, we characterized changes in Fe0 composition during treatment of metolachlor with and without iron and aluminum salts. Raman microspectroscopy and X-ray diffraction (XRD) indicated that the iron source was initially coated with a thin layer of magnetite (Fe3O4), maghemite (gamma-Fe2O3), and wüstite (FeO). Time-resolved analysis indicated that akaganeite (beta-FeOOH) was the dominant oxide formed during Fe0 treatment of metolachlor. Goethite (alpha-FeOOH) and some lepidocrocite (gamma-FeOOH) formed when Al2(SO4)3 was present, while goethite and magnetite (Fe3O4) were identified in Fe0 treatments containing FeSO4. Although conditions favoring formation of sulfate green rust (GR(II); Fe6(OH)12SO4) facilitated Fe0-mediated dechlorination of metolachlor, only adsorption was observed when GR(II) was synthesized (without Fe0) in the presence of metolachlor and Eh/pH changed to favor Fe(III)oxyhydroxide or magnetite formation. In contrast, dechlorination occurred when magnetite or natural goethite was amended with Fe(II) (as FeSO4) at pH 8 and continued as long as additional Fe(II) was provided. While metolachlor was not dechlorinated by GR(II) itself during a 48-h incubation, the GR(II) provided a source of Fe(II) and produced magnetite (and other oxide surfaces) that coordinated Fe(II), which then facilitated dechlorination.

  18. Altering the structure and properties of iron oxide nanoparticles and graphene oxide/iron oxide composites by urea

    NASA Astrophysics Data System (ADS)

    Naghdi, Samira; Rhee, Kyong Yop; Jaleh, Babak; Park, Soo Jin

    2016-02-01

    Iron oxide (Fe2O3) nanoparticles were grown on graphene oxide (GO) using a simple microwave-assisted method. The effects of urea concentration on Fe2O3 nanoparticles and GO/Fe2O3 composite were examined. The as-prepared samples were characterized using X-ray powder diffraction, Raman spectroscopy, and transmission electron microscopy. The Fe2O3 nanoparticles were uniformly developed on GO sheets. The results showed that urea affects both Fe2O3 morphology and particle size. In the absence of urea, the Fe2O3 nanostructures exhibited a rod-like morphology. However, increasing urea concentration altered the morphology and decreased the particle size. The Raman results of GO/Fe2O3 showed that the intensity ratio of D band to G band (ID/IG) was decreased by addition of urea, indicating that urea can preserve the GO sheets during synthesis of the composite from exposing more defects. The surface area and thermal stability of GO/Fe2O3 and Fe2O3 were compared using the Brunauer-Emmett-Teller method and thermal gravimetric analysis, respectively. The results showed that the increased concentration of urea induced a larger surface area with more active sites in the Fe2O3 nanoparticles. However, the increase in urea concentration led to decreased thermal stability of the Fe2O3 nanoparticles. The magnetic properties of Fe2O3 nanoparticles were characterized by a vibrating sample magnetometer and results revealed that the magnetic properties of Fe2O3 nanoparticles are affected by the morphology.

  19. Studies on N-vinylformamide cross-linked copolymers

    NASA Astrophysics Data System (ADS)

    Świder, Joanna; Tąta, Agnieszka; Sokołowska, Katarzyna; Witek, Ewa; Proniewicz, Edyta

    2015-12-01

    Copolymers of N-vinylformamide (NVF) cross-linked with three multifunctional monomers, including divinylbenzene (DVB), ethylene glycol dimethacrylate (EGDMA), and N,N‧-methylenebisacrylamide (MBA) were synthetized by a three-dimensional free radical polymerization in inverse suspension using 2,2‧-azobis(2-methylpropionamide) dihydrochloride (AIBA) as an initiator. Methyl silicon oil was used as the continuous phase during the polymerization processes. Fourier-transform adsorption infrared (FT-IR) spectra revealed the presence of silicone oil traces and suggested that silicone oil strongly interacted with the copolymers surface. Purification procedure allowed to completely remove the silicon oil traces from P(NVF-co-DVB) only. The morphology and the structure of the investigated copolymers were examined by optical microscopy, FT-IR, and FT-Raman (Fourier-transform Raman spectroscopy) methods.

  20. Tough Stretchable Physically-Cross-linked Electrospun Hydrogel Fiber Mats.

    PubMed

    Yang, Yiming; Wang, Chao; Wiener, Clinton G; Hao, Jinkun; Shatas, Sophia; Weiss, R A; Vogt, Bryan D

    2016-09-01

    Nature uses supramolecular interactions and hierarchical structures to produce water-rich materials with combinations of properties that are challenging to obtain in synthetic systems. Here, we demonstrate hierarchical supramolecular hydrogels from electrospun, self-associated copolymers with unprecedented elongation and toughness for high porosity hydrogels. Hydrophobic association of perfluoronated comonomers provides the physical cross-links for these hydrogels based on copolymers of dimethyl acrylamide and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM). Intriguingly, the hydrogel fiber mats show an enhancement in toughness in comparison to compression molded bulk hydrogels. This difference is attributed to the size distribution of the hydrophobic aggregates where narrowing the distribution in the electrospun material enhances the toughness of the hydrogel. These hydrogel fiber mats exhibit extensibility more than double that of the bulk hydrogel and a comparable modulus despite the porosity of the fiber mat leading to >25 wt % increase in water content. PMID:27548013

  1. Conventional Versus Cross-Linked Polyethylene for Total Hip Arthroplasty.

    PubMed

    Surace, Michele F; Monestier, Luca; Vulcano, Ettore; Harwin, Steven F; Cherubino, Paolo

    2015-09-01

    The clinical and radiographic outcomes of 88 patients who underwent primary total hip arthroplasty with either conventional polyethylene or cross-linked polyethylene (XLPE) from the same manufacturer were compared. There were no significant differences between the 2 subpopulations regarding average age, gender, side affected, or prosthetic stem and cup size. The average follow-up was 104 months (range, 55 to 131 months). To the authors' knowledge, this is the longest follow-up for this particular insert. Clinical and radiographic evaluations were performed at 1, 3, 6, and 12 months and then annually. Results showed that XLPE has a significantly greater wear reduction than that of standard polyethylene in primary total hip arthroplasty. At the longest available follow-up for these specific inserts, XLPE proved to be effective in reducing wear. PMID:26375527

  2. Protein cross-linking tools for the construction of nanomaterials.

    PubMed

    Domeradzka, Natalia E; Werten, Marc Wt; Wolf, Frits A de; de Vries, Renko

    2016-06-01

    Across bioengineering there is a need to couple proteins to other proteins, or to peptides. Although traditional chemical conjugations have dominated in the past, more and more highly specific coupling strategies are becoming available that are based on protein engineering. Here we review the use of protein modification approaches such as enzymatic and autocatalytic protein-protein coupling, as well as the use of hetero-dimerizing (or hetero-oligomerizing) modules, applied to the specific case of linking together de novo designed recombinant polypeptides into precisely structured nanomaterials. Such polypeptides are increasingly being investigated for biomedical and other applications. In this review, we describe the protein-engineering based cross-linking strategies that dramatically expand the repertoire of possible molecular structures and, hence, the range of materials that can be produced from them. PMID:26871735

  3. Core cross-linked micelle-based nanoreactors for efficient photocatalysis.

    PubMed

    Zheng, Min; Sun, Zaicheng; Xie, Zhigang; Jing, Xiabin

    2013-11-01

    Stable nanoscale cross-linked polymer micelles containing Ru complexes (Ru-CMs) were prepared from monomethoxy[poly(ethylene glycol)]-block-poly(L-lysine) (MPEG-PLys) and [(bpy)2Ru(fmbpy)](PF6)2 (bpy=bipyridine, fmbpy=5-formy-5'-methyl-2,2'-bipyridine). To stabilize the micelles, bifunctional glutaraldehyde was used as a cross-linker to react with the free amino groups of the PLys block. After that, the Ru-CMs showed very good stability in common solvents. The Ru-CMs showed photocatalytic activity and selectivity in the oxidation of sulfides that were as high as those of the well-known [Ru(bpy)3(PF6)2] complex, because the micelles were swollen in the methanol-sulfide mixture. Moreover, because of the nanoscale size of the particles and their high stability, the Ru-CM photocatalysts can be readily recovered by ultrafiltration and reused without loss of photocatalytic activity. This work highlights the potential of using cross-linked micelles as a platform for developing highly efficient heterogeneous photocatalysts for a number of important organic transformations.

  4. Enzymatically cross-linked alginic-hyaluronic acid composite hydrogels as cell delivery vehicles.

    PubMed

    Ganesh, Nitya; Hanna, Craig; Nair, Shantikumar V; Nair, Lakshmi S

    2013-04-01

    An injectable composite gel was developed from alginic and hyaluronic acid. The enzymatically cross-linked injectable gels were prepared via the oxidative coupling of tyramine modified sodium algiante and sodium hyaluronate in the presence of horse radish peroxidase (HRP) and hydrogen peroxide (H2O2). The composite gels were prepared by mixing equal parts of the two tyraminated polymer solutions in 10U HRP and treating with 1.0% H2O2. The properties of the alginate gels were significantly affected by the addition of hyaluronic acid. The percentage water absorption and storage modulus of the composite gels were found to be lower than the alginate gels. The alginate and composite gels showed lower protein release compared to hyaluronate gels in the absence of hyaluronidase. Even hyaluronate gels showed only approximately 10% protein release after 14 days incubation in phosphate buffer solution. ATDC-5 cells encapsulated in the injectable gels showed high cell viability. The composite gels showed the presence of enlarged spherical cells with significantly higher metabolic activity compared to cells in hyaluronic and alginic acid gels. The results suggest the potential of the composite approach to develop covalently cross-linked hydrogels with tuneable physical, mechanical, and biological properties. PMID:23357799

  5. Enzymatically Cross-linked Alginic-Hyaluronic acid Composite Hydrogels As Cell Delivery Vehicles

    PubMed Central

    Ganesh, Nitya; Hanna, Craig; Nair, Shantikumar V.; Nair, Lakshmi S.

    2013-01-01

    An injectable composite gel was developed from alginic and hyaluronic acid. The ezymatically cross-linked injectable gels were prepared via the oxidative coupling of tyramine modified sodium algiante and sodium hyaluronate in the presence of horse radish peroxidase (HRP) and hydrogen peroxide (H2O2). The composite gels were prepared by mixing equal parts of the two tryaminated polymer solutions in 10U HRP and treating with 1.0% H2O2. The properties of the alginate gels were significanly affected by the addition of hyaluronic acid. The percentage water absorption and storage modulus of the composite gels were found to be lower than the alginate gels. The alginate and composite gels showed lower protein release compared to hyaluronate gels in the absence of hyaluronidase. Even hyaluronate gels showed only approximately 10% protein release after 14 days incubation in phosphate buffer solution. ATDC-5 cells encapsulated in the injectable gels showed high cell viability. The composite gels showed the presence of enlarged spherical cells with significantly higher metabolic activity compared to cells in hyaluronic and alginic acid gels. The results suggest the potential of the composite approach to develop covalently cross-linked hydrogels with tuneable physical, mechanical, and biological properties. PMID:23357799

  6. Using a magnetic field to redirect an oncolytic adenovirus complexed with iron oxide augments gene therapy efficacy.

    PubMed

    Choi, Joung-Woo; Park, Ji Won; Na, Youjin; Jung, Soo-Jung; Hwang, June Kyu; Choi, Dongho; Lee, Kyeong Geun; Yun, Chae-Ok

    2015-10-01

    Adenovirus (Ad) is a widely used vector for cancer gene therapy but its therapeutic efficacy is limited by low coxsackievirus and adenovirus receptor (CAR) expression in tumors and non-specifically targeted infection. Ad infectivity and specificity can be markedly improved by creating Ad-magnetic nanoparticles cluster complexes and directing their migration with an external magnetic field (MGF). We electrostatically complexed GFP-expressing, replication-incompetent Ad (dAd) with PEGylated and cross-linked iron oxide nanoparticles (PCION), generating dAd-PCION complexes. The dAd-PCION showed increased transduction efficiency, independent of CAR expression, in the absence or presence of an MGF. Cancer cell killing and intracellular oncolytic Ad (HmT)-PCION replication significantly increased with MGF exposure. Site-directed, magnetically-targeted delivery of the HmT-PCION elicited significantly greater therapeutic efficacy versus treatment with naked HmT or HmT-PCION without MGF in CAR-negative MCF7 tumors. Immunohistochemical tumor analysis showed increased oncolytic Ad replication in tumors following infection by HmT-PCION using an MGF. Whole-body bioluminescence imaging of tumor-bearing mice showed a 450-fold increased tumor-to-liver ratio for HmT-PCION with, versus without, MGF. These results demonstrate the feasibility and potential of external MGF-responsive PCION-coated oncolytic Ads as smart hybrid vectors for cancer gene therapy. PMID:26164117

  7. Pulmonary toxicity and kinetic study of Cy5.5-conjugated superparamagnetic iron oxide nanoparticles by optical imaging

    SciTech Connect

    Cho, Wan-Seob; Park, Sue Nie; Yu, Mi Kyung; Jon, Sangyong; Jeong, Jayoung

    2009-08-15

    Recent advances in the development of nanotechnology and devices now make it possible to accurately deliver drugs or genes to the lung. Magnetic nanoparticles can be used as contrast agents, thermal therapy for cancer, and be made to concentrate to target sites through an external magnetic field. However, these advantages may also become problematic when taking into account safety and toxicological factors. This study demonstrated the pulmonary toxicity and kinetic profile of anti-biofouling polymer coated, Cy5.5-conjugated thermally cross-linked superparamagnetic iron oxide nanoparticles (TCL-SPION) by optical imaging. Negatively charged, 36 nm-sized, Cy5.5-conjugated TCL-SPION was prepared for optical imaging probe. Cy5.5-conjugated TCL-SPION was intratracheally instilled into the lung by a non-surgical method. Cy5.5-conjugated TCL-SPION slightly induced pulmonary inflammation. The instilled nanoparticles were distributed mainly in the lung and excreted in the urine via glomerular filtration. Urinary excretion was peaked at 3 h after instillation. No toxicity was found under the concentration of 1.8 mg/kg and the half-lives of nanoparticles in the lung and urine were estimated to be about 14.4 {+-} 0.54 h and 24.7 {+-} 1.02 h, respectively. Although further studies are required, our results showed that Cy5.5-conjugated TCL-SPION can be a good candidate for use in pulmonary delivery vehicles and diagnostic probes.

  8. Mercury removal in wastewater by iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Vélez, E.; Campillo, G. E.; Morales, G.; Hincapié, C.; Osorio, J.; Arnache, O.; Uribe, J. I.; Jaramillo, F.

    2016-02-01

    Mercury is one of the persistent pollutants in wastewater; it is becoming a severe environmental and public health problem, this is why nowadays its removal is an obligation. Iron oxide nanoparticles are receiving much attention due to their properties, such as: great biocompatibility, ease of separation, high relation of surface-area to volume, surface modifiability, reusability, excellent magnetic properties and relative low cost. In this experiment, Fe3O4 and γ-Fe2O3 nanoparticles were synthesized using iron salts and NaOH as precipitation agents, and Aloe Vera as stabilizing agent; then these nanoparticles were characterized by three different measurements: first, using a Zetasizer Nano ZS for their size estimation, secondly UV-visible spectroscopy which showed the existence of resonance of plasmon at λmax∼360 nm, and lastly by Scanning Electron Microscopy (SEM) to determine nanoparticles form. The results of this characterization showed that the obtained Iron oxides nanoparticles have a narrow size distribution (∼100nm). Mercury removal of 70% approximately was confirmed by atomic absorption spectroscopy measurements.

  9. Cross-links between ribosomal proteins of 30S subunits in 70S tight couples and in 30S subunits.

    PubMed

    Lambert, J M; Boileau, G; Cover, J A; Traut, R R

    1983-08-01

    Ribosome 70S tight couples and 30S subunits derived from them were modified with 2-iminothiolane under conditions where about two sulfhydryl groups per protein were added to the ribosomal particles. The 70S and 30S particles were not treated with elevated concentrations of NH4Cl, in contrast to those used in earlier studies. The modified particles were oxidized to promote disulfide bond formation. Proteins were extracted from the cross-linked particles by using conditions to preclude disulfide interchange. Disulfide-linked protein complexes were fractionated on the basis of charge by electrophoresis in polyacrylamide/urea gels at pH 5.5. The proteins from sequential slices of the urea gels were analyzed by two-dimensional diagonal polyacrylamide/sodium dodecyl sulfate gel electrophoresis. Final identification of proteins in cross-linked complexes was made by radioiodination of the proteins, followed by two-dimensional polyacrylamide/urea gel electrophoresis. Attention was focused on cross-links between 30S proteins. We report the identification of 27 cross-linked dimers and 2 trimers of 30S proteins, all but one of which were found in both 70S ribosomes and free 30S subunits in similar yield. Seven of the cross-links, S3-S13, S13-S21, S14-S19, S7-S12, S9-S13, S11-S21, and S6-S18-S21, have not been reported previously when 2-iminothiolane was used. Cross-links S3-S13, S13-S21, S7-S12, S11-S21, and S6-S18-S21 are reported for the first time. The identification of the seven new cross-links is illustrated and discussed in detail. Ten of the dimers reported in the earlier studies of Sommer & Traut (1976) [Sommer, A., & Traut, R. R. (1976) J. Mol. Biol. 106, 995-1015], using 30S subunits treated with high salt concentrations, were not found in the experiments reported here.

  10. Phase discrimination through oxidant selection in low-temperature atomic layer deposition of crystalline iron oxides.

    PubMed

    Riha, Shannon C; Racowski, Joy M; Lanci, Michael P; Klug, Jeffrey A; Hock, Adam S; Martinson, Alex B F

    2013-03-12

    Control over the oxidation state and crystalline phase of thin-film iron oxides was achieved by low-temperature atomic layer deposition (ALD), utilizing a novel iron precursor, bis(2,4-methylpentadienyl)iron. This low-temperature (T = 120 °C) route to conformal deposition of crystalline Fe3O4 or α-Fe2O3 thin films is determined by the choice of oxygen source selected for the second surface half-reaction. The approach employs ozone to produce fully oxidized α-Fe2O3 or a milder oxidant, H2O2, to generate the Fe(2+)/Fe(3+) spinel, Fe3O4. Both processes show self-limiting surface reactions and deposition rates of at least 0.6 Å/cycle, a significantly high growth rate at such mild conditions. We utilized this process to prepare conformal iron oxide thin films on a porous framework, for which α-Fe2O3 is active for photocatalytic water splitting.

  11. Structural and spectral characteristics of the cross-linked dimer derived from electrooxidation of cyclic 1,N2-propanoguanosine.

    PubMed

    Murakami, Hiroya; Esaka, Yukihiro; Uno, Bunji

    2011-01-01

    The acetaldehyde-derived cyclic propano adduct of 2'-deoxyguanosine was easily oxidized electrochemically into the cross-linked dimer as an oxidative product. The structural and spectroscopic characteristics of the dimer were investigated by MS, (1)H and (13)C-NMR, UV, and DFT calculations. The dimer formation was inferred from a molecular ionic peak of m/z 705 ([(2M-2H)+H](+), M being the molecular weight of the monomer) on the ESI-MS spectra and the chemical formula as C(28)H(36)N(10)O(12) provided by the high-resolution ESI-MS results. The C2-N5 linkage between the two monomers in the dimer was deduced from the (1)H- and (13)C-NMR spectral results. In addition, the correlations in the 2-dimensional NMR spectra (DQF-COSY and HMBC) were consistently explained by the structure of the C2-N5 cross-linked dimer. UV spectral measurements also support the C2-N5 linking in the dimer formation. The formation of the cross-link dimer as an oxidative lesion of the acetaldehyde-derived cyclic propano adduct of guanosine is expected to interfere with DNA replication and to contribute to acetaldehyde-mediated genotoxicity.

  12. Study of nanocomposites based on iron oxides and pectin

    NASA Astrophysics Data System (ADS)

    Chistyakova, Nataliya I.; Shapkin, Alexey A.; Sirazhdinov, Ruslan R.; Gubaidulina, Tatiana V.; Kiseleva, Tatiana Yu.; Kazakov, Alexander P.; Rusakov, Vyacheslav S.

    2014-10-01

    Mössbauer and X-ray diffraction study of nanocomposites based on iron oxides and pectin (PC) was carried out involving magnetization measurements. The concentrations of PC in nanocomposites varied from 0 to 10%. Mössbauer investigations of nanocomposites were carried out in the temperature range from 5 to 300 K. Many-state superparamagnetic relaxation model was used for spectra fitting. The magnetization, M(T,H), was measured in the temperature interval of 80-300 K and magnetic field up to 10 kOe. Formation of the "iron-polymer" interface was not observed. Particle sizes were estimated using the Mössbauer and X-ray powder diffraction data.

  13. Study of nanocomposites based on iron oxides and pectin

    SciTech Connect

    Chistyakova, Nataliya I. Shapkin, Alexey A. Sirazhdinov, Ruslan R. Gubaidulina, Tatiana V. Kiseleva, Tatiana Yu. Kazakov, Alexander P. Rusakov, Vyacheslav S.

    2014-10-27

    Mössbauer and X-ray diffraction study of nanocomposites based on iron oxides and pectin (PC) was carried out involving magnetization measurements. The concentrations of PC in nanocomposites varied from 0 to 10%. Mössbauer investigations of nanocomposites were carried out in the temperature range from 5 to 300 K. Many-state superparamagnetic relaxation model was used for spectra fitting. The magnetization, M(T,H), was measured in the temperature interval of 80-300 K and magnetic field up to 10 kOe. Formation of the 'iron-polymer' interface was not observed. Particle sizes were estimated using the Mössbauer and X-ray powder diffraction data.

  14. Cobalt-promoted Iron Oxide Nanoparticles for the Selective Oxidative Dehydrogenation of Cyclohexane

    NASA Astrophysics Data System (ADS)

    Rutter, Matthew

    Recent work has shown that both cobalt and iron oxide nanoparticles are active for the oxidative dehydrogenation (ODH) of cyclohexane to benzene, the former more active than the latter. Further study has shown that the addition of gold species as a minority component into iron oxide nanocrystals increases the selectivity of the reaction to benzene. Since a primary motivation for this work is the addition of catalysts in jet fuels to facilitate the dehydrogenation and cracking reactions preceding their combustion, a low-cost, sacrificial catalyst is sought after. In this application, catalyst nanoparticles suspended in the fuel stream will dehydrogenate cyclic alkanes (cyclohexane) to their aromatic counterparts (benzene). Alkenes and aromatics have a much higher rate of combustion, which decreases the amount of uncombusted fuel in the exhaust, thereby increasing performance. As these catalysts are not recyclable, there is significant impetus to substitute cheaper base metals for expensive noble metals. In this work, iron oxide nanoparticles are doped with varying levels of cobalt to examine the effect of cobalt content and oxidation state on the selectivity and activity of the iron oxide for the oxidative dehydrogenation of cyclohexane, used as a model cyclic alkane in jet fuel. We have shown previously that small (˜5nm) cobalt oxide nanoparticles favor the production of benzene over the partial dehydrogenation products cyclohexene and cyclohexadiene, or the complete oxidation product carbon dioxide. It is the aim of this work to examine the surface of these cobalt-iron oxide nanoparticles to determine the conditions most favorable for this selective oxidative dehydrogenation. Cobalt-doped iron nanoparticles were prepared by a surfactant-free hydrothermal co-precipitation technique that enabled a high degree of composition control and size control. These samples were characterized via Transmission Electron Microscopy (TEM), powder X-Ray Diffraction (XRD), X

  15. GAS-PHASE FLAME SYNTHESIS AND PROPERTIES OF MAGNETIC IRON OXIDE NANOPARTICLES WITH REDUCED OXIDATION STATE

    PubMed Central

    Kumfer, Benjamin M; Shinoda, Kozo; Jeyadevan, Balachandran; Kennedy, Ian M

    2010-01-01

    Iron oxide nanoparticles of reduced oxidation state, mainly in the form of magnetite, have been synthesized utilizing a new continuous, gas-phase, nonpremixed flame method using hydrocarbon fuels. This method takes advantage of the characteristics of the inverse flame, which is produced by injection of oxidizer into a surrounding flow of fuel. Unlike traditional flame methods, this configuration allows for the iron particle formation to be maintained in a more reducing environment. The effects of flame temperature, oxygen-enrichment and fuel dilution (i.e. the stoichiometric mixture fraction), and fuel composition on particle size, Fe oxidation state, and magnetic properties are evaluated and discussed. The crystallite size, Fe(II) fraction, and saturation magnetization were all found to increase with flame temperature. Flames of methane and ethylene were used, and the use of ethylene resulted in particles containing metallic Fe(0), in addition to magnetite, while no Fe(0) was present in samples synthesized using methane. PMID:20228941

  16. Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans

    PubMed Central

    Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu

    2000-01-01

    The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768

  17. Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

    PubMed

    de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

    2011-11-01

    Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation.

  18. RGD-conjugated iron oxide magnetic nanoparticles for magnetic resonance imaging contrast enhancement and hyperthermia.

    PubMed

    Zheng, S W; Huang, M; Hong, R Y; Deng, S M; Cheng, L F; Gao, B; Badami, D

    2014-03-01

    The purpose of this study was to develop a specific targeting magnetic nanoparticle probe for magnetic resonance imaging and therapy in the form of local hyperthermia. Carboxymethyl dextran-coated ultrasmall superparamagnetic iron oxide nanoparticles with carboxyl groups were coupled to cyclic arginine-glycine-aspartic peptides for integrin α(v)β₃ targeting. The particle size, magnetic properties, heating effect, and stability of the arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide were measured. The arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide demonstrates excellent stability and fast magneto-temperature response. Magnetic resonance imaging signal intensity of Bcap37 cells incubated with arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide was significantly decreased compared with that incubated with plain ultrasmall superparamagnetic iron oxide. The preferential uptake of arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide by target cells was further confirmed by Prussian blue staining and confocal laser scanning microscopy.

  19. Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

    NASA Astrophysics Data System (ADS)

    Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; Marlow, Jeffrey J.; Orphan, Victoria J.

    2014-10-01

    Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organic carbon oxidation or in diffusive sedimentary sulfate-methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. These results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.

  20. Chitosan-Iron Oxide Coated Graphene Oxide Nanocomposite Hydrogel: A Robust and Soft Antimicrobial Biofilm.

    PubMed

    Konwar, Achyut; Kalita, Sanjeeb; Kotoky, Jibon; Chowdhury, Devasish

    2016-08-17

    We report a robust biofilm with antimicrobial properties fabricated from chitosan-iron oxide coated graphene oxide nanocomposite hydrogel. For the first time, the coprecipitation method was used for the successful synthesis of iron oxide coated graphene oxide (GIO) nanomaterial. After this, films were fabricated by the gel-casting technique aided by the self-healing ability of the chitosan hydrogel network system. Both the nanomaterial and the nanocomposite films were characterized by techniques such as scanning electron microscopy, FT-IR spectroscopy, X-ray diffraction, and vibrating sample magnetometry. Measurements of the thermodynamic stability and mechanical properties of the films indictaed a significant improvement in their thermal and mechanical properties. Moreover, the stress-strain profile indicated the tough nature of the nanocomposite hydrogel films. These improvements, therefore, indicated an effective interaction and good compatibility of the GIO nanomaterial with the chitosan hydrogel matrix. In addition, it was also possible to fabricate films with tunable surface properties such as hydrophobicity simply by varying the loading percentage of GIO nanomaterial in the hydrogel matrix. Fascinatingly, the chitosan-iron oxide coated graphene oxide nanocomposite hydrogel films displayed significant antimicrobial activities against both Gram-positive and Gram-negative bacterial strains, such as methicillin-resistant Staphylococcus aureus, Staphylococcus aureus, and Escherichia coli, and also against the opportunistic dermatophyte Candida albicans. The antimicrobial activities of the films were tested by agar diffusion assay and antimicrobial testing based on direct contact. A comparison of the antimicrobial activity of the chitosan-GIO nanocomposite hydrogel films with those of individual chitosan-graphene oxide and chitosan-iron oxide nanocomposite films demonstrated a higher antimicrobial activity for the former in both types of tests. In vitro hemolysis

  1. Standard versus trans-epithelial collagen cross-linking in keratoconus patients suitable for standard collagen cross-linking

    PubMed Central

    Rossi, S; Orrico, A; Santamaria, C; Romano, V; De Rosa, L; Simonelli, F; De Rosa, G

    2015-01-01

    Purpose Evaluating the clinical results of trans-epithelial collagen cross-linking (CXL) and standard CXL in patients with progressive keratoconus. Methods This prospective study comprised 20 eyes of 20 patients with progressive keratoconus. Ten eyes were treated by standard CXL and ten by trans-epithelial cross-linking (TE-CXL, epithelium on) with 1 year of follow-up. All patients underwent complete ophthalmologic testing that included pre- and postoperative uncorrected visual acuity, corrected visual acuity, spherical error, spherical equivalent, corneal astigmatism, simulated maximum, minimum, and average keratometry, coma and spherical aberration, optical pachymetry, and endothelial cell density. Intra-and postoperative complications were recorded. The solution used for standard CXL comprised riboflavin 0.1% and dextran 20.0% (Ricrolin), while the solution for TE-CXL (Ricrolin, TE) comprised riboflavin 0.1%, dextran 15.0%, trometamol (Tris), and ethylenediaminetetraacetic acid. Ultraviolet-A treatment was performed with UV-X System at 3 mW/cm2. Results In both the standard CXL group (ten patients, ten eyes; mean age, 30.4±7.3 years) and the TE-CXL group (ten patients, ten eyes; mean age, 28±3.8 years), uncorrected visual acuity and corrected visual acuity improved significantly after treatment. Furthermore, a significant improvement in topographic outcomes, spherical error, and spherical equivalent was observed in both groups at month 12 posttreatment. No significant variations were recorded in other parameters. No complications were noted. Conclusion A 1-year follow-up showed stability of clinical and refractive outcomes after standard CXL and TE-CXL. PMID:25834386

  2. Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

    PubMed Central

    Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L.; Charnock, John M.; Polya, David A.; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R.

    2013-01-01

    Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit. PMID:23666325

  3. Superparamagnetic iron oxide nanoparticles: magnetic nanoplatforms as drug carriers

    PubMed Central

    Wahajuddin; Arora, Sumit

    2012-01-01

    A targeted drug delivery system is the need of the hour. Guiding magnetic iron oxide nanoparticles with the help of an external magnetic field to its target is the principle behind the development of superparamagnetic iron oxide nanoparticles (SPIONs) as novel drug delivery vehicles. SPIONs are small synthetic γ-Fe2O3 (maghemite) or Fe3O4 (magnetite) particles with a core ranging between 10 nm and 100 nm in diameter. These magnetic particles are coated with certain biocompatible polymers, such as dextran or polyethylene glycol, which provide chemical handles for the conjugation of therapeutic agents and also improve their blood distribution profile. The current research on SPIONs is opening up wide horizons for their use as diagnostic agents in magnetic resonance imaging as well as for drug delivery vehicles. Delivery of anticancer drugs by coupling with functionalized SPIONs to their targeted site is one of the most pursued areas of research in the development of cancer treatment strategies. SPIONs have also demonstrated their efficiency as nonviral gene vectors that facilitate the introduction of plasmids into the nucleus at rates multifold those of routinely available standard technologies. SPION-induced hyperthermia has also been utilized for localized killing of cancerous cells. Despite their potential biomedical application, alteration in gene expression profiles, disturbance in iron homeostasis, oxidative stress, and altered cellular responses are some SPION-related toxicological aspects which require due consideration. This review provides a comprehensive understanding of SPIONs with regard to their method of preparation, their utility as drug delivery vehicles, and some concerns which need to be resolved before they can be moved from bench top to bedside. PMID:22848170

  4. Arsenic bioremediation by biogenic iron oxides and sulfides.

    PubMed

    Omoregie, Enoma O; Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L; Charnock, John M; Polya, David A; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R

    2013-07-01

    Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit.

  5. Enriched Iron(III)-Reducing Bacterial Communities are Shaped by Carbon Substrate and Iron Oxide Mineralogy.

    PubMed

    Lentini, Christopher J; Wankel, Scott D; Hansel, Colleen M

    2012-01-01

    Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a large-scale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well-known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g., Enterobacter spp.) and sulfate-reducing bacteria (e.g., Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metal-respiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.

  6. Tuning nanoscale viscoelasticity of polyelectrolyte complexes with multiple types of cross-links

    NASA Astrophysics Data System (ADS)

    Ma, Tianzhu; Han, Biao; Lee, Daeyeon; Han, Lin

    Mechanical properties of hydrogels are manifestation of cross-link type and density, fixed charges and water-polymer interactions. In this study, we revealed how different types of cross-links regulate the nanoscale viscoelasticity of polyelectrolyte networks. Ionically cross-linked PAH/PAA layer-by-layer complexes were modified to include covalent cross-links using EDC. AFM-nanoindentation and force relaxation were performed at various ionic strength (0.01-1M) and pH (1.5-5.5). As-assembled networks, held only by ionic cross-links, underwent >95% relaxation, dominated by cross-link breaking and re-formation. Addition of covalent cross-links increased the instantaneous modulus by 1.6-fold and attenuated relaxation to ~80% of net neutral states (pH >=3.5), as covalent cross-links provide additional elastic components. The network remained stabilized when all ionic cross-links were dissociated at pH <=1.5, whereby further attenuation to 31% in relaxation could be due to viscoelastic polymer conformational changes and fluid flow-induced poroelasticity. Taken together, this study demonstrates the potential of using multiple cross-linking types to tune the viscoelastic mechanisms in polyelectrolyte complexes.

  7. Cross-linking of fibrinogen and fibrin by fibrin-stablizing factor (factor XIIIa).

    PubMed

    Kanaide, H; Shainoff, J R

    1975-04-01

    Factor XIIIa catalyzed intermolecular cross-linking of fibrinogen at initial rates that varied in direct (first order) proportion to the fibrinogen concentration, which differed from the well known zero order relationship in fibrin cross-linking. Preferential cross-linking of gamma-chains occurred with both substrates. The differences in rates and order of reaction were attributed mainly to effect of self-alignment of the gamma-chains in fibrin which enabled the cross-linking enzyme to interact with paired chains as a single rather than two independent entities. Studies on mixtures of fibrinogen and fibrin indicated factor XIIIa had near equal affinities for the two substrates. At low concentrations with which cross-linking of fibrinogen proceeded sluggishly compared to fibrin, fibrinogen inhibited stabilization of fibrin clots by competitively partitioning factor XIIIa away from the fribin. Additional inhibition arose from cross-linking of fibrin in soluble combination with fibrinogen in mixtures containing fibrinogen in large excess over fibrin. The observations demonstrate ways in which fibrinogen normally helps to suppress both polymerization and cross-linking of small amounts of fibrin produced within the circulation. At very high concentrations above 30 mg. per milliliter, fibrinogen underwent cross-linking at faster initial rates than the cross-linking of fibrin. Rapid cross-linking of concentrated fibrogen raises the possibility that filtration enrichment may be a factor contributing to abnormal formation of the highly insoluble fibrinogen deposits occurring in atheromatous tissue.

  8. Cellular level loading and heating of superparamagnetic iron oxide nanoparticles.

    PubMed

    Kalambur, Venkat S; Longmire, Ellen K; Bischof, John C

    2007-11-20

    Superparamagnetic iron oxide nanoparticles (NPs) hold promise for a variety of biomedical applications due to their properties of visualization using magnetic resonance imaging (MRI), heating with radio frequency (rf), and movement in an external magnetic field. In this study, the cellular loading (uptake) mechanism of dextran- and surfactant-coated iron oxide NPs by malignant prostate tumor cells (LNCaP-Pro5) has been studied, and the feasibility of traditional rf treatment and a new laser heating method was evaluated. The kinetics of cell loading was quantified using magnetophoresis and a colorimetric assay. The results showed that loading of surfactant-coated iron oxide NPs with LNCaP-Pro5 was saturable with time (at 24 h) and extracellular concentration (11 pg Fe/cell at 0.5 mg Fe/mL), indicating that the particles are taken up by an "adsorptive endocytosis" pathway. Dextran-coated NPs, however, were taken up less efficiently (1 pg Fe/cell at 0.5 mg Fe/mL). Loading did not saturate with concentration suggesting uptake by fluid-phase endocytosis. Magnetophoresis suggests that NP-loaded cells can be held using external magnetic fields in microcirculatory flow velocities in vivo or in an appropriately designed extracorporeal circuit. Loaded cells were heated using traditional rf (260A, 357 kHz) and a new laser method (532 nm, 7 ns pulse duration, 0.03 J/pulse, 20 pulse/s). Iron oxide in water was found to absorb sufficiently strongly at 532 nm such that heating of individual NPs and thus loaded cells (1 pg Fe/cell) was effective (<10% cell survival) after 30 s of laser exposure. Radio frequency treatment required higher loading (>10 pg Fe/cell) and longer duration (30 min) when compared to laser to accomplish cell destruction (50% viability at 10 pg Fe/cell). Scaling calculations show that the pulsed laser method can lead to single-cell (loaded with NPs) treatments (200 degrees C temperature change at the surface of an individual NP) unlike traditional rf heating

  9. Iron oxide hydroxide nanoflower assisted removal of arsenic from water

    SciTech Connect

    Raul, Prasanta Kumar; Devi, Rashmi Rekha; Umlong, Iohborlang M.; Thakur, Ashim Jyoti; Banerjee, Saumen; Veer, Vijay

    2014-01-01

    Graphical abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. TEM image clearly reveals that the nanoparticle looks flower like morphology with average particle size less than 20 nm. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature and the data fitted to different isotherm models indicate the heterogeneity of the adsorbent surface. The material can be regenerated up to 70% using dilute hydrochloric acid and it would be utilized for de-arsenification purposes. - Highlights: • The work includes synthesis of iron oxide hydroxide nanoflower and its applicability for the removal of arsenic from water. • The nanoparticle was characterized using modern instrumental methods like FESEM, TEM, BET, XRD, etc. • The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature. • The sorption is multilayered on the heterogeneous surface of the nano adsorbent. • The mechanism of arsenic removal of IOH nanoflower follows both adsorption and ion-exchange. - Abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. The nanoparticle was characterized by X-ray powder diffraction analysis (XRD), BET surface area, FTIR, FESEM and TEM images. TEM image clearly reveals flower like morphology with average particle size less than 20 nm. The nanoflower morphology is also supported by FESEM images. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic and the data fitted to different isotherm models indicate the

  10. Characterization of Interstrand DNA-DNA Cross-Links Using the α-Hemolysin Protein Nanopore.

    PubMed

    Zhang, Xinyue; Price, Nathan E; Fang, Xi; Yang, Zhiyu; Gu, Li-Qun; Gates, Kent S

    2015-12-22

    Nanopore-based sensors have been studied extensively as potential tools for DNA sequencing, characterization of epigenetic modifications such as 5-methylcytosine, and detection of microRNA biomarkers. In the studies described here, the α-hemolysin protein nanopore embedded in a lipid bilayer was used for the detection and characterization of interstrand cross-links in duplex DNA. Interstrand cross-links are important lesions in medicinal chemistry and toxicology because they prevent the strand separation that is required for read-out of genetic information from DNA in cells. In addition, interstrand cross-links are used for the stabilization of duplex DNA in structural biology and materials science. Cross-linked DNA fragments produced unmistakable current signatures in the nanopore experiment. Some cross-linked substrates gave irreversible current blocks of >10 min, while others produced long current blocks (10-100 s) before the double-stranded DNA cross-link translocated through the α-hemolysin channel in a voltage-driven manner. The duration of the current block for the different cross-linked substrates examined here may be dictated by the stability of the duplex region left in the vestibule of the nanopore following partial unzipping of the cross-linked DNA. Construction of calibration curves measuring the frequency of cross-link blocking events (1/τon) as a function of cross-link concentration enabled quantitative determination of the amounts of cross-linked DNA present in samples. The unique current signatures generated by cross-linked DNA in the α-HL nanopore may enable the detection and characterization of DNA cross-links that are important in toxicology, medicine, and materials science.

  11. Tailoring the magnetic and pharmacokinetic properties of iron oxide magnetic particle imaging tracers

    PubMed Central

    Ferguson, Richard Mathew; Khandhar, Amit P; Arami, Hamed; Hua, Loc; Hovorka, Ondrej; Krishnan, Kannan M.

    2014-01-01

    Magnetic particle imaging (MPI) is an attractive new modality for imaging distributions of iron oxide nanoparticle tracers in vivo. With exceptional contrast, high sensitivity, and good spatial resolution, MPI shows promise for clinical imaging in angiography and oncology. Critically, MPI requires high-quality iron oxide nanoparticle tracers with tailored magnetic and surface properties to achieve its full potential. In this review, we discuss optimizing iron oxide nanoparticles’ physical, magnetic, and pharmacokinetic properties for MPI, highlighting results from our recent work in which we demonstrated tailored, biocompatible iron oxide nanoparticle tracers that provided two times better linear spatial resolution and five times better signal-to-noise ratio than Resovist. PMID:23787461

  12. Catalytic effect of free iron ions and heme-iron on chromophore oxidation of a polyene antibiotic amphotericin B

    NASA Astrophysics Data System (ADS)

    Czernel, Grzegorz; Typek, Rafał; Klimek, Katarzyna; Czuryło, Aleksandra; Dawidowicz, Andrzej L.; Gagoś, Mariusz

    2016-05-01

    Owing to the presence of a chromophore in the amphotericin B (AmB) structure, the molecule can undergo the oxidation process. In this research, AmB chromophore oxidation was catalysed by iron ions (iron(III) chloride (FeCl3), pH 2.5) and by heme-iron (methemoglobin (HbFe(III)), and hemin (heme-Fe(III)) at pH 7.0). Additionally, we compared oxidation processes induced by the aforementioned oxidizing agents with autoxidation by dioxygen (O2) naturally occurring in a sample. The effects of the interaction of the oxidizing agents with AmB were analysed using molecular spectroscopies (electronic absorption (UV-Vis), fluorescence) and LC-MS. The use of a 1,10-phenanthroline (phen) chelator facilitated unambiguous determination of the oxidative effect of free iron(III) ions (FeIII) in an acidic solution on the AmB molecules. Also, the changes in the spectra of fluorescence emission centred at ∼470 nm indicate iron-catalysed processes of AmB chromophore oxidation. Unexpectedly, we found a similar spectroscopic effect for AmB induced by methemoglobin and hemin at pH 7.0. Methemoglobin and hemin at a concentration of 8 × 10-7 M (physiological) significantly increases the rate of the processes of AmB chromophore oxidation relative to the process of autoxidation.

  13. Synthesis of a novel supermagnetic iron oxide nanocomposite hydrogel based on graft copolymerization of poly((2-dimethylamino)ethyl methacrylate) onto salep for controlled release of drug.

    PubMed

    Bardajee, Ghasem Rezanejade; Hooshyar, Zari; Asli, Maryam Jahanbakhsh; Shahidi, Fatemeh Emamjome; Dianatnejad, Nastaran

    2014-03-01

    In this research, a novel supermagnetic iron oxide nanocomposite hydrogel was prepared using simultaneous in situ formation of iron oxide nanoparticles (IONs) and three-dimensional cross-linked polymer networks based on graft copolymerization of poly((2-dimethylamino)ethyl methacrylate) (PDMA) onto salep (PDMA-g-salep). The prepared ION-PDMA-g-salep hydrogel was systematically characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDAX), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). In addition, the ION-PDMA-g-salep hydrogel exhibits favorable swelling properties that are sensitive to temperature, pH, and external magnetic field (EMF). The drug release behavior of the prepared hydrogel under EMF, different temperatures and pHs was also studied for the evaluation of the release mechanism and determination of diffusion coefficients. Finally, the antibacterial activity and cytotoxicity studies of the prepared hydrogel were examined. These results suggested that the ION-PDMA-g-salep hydrogel could be a promising candidate for biological dressing applications. PMID:24433913

  14. Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria.

    PubMed

    Kappler, A; Johnson, C M; Crosby, H A; Beard, B L; Newman, D K

    2010-05-10

    Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)(aq) and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in (56)Fe/(54)Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ(56)Fe(Fe(OH)3 - Fe(II)aq) fractionation factor of +3.0 ‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)(aq) and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)(aq) by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)(aq) oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)(aq) and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of

  15. Development of a novel cross-linking strategy for fast and accurate identification of cross-linked peptides of protein complexes.

    PubMed

    Kao, Athit; Chiu, Chi-li; Vellucci, Danielle; Yang, Yingying; Patel, Vishal R; Guan, Shenheng; Randall, Arlo; Baldi, Pierre; Rychnovsky, Scott D; Huang, Lan

    2011-01-01

    Knowledge of elaborate structures of protein complexes is fundamental for understanding their functions and regulations. Although cross-linking coupled with mass spectrometry (MS) has been presented as a feasible strategy for structural elucidation of large multisubunit protein complexes, this method has proven challenging because of technical difficulties in unambiguous identification of cross-linked peptides and determination of cross-linked sites by MS analysis. In this work, we developed a novel cross-linking strategy using a newly designed MS-cleavable cross-linker, disuccinimidyl sulfoxide (DSSO). DSSO contains two symmetric collision-induced dissociation (CID)-cleavable sites that allow effective identification of DSSO-cross-linked peptides based on their distinct fragmentation patterns unique to cross-linking types (i.e. interlink, intralink, and dead end). The CID-induced separation of interlinked peptides in MS/MS permits MS(3) analysis of single peptide chain fragment ions with defined modifications (due to DSSO remnants) for easy interpretation and unambiguous identification using existing database searching tools. Integration of data analyses from three generated data sets (MS, MS/MS, and MS(3)) allows high confidence identification of DSSO cross-linked peptides. The efficacy of the newly developed DSSO-based cross-linking strategy was demonstrated using model peptides and proteins. In addition, this method was successfully used for structural characterization of the yeast 20 S proteasome complex. In total, 13 non-redundant interlinked peptides of the 20 S proteasome were identified, representing the first application of an MS-cleavable cross-linker for the characterization of a multisubunit protein complex. Given its effectiveness and simplicity, this cross-linking strategy can find a broad range of applications in elucidating the structural topology of proteins and protein complexes.

  16. Reactions of metal ions at surfaces of hydrous iron oxide

    USGS Publications Warehouse

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  17. Riboflavin-Ultraviolet A Corneal Cross-linking for Keratoconus

    PubMed Central

    El-Raggal, Tamer M.

    2009-01-01

    Purpose: To evaluate the safety, efficacy of riboflavin-ultraviolet A irradiation (UVA) corneal cross-linking and present refractive changes induced by the treatment in cases of keratoconus. Materials and Methods: The study includes 15 eyes of 9 patients with keratoconus with an average keratometric (K) reading less than 54 D and minimal corneal thickness greater than 420 microns. The corneal epithelium was removed manually within the central 8.5 mm diameter area and the cornea was soaked with riboflavin eye drops (0.1% in 20% dextran τ-500) for 30 minutes followed by exposure to UVA radiation (365 nm, 3 mW/cm2) for 30 minutes. During the follow-up period, uncorrected visual acuity (UCVA), best spectacle-corrected visual acuity (BSCVA), manifest refraction, slit lamp examination and topographic changes were recorded at the first week, first month, 3 and 6 months. Results: There was statistically significant improvement of UCVA from a preoperative mean of 0.11 ± 0.07 (range 0.05–0.3) to a postoperative mean of 0.15 ± 0.06 (range 0.1–0.3) (P < 0.05). None of the eyes lost lines of preoperative UCVA but 1 eye lost 1 line of preoperative BSCVA. The preoperative mean K of 49.97 ± 2.81 D (range 47.20–51.75) changed to 48.34 ± 2.64 D (range 45.75–50.40). This decrease in K readings was statistically significant (P < 0.05). All eyes developed minimal faint stromal haze that cleared in 14 eyes within 1 month. In only 1 eye, this resulted in a very faint corneal scar. Other sight threatening complications were not encountered in this series. Progression of the original disease was not seen in any of the treated eyes within 6 months of follow-up. Conclusion: Riboflavin-UVA corneal cross-linking is a safe and promising method for keratoconus. Larger studies with longer follow up are recommended. PMID:20404993

  18. Mediated glucose enzyme electrodes by cross-linking films of osmium redox complexes and glucose oxidase on electrodes.

    PubMed

    Ó Conghaile, Peter; Kamireddy, Sirisha; MacAodha, Domhnall; Kavanagh, Paul; Leech, Dónal

    2013-04-01

    Here, we report on a novel, versatile approach for the preparation of mediated enzyme electrodes, demonstrated using cross-linked films of glucose oxidase and a range of functionalised osmium complexes on graphite electrodes. Response of enzyme electrodes are optimised by evaluation of glucose response as a function of variation in ratios of [Os(2,2'-bipyridine)2(4-aminomethyl pyridine)Cl](+) redox mediator, polyallylamine support and glucose oxidase enzyme cross-linked using a di-epoxide reagent in films on graphite. Lowering of the redox potential required to mediate glucose oxidation is achieved by synthesis of complexes using (4,4'-dimethyl-2,2'-bipyridine) or (4,4'-dimethoxy-2,2'-bipyridine) as a ligand instead of (2,2'-bipyridine). Enzyme electrodes prepared using the complexes based on dimethoxy- or dimethyl-substituted bipyridines provide glucose oxidation current densities of 30 and 70 μA cm(-2) at 0.2 and 0.35 V applied potential compared to 120 μA cm(-2) at 0.45 V for the initial enzyme electrode, under pseudo-physiological conditions in 5 mM glucose, with stability of signals proving inadequate for long-term operation. Current output and stability may be improved by selection of alternate anchoring and cross-linking methodology, to provide enzyme electrodes capable for application to long-term glucose biosensors and anodes in enzymatic fuel cells.

  19. Role of humic substances in promoting autotrophic growth in nitrate-dependent iron-oxidizing bacteria.

    PubMed

    Kanaparthi, Dheeraj; Conrad, Ralf

    2015-05-01

    Nitrate-dependent iron oxidation was discovered in 1996 and has been reported from various environments ever since. To date, despite the widespread nature of this process, all attempts to cultivate chemolithoautotrophic nitrate-dependent iron oxidizers have been unsuccessful. The present study was focused on understanding the influence of natural chelating agents of iron, like humic substances, on the culturability, activity, and enumeration, of these microorganisms. Pure culture studies conducted with Thiobacillus denitrificans showed a constant increase in cell mass with a corresponding nitrate-dependent iron oxidation activity only when Fe(II) was provided together with humic substances, compared to no growth in control incubations without humic substances. The presence of a relatively strong chelating agent, such as EDTA, inhibited the growth of Thiobacillus denitrificans. It was concluded that complex formation between humic substances and iron was required for chemolithoautotrophic nitrate-dependent iron oxidation. Most probable number enumerations showed that numbers of chemolithoautotrophic nitrate-dependent iron-oxidizing bacteria were one to three orders of magnitude higher in the presence of humic substances compared to media without. Similar results were obtained when potential nitrate-dependent iron oxidation activity was determined in soil samples. In summary, this study showed that humic substances significantly enhanced the growth and activity of autotrophic nitrate-dependent iron-oxidizing microorganisms, probably by chelation of iron.

  20. Antioxidant films based on cross-linked methyl cellulose and native Chilean berry for food packaging applications.

    PubMed

    López de Dicastillo, Carol; Rodríguez, Francisco; Guarda, Abel; Galotto, Maria José

    2016-01-20

    Development of antioxidant and antimicrobial active food packaging materials based on biodegradable polymer and natural plant extracts has numerous advantages as reduction of synthetic additives into the food, reduction of plastic waste, and food protection against microorganisms and oxidation reactions. In this way, active films based on methylcellulose (MC) and maqui (Aristotelia chilensis) berry fruit extract, as a source of antioxidants agents, were studied. On the other hand, due to the high water affinity of MC, this polymer was firstly cross-linked with glutaraldehyde (GA) at different concentrations. The results showed that the addition of GA decreased water solubility, swelling, water vapor permeability of MC films, and the release of antioxidant substances from the active materials increased with the concentration of GA. Natural extract and active cross-linked films were characterized in order to obtain the optimal formulation with the highest antioxidant activity and the best physical properties for latter active food packaging application.

  1. Antioxidant films based on cross-linked methyl cellulose and native Chilean berry for food packaging applications.

    PubMed

    López de Dicastillo, Carol; Rodríguez, Francisco; Guarda, Abel; Galotto, Maria José

    2016-01-20

    Development of antioxidant and antimicrobial active food packaging materials based on biodegradable polymer and natural plant extracts has numerous advantages as reduction of synthetic additives into the food, reduction of plastic waste, and food protection against microorganisms and oxidation reactions. In this way, active films based on methylcellulose (MC) and maqui (Aristotelia chilensis) berry fruit extract, as a source of antioxidants agents, were studied. On the other hand, due to the high water affinity of MC, this polymer was firstly cross-linked with glutaraldehyde (GA) at different concentrations. The results showed that the addition of GA decreased water solubility, swelling, water vapor permeability of MC films, and the release of antioxidant substances from the active materials increased with the concentration of GA. Natural extract and active cross-linked films were characterized in order to obtain the optimal formulation with the highest antioxidant activity and the best physical properties for latter active food packaging application. PMID:26572446

  2. Partial oxidation of {alpha}-olefins over iron antimony oxide - influence of carbon number

    SciTech Connect

    Steen, E. van; Schnobel, M.; O`Connor, C.T.

    1996-10-01

    Iron antimony oxide is a well known catalyst for the partial oxidation of propane and 1-butene. Kinetic studies of the partial oxidation of {alpha}-olefins (C{sub 2}-C{sub 9}) revealed that the activity showed a maximum at C{sub 4}. The main products of the partial oxidation of {alpha}-olefins (larger than C{sub 2}) are the conjugated alkenal (acrolein) and dienes. The selectivity to these desired products decreases with increasing chain length probably caused by both the decrease in number of allylic hydrogen atoms and the shielding of them. Ethene could only be oxidized at relatively high temperatures (over 450{degrees}C) and the only observed products were CO and CO{sub 2} indicating the need for the presence of allylic hydrogen for low temperature selective partial oxidation. Increasing the carbon number increases the yield of CO and CO{sub 2} due to shielding of the allylic hydrogen.

  3. Once Annealed Highly Cross-Linked Polyethylene Exhibits Low Wear at 9 to 15 Years.

    PubMed

    D'Antonio, James; Capello, William N; Ramakrishnan, Rama

    2016-05-01

    A once annealed highly cross-linked polyethylene (HXLPE) was introduced in 1998. Concerns regarding its long-term performance and oxidative resistance exist because of the presence of retained free radicals. The authors studied 48 patients with 50 hip implants having an average age of 62 years. They were followed for 9 to 15 years. The purpose of this study was to determine linear wear rate and the incidence of osteolysis and/or mechanical failure. At an average follow-up of 12.2 years, the annual linear wear rate was 0.018 mm (SD, 0.024 mm). No mechanical failures or osteolysis have been found to date. The clinical performance of this HXLPE continues to meet expectations despite the presence of free radicals. [Orthopedics. 2016; 39(3):e565-e571.]. PMID:27088350

  4. Macroscopic and microscopic biodistribution of intravenously administered iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Misra, Adwiteeya; Petryk, Alicia A.; Strawbridge, Rendall R.; Hoopes, P. Jack

    2015-03-01

    Iron oxide nanoparticles (IONP) are being developed for use as a cancer treatment. They have demonstrated efficacy when used either as a monotherapy or in conjunction with conventional chemotherapy and radiation. The success of IONP as a therapeutic tool depends on the delivery of a safe and controlled cytotoxic thermal dose to tumor tissue following activation with an alternating magnetic field (AMF). Prior to clinical approval, knowledge of IONP toxicity, biodistribution and physiological clearance is essential. This preliminary time-course study determines the acute toxicity and biodistribution of 110 nm dextran-coated IONP (iron) in mice, 7 days post systemic, at doses of 0.4, 0.6, and 1.0 mg Fe/ g mouse bodyweight. Acute toxicity, manifested as changes in the behavior of mice, was only observed temporarily at 1.0 mg Fe/ g mouse bodyweight, the highest dose administered. Regardless of dose, mass spectrometry and histological analysis demonstrated over 3 mg Fe/g tissue in organs within the reticuloendotheilial system (i.e. liver, spleen, and lymph nodes). Other organs (brain, heart, lungs, and kidney) had less than 0.5 mg Fe/g tissue with iron predominantly confined to the organ vasculature.

  5. Red Dawn: Characterizing Iron Oxide Minerals in Atmospheric Dust

    NASA Astrophysics Data System (ADS)

    Yauk, K.; Ottenfeld, C. F.; Reynolds, R. L.; Goldstein, H.; Cattle, S.; Berquo, T. S.; Moskowitz, B. M.

    2012-12-01

    Atmospheric dust is comprised of many components including small amounts of iron oxide minerals. Although the iron oxides make up a small weight percent of the bulk dust, they are important because of their roles in ocean fertilization, controls on climate, and as a potential health hazard to humans. Here we report on the iron oxide mineralogy in dust from a large dust storm, dubbed Red Dawn, which engulfed eastern Australia along a 3000 km front on 23 September 2009. Red Dawn originated from the lower Lake Eyre Basin of South Australia, western New South Wales (NSW) and southwestern Queensland and was the worst dust storm to have hit the city of Sydney in more than 60 years. Dust samples were collected from various locations across eastern Australia (Lake Cowal, Orange, Hornsby, Sydney) following the Red Dawn event. Our dust collection provides a good opportunity to study the physical and mineralogical properties of iron oxides from Red Dawn using a combination of reflectance spectroscopy, Mössbauer spectroscopy (MB), and magnetic measurements. Magnetization measurements from 20-400 K reveal that magnetite/maghemite, hematite and goethite are present in all samples with magnetite occurring in trace amounts (< 0.5wt%). However, the amount of magnetite/maghemite even in trace concentrations generally increases from Lake Cowal from west to east (0.01 to 0.29 wt%), with highest magnetite contents in the urban-Sydney sites. These observations indicate the additions of magnetite from local urban sources. Variable temperature Mössbauer spectroscopy (300 K and 4.2 K) indicate that goethite and hematite compose approximately 25-45 % of the Fe-bearing phases in the Orange and Lake Cowal samples. Goethite is more abundant than hematite in the Lake Cowal samples whereas the opposite is observed for Orange. Hematite is observed at both temperatures but goethite only at 4.2 K. The identification of goethite in Mössbauer analyses at low-temperature but not at room temperature

  6. Kinetic Parameters of Binary Iron/Oxidant Pyrolants

    NASA Astrophysics Data System (ADS)

    Shamsipur, Mojtaba; Mahdi Pourmortazavi, Seied; Fathollahi, Manochehr

    2012-04-01

    The thermal properties of pyrotechnic mixtures containing iron powder as fuel and KNO3, KClO3, and KClO4 as oxidants are reported. The thermogravimetry-differential thermal analysis results for pure components and corresponding pyrotechnic mixtures revealed that the melting point, decomposition temperature, and rate of oxygen releasing of the oxidants have dominant effects on ignition reaction of the pyrotechnic mixtures. The apparent activation energy and activation parameters for the combustion processes were evaluated from the differential scanning calorimetry experiments. Based on the ignition temperatures obtained and the resulting kinetic data, the thermal reactivity of the pyrotechnic mixtures was found to decrease as in the order Fe + KClO3 > Fe + KNO3 > Fe + KClO4.

  7. Detecting the Conformational Change of Transmembrane Signaling in a Bacterial Chemoreceptor by Measuring Effects on Disulfide Cross-Linking in vivo

    NASA Astrophysics Data System (ADS)

    Hughson, Andrew G.; Hazelbauer, Gerald L.

    1996-10-01

    Transmembrane signaling by bacterial chemoreceptors is thought to involve relative movement among the four transmembrane helices of the homodimer. We assayed that movement by measuring effects of ligand occupancy on rates of oxidative cross-linking between cysteines introduced into neighboring helices of the transmembrane domain of chemoreceptor Trg from Escherichia coli. Measurements were done on chemoreceptors in their native environment, intact cells that were motile and chemotactically responsive. Receptor occupancy did not appear to cause drastic rearrangement of the four-helix structure since, among 67 cysteine pairs tested, the same 19 exhibited oxidative cross-linking in the presence or absence of saturating chemoattractant. However, occupancy did cause subtle changes that were detected as effects on rates of cross-linking. Among the seven disulfides appropriate for measurements of initial rates of formation, ligand occupancy had significant and different effects on all three cross-links that connected the two helices within a subunit but had minimal effects on the four that spanned the packing interface between subunits. This constitutes direct evidence that the conformational change of transmembrane signaling involves significant movement within a subunit and minimal movement between subunits, a pattern deduced from several previous studies and now documented directly. Among possible modes of movement between the two helices of a subunit, axial sliding of one helix relative to the other was the conformational change that best accounted for the observed effects on cross-linking.

  8. Rapid Spectrophotometric Technique for Quantifying Iron in Cells Labeled with Superparamagnetic Iron Oxide Nanoparticles: Potential Translation to the Clinic

    PubMed Central

    Dadashzadeh, Esmaeel R.; Hobson, Matthew; Bryant, L. Henry; Dean, Dana D.; Frank, Joseph A.

    2012-01-01

    Labeling cells with superparamagnetic iron oxide (SPIO) nanoparticles provides the ability to track cells by Magnetic Resonance Imaging. Quantifying intracellular iron concentration in SPIO labeled cells would allow for the comparison of agents and techniques used to magnetically label cells. Here we describe a rapid spectrophotometric technique (ST) to quantify iron content of SPIO labeled cells, circumventing the previous requirement of an overnight acid digestion. Following lysis with 10% SDS of magnetically labeled cells, quantification of SPIO doped or labeled cells was performed using commonly available spectrophotometric instrument(s) by comparing absorptions at 370 and 750 nm with correction for turbidity of cellular products to determine iron content of each sample. Standard curves demonstrated high linear correlation (R2 = 0.998) between absorbance spectra of iron oxide nanoparticles and concentration in known SPIO doped cells. Comparisons of the ST to ICP-MS or NMR relaxometric (R2) determinations of intracellular iron contents in SPIO containing samples resulted in significant linear correlation between the techniques (R2 vs. ST, R2>0.992, p<0.0001, ST vs. ICP-MS, R2>0.995, p<0.0001) with the limit of detection of ST for iron = 0.66μg/ml. We have developed a rapid straightforward protocol that does not require overnight acid digestion for quantifying iron oxide content in magnetically labeled cells using readily available analytic instrumentation that should greatly expedite advances in comparing SPIO agents and protocols for labeling cells. PMID:23109392

  9. Morphology of biogenic iron oxides records microbial physiology and environmental conditions: toward interpreting iron microfossils.

    PubMed

    Krepski, S T; Emerson, D; Hredzak-Showalter, P L; Luther, G W; Chan, C S

    2013-09-01

    Despite the abundance of Fe and its significance in Earth history, there are no established robust biosignatures for Fe(II)-oxidizing micro-organisms. This limits our ability to piece together the history of Fe biogeochemical cycling and, in particular, to determine whether Fe(II)-oxidizers played a role in depositing ancient iron formations. A promising candidate for Fe(II)-oxidizer biosignatures is the distinctive morphology and texture of extracellular Fe(III)-oxyhydroxide stalks produced by mat-forming microaerophilic Fe(II)-oxidizing micro-organisms. To establish the stalk morphology as a biosignature, morphologic parameters must be quantified and linked to the microaerophilic Fe(II)-oxidizing metabolism and environmental conditions. Toward this end, we studied an extant model organism, the marine stalk-forming Fe(II)-oxidizing bacterium, Mariprofundus ferrooxydans PV-1. We grew cultures in flat glass microslide chambers, with FeS substrate, creating opposing oxygen/Fe(II) concentration gradients. We used solid-state voltammetric microelectrodes to measure chemical gradients in situ while using light microscopy to image microbial growth, motility, and mineral formation. In low-oxygen (2.7-28 μm) zones of redox gradients, the bacteria converge into a narrow (100 μm-1 mm) growth band. As cells oxidize Fe(II), they deposit Fe(III)-oxyhydroxide stalks in this band; the stalks orient directionally, elongating toward higher oxygen concentrations. M. ferrooxydans stalks display a narrow range of widths and uniquely biogenic branching patterns, which result from cell division. Together with filament composition, these features (width, branching, and directional orientation) form a physical record unique to microaerophilic Fe(II)-oxidizer physiology; therefore, stalk morphology is a biosignature, as well as an indicator of local oxygen concentration at the time of formation. Observations of filamentous Fe(III)-oxyhydroxide microfossils from a ~170 Ma marine Fe

  10. Morphology of biogenic iron oxides records microbial physiology and environmental conditions: toward interpreting iron microfossils.

    PubMed

    Krepski, S T; Emerson, D; Hredzak-Showalter, P L; Luther, G W; Chan, C S

    2013-09-01

    Despite the abundance of Fe and its significance in Earth history, there are no established robust biosignatures for Fe(II)-oxidizing micro-organisms. This limits our ability to piece together the history of Fe biogeochemical cycling and, in particular, to determine whether Fe(II)-oxidizers played a role in depositing ancient iron formations. A promising candidate for Fe(II)-oxidizer biosignatures is the distinctive morphology and texture of extracellular Fe(III)-oxyhydroxide stalks produced by mat-forming microaerophilic Fe(II)-oxidizing micro-organisms. To establish the stalk morphology as a biosignature, morphologic parameters must be quantified and linked to the microaerophilic Fe(II)-oxidizing metabolism and environmental conditions. Toward this end, we studied an extant model organism, the marine stalk-forming Fe(II)-oxidizing bacterium, Mariprofundus ferrooxydans PV-1. We grew cultures in flat glass microslide chambers, with FeS substrate, creating opposing oxygen/Fe(II) concentration gradients. We used solid-state voltammetric microelectrodes to measure chemical gradients in situ while using light microscopy to image microbial growth, motility, and mineral formation. In low-oxygen (2.7-28 μm) zones of redox gradients, the bacteria converge into a narrow (100 μm-1 mm) growth band. As cells oxidize Fe(II), they deposit Fe(III)-oxyhydroxide stalks in this band; the stalks orient directionally, elongating toward higher oxygen concentrations. M. ferrooxydans stalks display a narrow range of widths and uniquely biogenic branching patterns, which result from cell division. Together with filament composition, these features (width, branching, and directional orientation) form a physical record unique to microaerophilic Fe(II)-oxidizer physiology; therefore, stalk morphology is a biosignature, as well as an indicator of local oxygen concentration at the time of formation. Observations of filamentous Fe(III)-oxyhydroxide microfossils from a ~170 Ma marine Fe

  11. Disulfide cross-linking influences symbiotic activities of nodule peptide NCR247.

    PubMed

    Shabab, Mohammed; Arnold, Markus F F; Penterman, Jon; Wommack, Andrew J; Bocker, Hartmut T; Price, Paul A; Griffitts, Joel S; Nolan, Elizabeth M; Walker, Graham C

    2016-09-01

    Interactions of rhizobia with legumes establish the chronic intracellular infection that underlies symbiosis. Within nodules of inverted repeat-lacking clade (IRLC) legumes, rhizobia differentiate into nitrogen-fixing bacteroids. This terminal differentiation is driven by host nodule-specific cysteine-rich (NCR) peptides that orchestrate the adaptation of free-living bacteria into intracellular residents. Medicago truncatula encodes a family of >700 NCR peptides that have conserved cysteine motifs. NCR247 is a cationic peptide with four cysteines that can form two intramolecular disulfide bonds in the oxidized forms. This peptide affects Sinorhizobium meliloti transcription, translation, and cell division at low concentrations and is antimicrobial at higher concentrations. By preparing the three possible disulfide-cross-linked NCR247 regioisomers, the reduced peptide, and a variant lacking cysteines, we performed a systematic study of the effects of intramolecular disulfide cross-linking and cysteines on the activities of an NCR peptide. The relative activities of the five NCR247 variants differed strikingly among the various bioassays, suggesting that the NCR peptide-based language used by plants to control the development of their bacterial partners during symbiosis is even greater than previously recognized. These patterns indicate that certain NCR bioactivities require cysteines whereas others do not. The results also suggest that NCR247 may exert some of its effects within the cell envelope whereas other activities occur in the cytoplasm. BacA, a membrane protein that is critical for symbiosis, provides protection against all bactericidal forms of NCR247. Oxidative folding protects NCR247 from degradation by the symbiotically relevant metalloprotease HrrP (host range restriction peptidase), suggesting that disulfide bond formation may additionally stabilize NCR peptides during symbiosis. PMID:27551097

  12. Enhancing the Performance of the Rechargeable Iron Electrode in Alkaline Batteries with Bismuth Oxide and Iron Sulfide Additives

    SciTech Connect

    Manohar, AK; Yang, CG; Malkhandi, S; Prakash, GKS; Narayanan, SR

    2013-09-07

    Iron-based alkaline rechargeable batteries have the potential of meeting the needs of large-scale electrical energy storage because of their low-cost, robustness and eco-friendliness. However, the widespread commercial deployment of iron-based batteries has been limited by the low charging efficiency and the poor discharge rate capability of the iron electrode. In this study, we have demonstrated iron electrodes containing bismuth oxide and iron sulfide with a charging efficiency of 92% and capable of being discharged at the 3C rate. Such a high value of charging efficiency combined with the ability to discharge at high rates is being reported for the first time. The bismuth oxide additive led to the in situ formation of elemental bismuth and a consequent increase in the overpotential for the hydrogen evolution reaction leading to an increase in the charging efficiency. We observed that the sulfide ions added to the electrolyte and iron sulfide added to the electrode mitigated-electrode passivation and allowed for continuous discharge at high rates. At the 3C discharge rate, a utilization of 0.2 Ah/g was achieved. The performance level of the rechargeable iron electrode demonstrated here is attractive for designing economically-viable large-scale energy storage systems based on alkaline nickel-iron and iron-air batteries. (C) 2013 The Electrochemical Society. All rights reserved.

  13. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Kang, J.-K.; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ??REEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ??REE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect

  14. Zinc cross-linked hydroxamated alginates for pulsed drug release

    PubMed Central

    Raut, Neha S; Deshmukh, Prasad R; Umekar, Milind J; Kotagale, Nandkishor R

    2013-01-01

    Introduction: Alginates can be tailored chemically to improve solubility, physicochemical, and biological properties and its complexation with metal ion is useful for controlling the drug release. Materials And Methods: Synthesized N,O-dimethyl, N-methyl, or N-Benzyl hydroxylamine derivatives of sodium alginate were subsequently complexed with zinc to form beads. Hydroxamation of sodium alginate was confirmed by Fourier transform infra-red spectroscopy (FTIR) and differential scanning calorimetry (DSC). Results: The synthesized polymeric material exhibited reduced aqueous, HCl and NaOH solubility. The hydroxamated derivatives demonstrated pulsed release where change in pH of the dissolution medium stimulated the atenolol release. Conclusion: Atenolol loaded Zn cross-linked polymeric beads demonstrated the sustained the plasma drug levels with increased half-life. Although the synthesized derivatives greatly altered the aqueous solubility of sodium alginate, no significant differences in in vitro and in vivo atenolol release behavior amongst the N,O-dimethyl, N-methyl, or N-Benzyl hydroxylamine derivatives of sodium alginate were observed. PMID:24350039

  15. Pyridinium cross-links in heritable disorders of collagen

    SciTech Connect

    Pasquali, M.; Still, M.J.; Dembure, P.P.

    1995-12-01

    Ehlers-Danlos syndrome (EDS) is a heterogeneous group of inherited disorders of collagen that is characterized by skin fragility, skin hyperextensibility, and joint hypermobility. EDS type VI is caused by impaired collagen lysyl hydroxylase (procollagen-lysine, 2-oxoglutarate 5-dioxygenase; E.C.1.14.11.4), the ascorbate-dependent enzyme that hydroxylates lysyl residues on collagen neopeptides. Different alterations in the gene for collagen lysyl hydroxylase have been reported in families with EDS type VI. In EDS type VI, impairment of collagen lysyl hydroxylase results in a low hydroxylysine content in mature collagen. Hydroxylysine is a precursor of the stable, covalent, intermolecular cross-links of collagen, pyridinoline (Pyr), and deoxypyridinoline (Dpyr). Elsewhere we reported in preliminary form that patients with EDS type VI had a distinctive alteration in the urinary excretion of Pyr and Dpyr. In the present study, we confirm that the increased Dpyr/Pyr ratio is specific for EDS type VI and is not observed in other inherited or acquired collagen disorders. In addition, we find that skin from patients with EDS type VI has reduced Pyr and increased Dpyr, which could account for the organ pathology. 19 refs., 1 tab.

  16. Cross-links between stereocilia in the guinea pig cochlea.

    PubMed

    Furness, D N; Hackney, C M

    1985-05-01

    Cross-links between stereocilia on guinea pig cochlear hair cells have been examined using high resolution scanning (SEM) and transmission electron microscopy (TEM), confirming recent descriptions of these structures. Links from the tips of shorter stereocilia to the sides of the adjacent taller stereocilia (upward-pointing links), between stereocilia of the same row (side-to-side links) and between adjacent rows (row-to-row links), have been observed on inner and outer hair cells. These links have been seen in material fixed using (1) glutaraldehyde only, (2) glutaraldehyde/osmium and (3) glutaraldehyde/osmium/thiocarbohydrazide (a technique which makes gold coating unnecessary). Upward-pointing links were seen less frequently, and the surfaces of stereocilia and microvilli were smoother after fixation (3) compared with fixations (1) and (2) in which they were usually roughened in appearance. In TEM, side-to-side and row-to-row links form a regular lattice between stereocilia, and consist of a number of strands. Upward-pointing links consist of a single strand, the ends of which are associated with electron-dense material. This lies between the stereociliary membrane and the actin filament bundle, at the tip of the shorter stereocilium and the side of the taller stereocilium.

  17. Enzymatic cross-linking of carboxymethylpullulan grafted with ferulic acid.

    PubMed

    Dulong, Virginie; Hadrich, Ahdi; Picton, Luc; Le Cerf, Didier

    2016-10-20

    Carboxymethylpullulan (CMP) has been modified in a two-step grafting reaction of ferulic acid (FA). Acid adipic dihydrazyde (ADH) was first reacted with FA activated with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC). Then the product of this first reaction was reacted with CMP (activated with EDC). Grafted polysaccharides structure was confirmed by FTIR and (1)H NMR spectroscopy. Analyses by size-exclusion chromatography (SEC) coupling on-line with a multi-angle light scattering detector (MALS), a viscometer and a differential refractive index detector (DRI) (SEC/MALS/DRI/Visco) showed that associations between FA moieties occurred due to hydrophobic interactions. The grafting rates of FA were determined by the Folin-Ciocalteu method and were found between 1.0% and 11.2% (mol/mol anhydroglucose unit). The CMP-FA were then enzymatically cross-linked with laccase from Pleurotus ostreatus. The crosslinking reactions were followed by rheological measurements, demonstrating the influence of laccase concentration on kinetics. Elastic modulus and swelling rates of hydrogels depends on FA content only for low values. PMID:27474545

  18. Energy harvesting from vibration with cross-linked polypropylene piezoelectrets

    SciTech Connect

    Zhang, Xiaoqing; Wu, Liming; Sessler, Gerhard M.

    2015-07-15

    Piezoelectret films are prepared by modification of the microstructure of polypropylene foam sheets cross-linked by electronic irradiation (IXPP), followed by proper corona charging. Young’s modulus, relative permittivity, and electromechanical coupling coefficient of the fabricated films, determined by dielectric resonance spectra, are about 0.7 MPa, 1.6, and 0.08, respectively. Dynamic piezoelectric d{sub 33} coefficients up to 650 pC/N at 200 Hz are achieved. The figure of merit (FOM, d{sub 33} ⋅ g{sub 33}) for a more typical d{sub 33} value of 400 pC/N is about 11.2 GPa{sup −1}. Vibration-based energy harvesting with one-layer and two-layer stacks of these films is investigated at various frequencies and load resistances. At an optimum load resistance of 9 MΩ and a resonance frequency of 800 Hz, a maximum output power of 120 μW, referred to the acceleration g due to gravity, is obtained for an energy harvester consisting of a one-layer IXPP film with an area of 3.14 cm{sup 2} and a seismic mass of 33.7 g. The output power can be further improved by using two-layer stacks of IXPP films in electric series. IXPP energy harvesters could be used to energize low-power electronic devices, such as wireless sensors and LED lights.

  19. Energy harvesting from vibration with cross-linked polypropylene piezoelectrets

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoqing; Wu, Liming; Sessler, Gerhard M.

    2015-07-01

    Piezoelectret films are prepared by modification of the microstructure of polypropylene foam sheets cross-linked by electronic irradiation (IXPP), followed by proper corona charging. Young's modulus, relative permittivity, and electromechanical coupling coefficient of the fabricated films, determined by dielectric resonance spectra, are about 0.7 MPa, 1.6, and 0.08, respectively. Dynamic piezoelectric d33 coefficients up to 650 pC/N at 200 Hz are achieved. The figure of merit (FOM, d33 ṡ g33) for a more typical d33 value of 400 pC/N is about 11.2 GPa-1. Vibration-based energy harvesting with one-layer and two-layer stacks of these films is investigated at various frequencies and load resistances. At an optimum load resistance of 9 MΩ and a resonance frequency of 800 Hz, a maximum output power of 120 μW, referred to the acceleration g due to gravity, is obtained for an energy harvester consisting of a one-layer IXPP film with an area of 3.14 cm2 and a seismic mass of 33.7 g. The output power can be further improved by using two-layer stacks of IXPP films in electric series. IXPP energy harvesters could be used to energize low-power electronic devices, such as wireless sensors and LED lights.

  20. Synthesis and Properties of Cross-Linked Polyamide Aerogels

    NASA Technical Reports Server (NTRS)

    Williams, Jarrod C.; Meador, Mary Ann; McCorkle, Linda

    2015-01-01

    We report the first synthesis of cross-linked polyamide aerogels through step growth polymerization using a combination of diamines, diacid chloride and triacid chloride. Polyamide oligomers endcapped with amines are prepared as stable solutions in N-methylpyrrolidinone from several different diamine precursors and 1,3-benzenedicarbonyl dichloride. Addition of 1,3,5-benzenetricarbonyl trichloride yields gels which form in under five minutes according to the scheme shown. Solvent exchange of the gels into ethanol, followed by drying using supercritical CO2 extraction gives colorless aerogels with densities around 0.1 to 0.2 gcm3. Thicker monolithes of the polyamide aerogels are stiff and strong, while thin films of certain formulations are highly flexible, durable, and even translucent. These materials may have use as insulation for deployable space structures, rovers, habitats or extravehicular activity suits as well as in many terrestrial applications. Strucure property relationships of the aerogels, including surface area, mechanical properties, and thermal conductivity will be discussed.

  1. An Open Data Format for Visualization and Analysis of Cross-Linked Mass Spectrometry Results

    NASA Astrophysics Data System (ADS)

    Hoopmann, Michael R.; Mendoza, Luis; Deutsch, Eric W.; Shteynberg, David; Moritz, Robert L.

    2016-11-01

    Protein-protein interactions are an important element in the understanding of protein function, and chemical cross-linking shotgun mass spectrometry is rapidly becoming a routine approach to identify these specific interfaces and topographical interactions. Protein cross-link data analysis is aided by dozens of algorithm choices, but hindered by a lack of a common format for representing results. Consequently, interoperability between algorithms and pipelines utilizing chemical cross-linking remains a challenge. pepXML is an open, widely-used format for representing spectral search algorithm results that has facilitated information exchange and pipeline development for typical shotgun mass spectrometry analyses. We describe an extension of this format to incorporate cross-linking spectral search results. We demonstrate application of the extension by representing results of multiple cross-linking search algorithms. In addition, we demonstrate adapting existing pepXML-supporting software pipelines to analyze protein cross-linking results formatted in pepXML.

  2. Effect of glucose content on thermally cross-linked fibrous gelatin scaffolds for tissue engineering.

    PubMed

    Siimon, Kaido; Reemann, Paula; Põder, Annika; Pook, Martin; Kangur, Triin; Kingo, Külli; Jaks, Viljar; Mäeorg, Uno; Järvekülg, Martin

    2014-09-01

    Thermally cross-linked glucose-containing electrospun gelatin meshes were studied as possible cell substrate materials. FTIR analysis was used to study the effect of glucose on cross-linking reactions. It was found that the presence of glucose increases the extent of cross-linking of fibrous gelatin scaffolds, which in return determines scaffold properties and their usability in tissue engineering applications. Easy to handle fabric-like scaffolds were obtained from blends containing up to 15% glucose. Maximum extent of cross-linking was reached at nearly 20% glucose content. Cross-linking effectively resulted in decreased solubility and increased resistance to enzymatic degradation. Preliminary short-term cell culture experiments indicate that such thermally cross-linked gelatin-glucose scaffolds are suitable for tissue engineering applications. PMID:25063151

  3. Characterization of the Deoxyguanosine–Lysine Cross-Link of Methylglyoxal

    PubMed Central

    2015-01-01

    Methylglyoxal is a mutagenic bis-electrophile that is produced endogenously from carbohydrate precursors. Methylglyoxal has been reported to induce DNA–protein cross-links (DPCs) in vitro and in cultured cells. Previous work suggests that these cross-links are formed between guanine and either lysine or cysteine side chains. However, the chemical nature of the methylglyoxal induced DPC have not been determined. We have examined the reaction of methylglyoxal, deoxyguanosine (dGuo), and Nα-acetyllysine (AcLys) and determined the structure of the cross-link to be the N2-ethyl-1-carboxamide with the lysine side chain amino group (1). The cross-link was identified by mass spectrometry and the structure confirmed by comparison to a synthetic sample. Further, the cross-link between methylglyoxal, dGuo, and a peptide (AcAVAGKAGAR) was also characterized. The mechanism of cross-link formation is likely to involve an Amadori rearrangement. PMID:24801980

  4. Microemulsion Synthesis of Iron Core/Iron Oxide Shell Magnetic Nanoparticles and Their Physicochemical Properties

    PubMed Central

    Kekalo, Katsiaryna; Koo, Katherine; Zeitchick, Evan; Baker, Ian

    2015-01-01

    Iron magnetic nanoparticles were synthesized under an inert atmosphere via the reaction between FeCl3 and NaBH4 in droplets of water in a microemulsion consisting of octane with cetyl trimethylammonium bromide and butanol as surfactants. A thin Fe3O4 layer was produced on the iron nanoparticles using slow, controlled oxidation at room temperature. A silica shell was deposited on the Fe3O4 using 3-aminopropyltrimethoxysilane following the method of Zhang et al. [Mater. Sci. Eng. C 30 (2010) 92–97]. The structure and chemistry of the resulting nanoparticles were studied using variety of methods and their magnetic properties were determined. The diameter of the iron core was typically 8–16 nm, while the thickness of the Fe3O4 shell was 2–3 nm. The presence of the silica layer was confirmed using Fourier transform infra-red spectroscopy and the number of NH2-groups on each nanoparticle was determined based on colorimetric tests using ortho-phthalaldehyde. PMID:26549922

  5. Formation of the first oxidized iron in the solar system

    NASA Astrophysics Data System (ADS)

    Grossman, Lawrence; Fedkin, Alexei V.; Simon, Steven B.

    2012-12-01

    Abstract-For fayalite formation times of several thousand years, and systems enriched in water by a factor of ten relative to solar composition, 1 μm radius olivine grains could reach 2 mole% fayalite and 0.1 μm grains 5 mole% by nebular condensation, well short of the values appropriate for precursors of most chondrules and the values found in the matrices of unequilibrated ordinary chondrites. Even 10 μm olivine crystals could reach 30 mole% fayalite above 1100 K in solar gas if condensation of metallic nickel-<span class="hlt">iron</span> were delayed sufficiently by supersaturation. Consideration of the surface tensions of several phases with equilibrium condensation temperatures above that of metallic <span class="hlt">iron</span> shows that, even if they were supersaturated, they would still nucleate homogeneously above the equilibrium condensation temperature of metallic <span class="hlt">iron</span>. This phenomenon would have provided nuclei for heterogeneous nucleation of metallic nickel-<span class="hlt">iron</span>, thus preventing the latter from supersaturating significantly and preventing olivine from becoming fayalitic. Unless a way is found to make nebular regions far more <span class="hlt">oxidizing</span> than in existing models, it is unlikely that chondrule precursors or the matrix olivine grains of unequilibrated ordinary chondrites obtained their fayalite contents by condensation processes. Perhaps stabilization of FeO occurred after condensation of water ice and accretion of icy planetesimals, during heating of the planetesimals and/or in hot, dense, water-rich vapor plumes generated by impacts on them. This would imply that FeO is a relatively young feature of nebular materials.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=4007256','PMC'); return false;" href="https://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=4007256"><span id="translatedtitle">Evaluation of Nanodispersion of <span class="hlt">Iron</span> <span class="hlt">Oxides</span> Using Various Polymers</span></a></p> <p><a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pmc">PubMed Central</a></p> <p>Tanaka, Y.; Ueyama, H.; Ogata, M.; Daikoku, T.; Morimoto, M.; Kitagawa, A.; Imajo, Y.; Tahara, T.; Inkyo, M.; Yamaguchi, N.; Nagata, S.</p> <p>2014-01-01</p> <p>In order to create Fe2O3 and Fe2O3·H2O nanoparticles, various polymers were used as dispersing agents, and the resulting effects on the dispersibility and nanoparticulation of the <span class="hlt">iron</span> <span class="hlt">oxides</span> were evaluated. It was revealed that not only the solution viscosity but also the molecular length of the polymers and the surface tension of the particles affected the dispersibility of Fe2O3 and Fe2O3·H2O particles. Using the dispersing agents 7.5% hydroxypropylcellulose-SSL, 6.0% Pharmacoat 603, 5.0% and 6.5% Pharmacoat 904 and 7.0% Metolose SM-4, Fe2O3 nanoparticles were successfully fabricated by wet milling using Ultra Apex Mill. Fe2O3·H2O nanoparticles could also be produced using 5.0% hydroxypropylcellulose-SSL and 4.0 and 7.0% Pharmacoat 904. The index for dispersibility developed in this study appears to be an effective indicator of success in fabricating nanoparticles of <span class="hlt">iron</span> <span class="hlt">oxides</span> by wet milling using Ultra Apex Mill. PMID:24799739</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.ncbi.nlm.nih.gov/pubmed/27448065','PUBMED'); return false;" href="http://www.ncbi.nlm.nih.gov/pubmed/27448065"><span id="translatedtitle">Tuning the structure and habit of <span class="hlt">iron</span> <span class="hlt">oxide</span> mesocrystals.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; Josten, Elisabeth; Hermann, Raphaël P; Rücker, Ulrich; Brückel, Thomas; Bergström, Lennart; Salazar-Alvarez, German</p> <p>2016-08-25</p> <p>A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6-12.6 nm) are isostructural with a body centred tetragonal (bct) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocube mesocrystals based on nanocube edge length and magnetic field strength. PMID:27448065</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.osti.gov/pages/biblio/1319205-tuning-structure-habit-iron-oxide-mesocrystals','SCIGOV-DOEP'); return false;" href="http://www.osti.gov/pages/biblio/1319205-tuning-structure-habit-iron-oxide-mesocrystals"><span id="translatedtitle">Tuning the structure and habit of <span class="hlt">iron</span> <span class="hlt">oxide</span> mesocrystals</span></a></p> <p><a target="_blank" href="http://www.osti.gov/pages">DOE PAGESBeta</a></p> <p>Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; Josten, Elisabeth; Hermann, Raphaël P.; Rücker, Ulrich; Brückel, Thomas; Bergström, Lennart; Salazar-Alvarez, German</p> <p>2016-07-11</p> <p>A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and themore » quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocube mesocrystals based on nanocube edge length and magnetic field strength.« less</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/27261762','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/27261762"><span id="translatedtitle">Thermal and magnetic properties of chitosan-<span class="hlt">iron</span> <span class="hlt">oxide</span> nanoparticles.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Soares, Paula I P; Machado, Diana; Laia, César; Pereira, Laura C J; Coutinho, Joana T; Ferreira, Isabel M M; Novo, Carlos M M; Borges, João Paulo</p> <p>2016-09-20</p> <p>Chitosan is a biopolymer widely used for biomedical applications such as drug delivery systems, wound healing, and tissue engineering. Chitosan can be used as coating for other types of materials such as <span class="hlt">iron</span> <span class="hlt">oxide</span> nanoparticles, improving its biocompatibility while extending its range of applications. In this work <span class="hlt">iron</span> <span class="hlt">oxide</span> nanoparticles (Fe3O4 NPs) produced by chemical precipitation and thermal decomposition and coated with chitosan with different molecular weights were studied. Basic characterization on bare and chitosan-Fe3O4 NPs was performed demonstrating that chitosan does not affect the crystallinity, chemical composition, and superparamagnetic properties of the Fe3O4 NPs, and also the incorporation of Fe3O4 NPs into chitosan nanoparticles increases the later hydrodynamic diameter without compromising its physical and chemical properties. The nano-composite was tested for magnetic hyperthermia by applying an alternating current magnetic field to the samples demonstrating that the heating ability of the Fe3O4 NPs was not significantly affected by chitosan.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.osti.gov/scitech/biblio/1319205','SCIGOV-STC'); return false;" href="http://www.osti.gov/scitech/biblio/1319205"><span id="translatedtitle">Tuning the structure and habit of <span class="hlt">iron</span> <span class="hlt">oxide</span> mesocrystals</span></a></p> <p><a target="_blank" href="http://www.osti.gov/scitech">SciTech Connect</a></p> <p>Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; Josten, Elisabeth; Hermann, Raphael P; Ruecker, Ulrich; Brueckel, Th.; Bergstrom, Lennart; Salazar-Alvarez, G.</p> <p>2016-01-01</p> <p>A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic <span class="hlt">iron</span> <span class="hlt">oxide</span> nanocube mesocrystals based on nanocube edge length and magnetic field strength.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.ncbi.nlm.nih.gov/pubmed/27248668','PUBMED'); return false;" href="http://www.ncbi.nlm.nih.gov/pubmed/27248668"><span id="translatedtitle">Magnetic <span class="hlt">Iron</span> <span class="hlt">Oxide</span> Nanoparticle Seeded Growth of Nucleotide Coordinated Polymers.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Liang, Hao; Liu, Biwu; Yuan, Qipeng; Liu, Juewen</p> <p>2016-06-22</p> <p>The introduction of functional molecules to the surface of magnetic <span class="hlt">iron</span> <span class="hlt">oxide</span> nanoparticles (NPs) is of critical importance. Most previously reported methods were focused on surface ligand attachment either by physisorption or covalent conjugation, resulting in limited ligand loading capacity. In this work, we report the seeded growth of a nucleotide coordinated polymer shell, which can be considered as a special form of adsorption by forming a complete shell. Among all of the tested metal ions, Fe(3+) is the most efficient for this seeded growth. A diverse range of guest molecules, including small organic dyes, proteins, DNA, and gold NPs, can be encapsulated in the shell. All of these molecules were loaded at a much higher capacity compared to that on the naked <span class="hlt">iron</span> <span class="hlt">oxide</span> NP core, confirming the advantage of the coordination polymer (CP) shell. In addition, the CP shell provides better guest protein stability compared to that of simple physisorption while retaining guest activity as confirmed by the entrapped glucose oxidase assay. Use of this system as a peroxidase nanozyme and glucose biosensor was demonstrated, detecting glucose as low as 1.4 μM with excellent stability. This work describes a new way to functionalize inorganic materials with a biocompatible shell. PMID:27248668</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/26011415','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/26011415"><span id="translatedtitle">Dechlorination of polychlorinated biphenyls by <span class="hlt">iron</span> and its <span class="hlt">oxides</span>.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo</p> <p>2015-10-01</p> <p>The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental <span class="hlt">iron</span> (Fe) and three <span class="hlt">iron</span> (hydr)<span class="hlt">oxides</span>, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, <span class="hlt">oxidizing</span> or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the <span class="hlt">iron</span> compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/25504232','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/25504232"><span id="translatedtitle">Self-beating artificial cells: design of <span class="hlt">cross-linked</span> polymersomes showing self-oscillating motion.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Tamate, Ryota; Ueki, Takeshi; Yoshida, Ryo</p> <p>2015-02-01</p> <p>Biomimetic <span class="hlt">cross-linked</span> polymersomes that exhibit a self-beating motion without any on-off switching are developed. The polymersomes are made from a well-defined synthetic thermoresponsive diblock copolymer, and the thermoresponsive segment includes ruthenium catalysts for the oscillatory chemical reaction and vinylidene groups to <span class="hlt">cross-link</span> the polymersomes. Autonomous volume and shape oscillations of the <span class="hlt">cross-linked</span> polymersomes are realized following redox changes of the catalysts.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://adsabs.harvard.edu/abs/2015SPIE.9326E..0PM','NASAADS'); return false;" href="http://adsabs.harvard.edu/abs/2015SPIE.9326E..0PM"><span id="translatedtitle">Effect of radiation energy and intracellular <span class="hlt">iron</span> dose on <span class="hlt">iron</span> <span class="hlt">oxide</span> nanoparticle enhancement of radiation cytotoxicity</span></a></p> <p><a target="_blank" href="http://adsabs.harvard.edu/abstract_service.html">NASA Astrophysics Data System (ADS)</a></p> <p>Mazur, Courtney M.; Strawbridge, Rendall R.; Thompson, Ella S.; Petryk, Alicia A.; Gladstone, David J.; Hoopes, P. Jack</p> <p>2015-03-01</p> <p><span class="hlt">Iron</span> <span class="hlt">oxide</span> nanoparticles (IONPs) are one of several high-Z materials currently being investigated for their ability to enhance the cytotoxic effects of therapeutic ionizing radiation. Studies with <span class="hlt">iron</span> <span class="hlt">oxide</span>, silver, gold, and hafnium <span class="hlt">oxide</span> suggest radiation dose, radiation energy, cell type, and the type and level of metallic nanoparticle are all critical factors in achieving radiation enhancement in tumor cells. Using a single 4 Gy radiation dose, we compared the level of tumor cell cytotoxicity at two different intracellular <span class="hlt">iron</span> concentrations and two different radiation energies in vitro. IONPs were added to cell culture media at concentrations of 0.25 mg Fe/mL and 1.0 mg Fe/mL and incubated with murine breast adenocarcinoma (MTG-B) cells for 72 hours. Extracellular <span class="hlt">iron</span> was then removed and cells were irradiated at either 662 keV or 10 MV. At the 0.25 mg Fe/mL dose (4 pg Fe/cell), radiation energy did not affect the level of cytotoxicity. However with 1.0 mg Fe/mL (9 pg Fe/cell), the higher 10 MV radiation energy resulted in 50% greater cytotoxicity as compared to cells without IONPs irradiated at this energy. These results suggest IONPs may be able to significantly enhance the cytotoxic effects of radiation and improve therapeutic ratio if they can be selectively associated with cancer cells and/or tumors. Ongoing in vivo studies of IONP radiation enhancement in a murine tumor model are too immature to draw conclusions from at this time, however preliminary data suggests similar effectiveness of IONP radiation enhancement at 6 MV and 18 MV energy levels. In addition to the IONP-based radiation enhancement demonstrated here, the use of tumor-localized IONP with an externally delivered, non-toxic alternating magnetic field affords the opportunity to selectively heat and kill tumor cells. Combining IONP-based radiation sensitization and heat-based cytotoxicity provides a unique and potentially highly effective opportunity for therapeutic ratio enhancement.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/27605075','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/27605075"><span id="translatedtitle">Discovery of Fe7O9: a new <span class="hlt">iron</span> <span class="hlt">oxide</span> with a complex monoclinic structure.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V; McCammon, Catherine; Kupenko, Ilya; Ismailova, Leyla; Dubrovinsky, Leonid</p> <p>2016-01-01</p> <p><span class="hlt">Iron</span> <span class="hlt">oxides</span> are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary <span class="hlt">iron</span> <span class="hlt">oxide</span> with the hitherto unknown stoichiometry of Fe7O9. This new <span class="hlt">oxide</span> was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary <span class="hlt">iron</span> <span class="hlt">oxides</span> known to date. The synthesis of Fe7O9 opens a new portal to exotic <span class="hlt">iron</span>-rich (M,Fe)7O9 <span class="hlt">oxides</span> with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new <span class="hlt">iron</span> <span class="hlt">oxide</span> groups may provide new insight into the cycling of volatiles in the Earth's interior.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/20446731','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/20446731"><span id="translatedtitle">Photoreductive dissolution of <span class="hlt">iron</span> <span class="hlt">oxides</span> trapped in ice and its environmental implications.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Kim, Kitae; Choi, Wonyong; Hoffmann, Michael R; Yoon, Ho-Il; Park, Byong-Kwon</p> <p>2010-06-01</p> <p>The availability of <span class="hlt">iron</span> has been thought to be a main limiting factor for the productivity of phytoplankton and related with the uptake of atmospheric CO(2) and algal blooms in fresh and sea waters. In this work, the formation of bioavailable <span class="hlt">iron</span> (Fe(II)(aq)) from the dissolution of <span class="hlt">iron</span> <span class="hlt">oxide</span> particles was investigated in the ice phase under both UV and visible light irradiation. The photoreductive dissolution of <span class="hlt">iron</span> <span class="hlt">oxides</span> proceeded slowly in aqueous solution (pH 3.5) but was significantly accelerated in polycrystalline ice, subsequently releasing more bioavailable ferrous <span class="hlt">iron</span> upon thawing. The enhanced photogeneration of Fe(II)(aq) in ice was confirmed regardless of the type of <span class="hlt">iron</span> <span class="hlt">oxides</span> [hematite, maghemite (gamma-Fe(2)O(3)), goethite (alpha-FeOOH)] and the kind of electron donors. The ice-enhanced dissolution of <span class="hlt">iron</span> <span class="hlt">oxides</span> was also observed under visible light irradiation, although the dissolution rate was much slower compared with the case of UV radiation. The <span class="hlt">iron</span> <span class="hlt">oxide</span> particles and organic electron donors (if any) in ice are concentrated and aggregated in the liquid-like grain boundary region (freeze concentration effect) where protons are also highly concentrated (lower pH). The enhanced photodissolution of <span class="hlt">iron</span> <span class="hlt">oxides</span> should occur in this confined boundary region. We hypothesized that electron hopping through the interconnected grain boundaries of <span class="hlt">iron</span> <span class="hlt">oxide</span> particles facilitates the separation of photoinduced charge pairs. The outdoor experiments carried out under ambient solar radiation of Ny-Alesund (Svalbard, 78 degrees 55'N) also showed that the generation of dissolved Fe(II)(aq) via photoreductive dissolution is enhanced when <span class="hlt">iron</span> <span class="hlt">oxides</span> are trapped in ice. Our results imply that the ice(snow)-covered surfaces and ice-cloud particles containing <span class="hlt">iron</span>-rich mineral dusts in the polar and cold environments provide a source of bioavailable <span class="hlt">iron</span> when they thaw.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.osti.gov/scitech/servlets/purl/866527','DOE-PATENT-XML'); return false;" href="http://www.osti.gov/scitech/servlets/purl/866527"><span id="translatedtitle">Nickel aluminides and nickel-<span class="hlt">iron</span> aluminides for use in <span class="hlt">oxidizing</span> environments</span></a></p> <p><a target="_blank" href="http://www.osti.gov/doepatents">DOEpatents</a></p> <p>Liu, Chain T.</p> <p>1988-03-15</p> <p>Nickel aluminides and nickel-<span class="hlt">iron</span> aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and <span class="hlt">oxidation</span> properties in <span class="hlt">oxidizing</span> environments.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('https://www.ncbi.nlm.nih.gov/pubmed/21504536','PUBMED'); return false;" href="https://www.ncbi.nlm.nih.gov/pubmed/21504536"><span id="translatedtitle"><span class="hlt">Iron</span> isotope fractionation during microbial dissimilatory <span class="hlt">iron</span> <span class="hlt">oxide</span> reduction in simulated Archaean seawater.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Percak-Dennett, E M; Beard, B L; Xu, H; Konishi, H; Johnson, C M; Roden, E E</p> <p>2011-05-01</p> <p>The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded <span class="hlt">iron</span> formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory <span class="hlt">iron</span> reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) <span class="hlt">oxide</span> substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) <span class="hlt">oxide</span>-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. <span class="hlt">Iron</span> isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-δ(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks.</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://www.ncbi.nlm.nih.gov/pubmed/21504536','PUBMED'); return false;" href="http://www.ncbi.nlm.nih.gov/pubmed/21504536"><span id="translatedtitle"><span class="hlt">Iron</span> isotope fractionation during microbial dissimilatory <span class="hlt">iron</span> <span class="hlt">oxide</span> reduction in simulated Archaean seawater.</span></a></p> <p><a target="_blank" href="https://www.ncbi.nlm.nih.gov/entrez/query.fcgi?DB=pubmed">PubMed</a></p> <p>Percak-Dennett, E M; Beard, B L; Xu, H; Konishi, H; Johnson, C M; Roden, E E</p> <p>2011-05-01</p> <p>The largest Fe isotope excursion yet measured in marine sedimentary rocks occurs in shales, carbonates, and banded <span class="hlt">iron</span> formations of Neoarchaean and Paleoproterozoic age. The results of field and laboratory studies suggest a potential role for microbial dissimilatory <span class="hlt">iron</span> reduction (DIR) in producing this excursion. However, most experimental studies of Fe isotope fractionation during DIR have been conducted in simple geochemical systems, using pure Fe(III) <span class="hlt">oxide</span> substrates that are not direct analogues to phases likely to have been present in Precambrian marine environments. In this study, Fe isotope fractionation was investigated during microbial reduction of an amorphous Fe(III) <span class="hlt">oxide</span>-silica coprecipitate in anoxic, high-silica, low-sulphate artificial Archaean seawater at 30 °C to determine if such conditions alter the extent of reduction or isotopic fractionations relative to those observed in simple systems. The Fe(III)-Si coprecipitate was highly reducible (c. 80% reduction) in the presence of excess acetate. The coprecipitate did not undergo phase conversion (e.g. to green rust, magnetite or siderite) during reduction. <span class="hlt">Iron</span> isotope fractionations suggest that rapid and near-complete isotope exchange took place among all Fe(II) and Fe(III) components, in contrast to previous work on goethite and hematite, where exchange was limited to the outer few atom layers of the substrate. Large quantities of low-δ(56)Fe Fe(II) (aqueous and solid phase) were produced during reduction of the Fe(III)-Si coprecipitate. These findings shed new light on DIR as a mechanism for producing Fe isotope variations observed in Neoarchaean and Paleoproterozoic marine sedimentary rocks. PMID:21504536</p> </li> <li> <p><a target="_blank" onclick="trackOutboundLink('http://adsabs.harvard.edu/abs/2014MS%26E...60a2005G','NASAADS'); return false;" href="http://adsabs.harvard.edu/abs/2014MS%26E...60a2005G"><span id="translatedtitle">Effect of radiation <span class="hlt">cross-linking</span> on the abrasive wear behaviour of polyethylenes</span></a></p> <p><a target="_blank" href="http://adsabs.harvard.edu/abstract_service.html">NASA Astrophysics Data System (ADS)</a></p> <p>Gul, Rizwan M.; Khan, Tahir I.</p> <p>2014-06-01</p> <p>This study explores the differences in the dry abrasive wear behavior of different polyethylenes, and compares the effect of radiation <span class="hlt">cross-linking</span> on the wear behavior. Four different types of polyethylenes: LDPE, LLDPE, HDPE and UHMWPE were studied. <span class="hlt">Cross-linking</span> was carried out by high energy electron beam with radiation dose of 200 kGy. The results show that in unirradiated state UHMWPE has excellent wear resistance, with HDPE showing comparable wear properties; both LDPE and LLDPE exhibit high wear rate. <span class="hlt">Cross-linking</span> improves wear rate of LDPE and UHMWPE, however, the wear rate of HDPE and LLDPE increases with <span class="hlt">cross-linking</span>.</p> </li> </ol> <div class="pull-right"> <ul class="pagination"> <li><a href="#" onclick='return showDiv("page_1");'>«</a></li> <li><a href="#" onclick='return showDiv("page_21");'>21</a></li> <li><a href="#" onclick='return showDiv("page_22");'>22</a></li> <li><a href="#" onclick='return showDiv("page_23");'>23</a></li> <li><a href="#" onclick='return showDiv("page_24");'>24</a></li> <li class="active"><span>25</span></li> <li><a href="#" onclick='return showDiv("page_25");'>»</a></li> </ul> </div> </div><!-- col-sm-12 --> </div><!-- row --> </div><!-- page_25 --> <center> <div class="footer-extlink text-muted"><small>Some links on this page may take you to non-federal websites. 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