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Sample records for metal-binding silica materials

  1. Metal-binding silica materials for wastewater cleanup

    SciTech Connect

    Kroh, F.O.

    1997-10-01

    In this Phase I Small Business Innovation Research program, TPL, Inc. is developing two series of high-efficiency covalently modified silica materials for removing heavy metal ions from wastewater. These materials have metal ion capacities greatly exceeding those of commercial ion exchange resins. One series, containing thiol groups, has high capacity for {open_quotes}soft{close_quotes} heavy metal ions such as Hg, Pb, Ag, and Cd; the other, containing quaternary ammonium groups, has high capacity for anionic metal ions such as pertechnetate, arsenate, selenite, and chromate. These materials have high selectivity for the contaminant metals and will function well in harsh systems that inactivate other systems.

  2. Silica Materials for Medical Applications

    PubMed Central

    Vallet-Regí, María; Balas, Francisco

    2008-01-01

    The two main applications of silica-based materials in medicine and biotechnology, i.e. for bone-repairing devices and for drug delivery systems, are presented and discussed. The influence of the structure and chemical composition in the final characteristics and properties of every silica-based material is also shown as a function of the both applications presented. The adequate combination of the synthesis techniques, template systems and additives leads to the development of materials that merge the bioactive behavior with the drug carrier ability. These systems could be excellent candidates as materials for the development of devices for tissue engineering. PMID:19662110

  3. Reusable silica surface-insulation material

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Smith, M.; Leiser, D.

    1973-01-01

    Material was specifically developed for manufacture of insulating tiles, but it can be molded into other shapes as required. Basic raw materials are high-purity silica fiber, fumed-silica powder, and reagent-grade starch. Only purest materials are used, and care must be taken to avoid contamination during processing.

  4. Metal-silica sol-gel materials

    NASA Technical Reports Server (NTRS)

    Stiegman, Albert E. (Inventor)

    2002-01-01

    The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

  5. Fused Silica and Other Transparent Window Materials

    NASA Technical Reports Server (NTRS)

    Salem, Jon

    2016-01-01

    Several transparent ceramics, such as spinel and AlONs are now being produced in sufficient large areas to be used in space craft window applications. The work horse transparent material for space missions from Apollo to the International Space Station has been fused silica due in part to its low coefficient of expansion and optical quality. Despite its successful use, fused silica exhibits anomalies in its crack growth behavior, depending on environmental preconditioning and surface damage. This presentation will compare recent optical ceramics to fused silica and discuss sources of variation in slow crack growth behavior.

  6. Ecodesign of ordered mesoporous silica materials.

    PubMed

    Gérardin, Corine; Reboul, Julien; Bonne, Magali; Lebeau, Bénédicte

    2013-05-01

    Characterized by a regular porosity in terms of pore size and pore network arrangement, ordered mesoporous solids have attracted increasing interest in the last two decades. These materials have been identified as potential candidates for several applications. However, more environmentally friendly and economical synthesis routes of mesoporous silica materials were found to be necessary in order to develop these applications on an industrial scale. Consequently, ecodesign of ordered mesoporous silica has been considerably developed with the objective of optimizing the chemistry and the processing aspects of the material synthesis. In this review, the main strategies developed with this aim are presented and discussed. PMID:23407854

  7. Improved Silica Aerogel Composite Materials

    NASA Technical Reports Server (NTRS)

    Paik, Jong-Ah; Sakamoto, Jeffrey; Jones, Steven

    2008-01-01

    A family of aerogel-matrix composite materials having thermal-stability and mechanical- integrity properties better than those of neat aerogels has been developed. Aerogels are known to be excellent thermal- and acoustic-insulation materials because of their molecular-scale porosity, but heretofore, the use of aerogels has been inhibited by two factors: (1) Their brittleness makes processing and handling difficult. (2) They shrink during production and shrink more when heated to high temperatures during use. The shrinkage and the consequent cracking make it difficult to use them to encapsulate objects in thermal-insulation materials. The underlying concept of aerogel-matrix composites is not new; the novelty of the present family of materials lies in formulations and processes that result in superior properties, which include (1) much less shrinkage during a supercritical-drying process employed in producing a typical aerogel, (2) much less shrinkage during exposure to high temperatures, and (3) as a result of the reduction in shrinkage, much less or even no cracking.

  8. Gated Silica Mesoporous Materials in Sensing Applications

    PubMed Central

    Sancenón, Félix; Pascual, Lluís; Oroval, Mar; Aznar, Elena; Martínez-Máñez, Ramón

    2015-01-01

    Silica mesoporous supports (SMSs) have a large specific surface area and volume and are particularly exciting vehicles for delivery applications. Such container-like structures can be loaded with numerous different chemical substances, such as drugs and reporters. Gated systems also contain addressable functions at openings of voids, and cargo delivery can be controlled on-command using chemical, biochemical or physical stimuli. Many of these gated SMSs have been applied for drug delivery. However, fewer examples of their use in sensing protocols have been reported. The approach of applying SMSs in sensing uses another concept—that of loading pores with a reporter and designing a capping mechanism that is selectively opened in the presence of a target analyte, which results in the delivery of the reporter. According to this concept, we provide herein a complete compilation of published examples of probes based on the use of capped SMSs for sensing. Examples for the detection of anions, cations, small molecules and biomolecules are provided. The diverse range of gated silica mesoporous materials presented here highlights their usefulness in recognition protocols. PMID:26491626

  9. Gated Silica Mesoporous Materials in Sensing Applications.

    PubMed

    Sancenón, Félix; Pascual, Lluís; Oroval, Mar; Aznar, Elena; Martínez-Máñez, Ramón

    2015-08-01

    Silica mesoporous supports (SMSs) have a large specific surface area and volume and are particularly exciting vehicles for delivery applications. Such container-like structures can be loaded with numerous different chemical substances, such as drugs and reporters. Gated systems also contain addressable functions at openings of voids, and cargo delivery can be controlled on-command using chemical, biochemical or physical stimuli. Many of these gated SMSs have been applied for drug delivery. However, fewer examples of their use in sensing protocols have been reported. The approach of applying SMSs in sensing uses another concept-that of loading pores with a reporter and designing a capping mechanism that is selectively opened in the presence of a target analyte, which results in the delivery of the reporter. According to this concept, we provide herein a complete compilation of published examples of probes based on the use of capped SMSs for sensing. Examples for the detection of anions, cations, small molecules and biomolecules are provided. The diverse range of gated silica mesoporous materials presented here highlights their usefulness in recognition protocols. PMID:26491626

  10. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    SciTech Connect

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  11. Titania-Silica Materials for Enhanced Photocatalysis.

    PubMed

    Rico-Santacruz, Marisa; Serrano, Elena; Marcì, Giuseppe; García-López, Elisa I; García-Martínez, Javier

    2015-12-01

    Mesoporous titania-organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co-condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4-bis(triethoxysilyl) benzene (BTEB) and 1,2-bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200-360 m(2)  g(-1) ) and pore volumes (0.3 cm(3)  g(-1) ) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calcination, there is a change in the Ti(IV) coordination and an increase in the content of SiOTi moieties in comparison with the uncalcined materials, which seems to be responsible for the enhanced photocatalytic activity of hybrid titania-silica materials as compared to both uncalcined samples and the control TiO2 . PMID:26503306

  12. Titania-Silica Materials for Enhanced Photocatalysis.

    PubMed

    Rico-Santacruz, Marisa; Serrano, Elena; Marcì, Giuseppe; García-López, Elisa I; García-Martínez, Javier

    2015-12-01

    Mesoporous titania-organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co-condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4-bis(triethoxysilyl) benzene (BTEB) and 1,2-bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200-360 m(2)  g(-1) ) and pore volumes (0.3 cm(3)  g(-1) ) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calcination, there is a change in the Ti(IV) coordination and an increase in the content of SiOTi moieties in comparison with the uncalcined materials, which seems to be responsible for the enhanced photocatalytic activity of hybrid titania-silica materials as compared to both uncalcined samples and the control TiO2 .

  13. Water confinement in nanoporous silica materials

    SciTech Connect

    Renou, Richard; Szymczyk, Anthony; Ghoufi, Aziz

    2014-01-28

    The influence of the surface polarity of cylindrical silica nanopores and the presence of Na{sup +} ions as compensating charges on the structure and dynamics of confined water has been investigated by molecular dynamics simulations. A comparison between three different matrixes has been included: a protonated nanopore (PP, with SiOH groups), a deprotonated material (DP, with negatively charged surface groups), and a compensated-charge framework (CC, with sodium cations compensating the negative surface charge). The structure of water inside the different pores shows significant differences in terms of layer organization and hydrogen bonding network. Inside the CC pore the innermost layer is lost to be replaced by a quasi bulk phase. The electrostatic field generated by the DP pore is felt from the surface to the centre of pore leading to a strong orientation of water molecules even in the central part of the pore. Water dynamics inside both the PP and DP pores shows significant differences with respect to the CC pore in which the sub-diffusive regime of water is lost for a superdiffusive regime.

  14. Nanodiamond-Decorated Silica Spheres as a Chromatographic Material.

    PubMed

    Xue, Zuqin; Vinci, John C; Colón, Luis A

    2016-02-17

    Nanodiamond (ND) particles (∼5 nm), obtained from detonation soot, were oxidized and/or thermally hydrogenated. Both, the non-hydrogenated and hydrogenated ND particles were successfully coupled to the surface of micrometer-size organo-silica particles. A thin layer of nanodiamonds (NDs) decorating the surface of the organo-silica particles was visible on transmission electron microscopy (TEM) images. X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) were used to characterize the NDs prior to coupling and to confirm attachment onto the organo-silica particles. Both, ultraviolet (UV) radiation and a chemical initiator were proved to be effective radical initiators for the ND-silica coupling reaction, although for scale-up purposes the chemical initiation was more advantageous to produce the ND-silica composite. Commercially available nanodiamond primary particles were also coupled to the surface of silica particles. The ND-containing silica particles were packed into chromatographic columns to study their initial feasibility as adsorbent material for liquid chromatography. The organo-silica particles decorated with hydrogenated NDs were shown to possess reversed phase type (i.e., hydrophobic) behavior toward the probe compounds, whereas silica particles decorated with the non-hydrogenated NDs showed polar (i.e., hydrophilic) interactions, both under liquid chromatographic conditions. PMID:26790050

  15. Fluorescent Functionalized Mesoporous Silica for Radioactive Material Extraction

    SciTech Connect

    Li, Juan; Zhu, Kake; Shang, Jianying; Wang, Donghai; Nie, Zimin; Guo, Ruisong; Liu, Chongxuan; Wang, Zheming; Li, Xiaolin; Liu, Jun

    2012-08-01

    Mesoporous silica with covalently bound salicylic acid molecules incorporated in the structure was synthesized with a one-pot, co-condensation reaction at room temperature. The as-synthesized material has a large surface area, uniform particle size, and an ordered pore structure as determined by characterization with transmission electron microscopy, thermal gravimetric analysis, and infrared spectra, etc. Using the strong fluorescence and metal coordination capability of salicylic acid, functionalized mesoporous silica (FMS) was developed to track and extract radionuclide contaminants, such as uranyl [U(VI)] ions encountered in subsurface environments. Adsorption measurements showed a strong affinity of the FMS toward U(VI) with a Kd value of 105 mL/g, which is four orders of magnitude higher than the adsorption of U(VI) onto most of the sediments in natural environments. The new materials have a potential for synergistic environmental monitoring and remediation of the radionuclide U(VI) from contaminated subsurface environments.

  16. Polymer-Silica Nanocomposites: A Versatile Platform for Multifunctional Materials

    NASA Astrophysics Data System (ADS)

    Chiu, Chi-Kai

    Solution sol-gel synthesis is a versatile approach to create polymer-silica nanocomposite materials. The solution-to-solid transformation results in a solid consisting of interconnected nanoporous structure in 3D space, making it the ideal material for filtration, encapsulation, optics, electronics, drug release, and biomaterials, etc. Although the pore between nano and meso size may be tunable using different reaction conditions, the intrinsic properties such as limited diffusion within pore structure, complicated interfacial interactions at the pore surfaces, shrinkage and stress-induced cracking and brittleness have limited the applications of this material. To overcome these problems, diffusion, pore size, shrinkage and stress-induced defects need further investigation. Thus, the presented thesis will address these important questions such as whether these limitations can be utilized as the novel method to create new materials and lead to new applications. First, the behaviors of polymers such as poly(ethylene glycol) inside the silica pores are examined by studying the nucleation and growth of AgCl at the surface of the porous matrix. The pore structure and the pressure induced by the shrinkage affect have been found to induce the growth of AgCl nanocrystals. When the same process is carried out at 160 °C, silver metallization is possible. Due to the shrinkage-induced stresses, the polymer tends to move into open crack spaces and exterior surfaces, forming interconnected silver structure. This interconnected silver structure is very unique because its density is not related to the size scale of nanopore structures. These findings suggest that it is possible to utilize defect surface of silica material as the template to create interconnected silver structure. When the scale is small, polymer may no longer be needed if the diffusion length of Ag is more than the size of silica particles. To validate our assumption, monoliths of sol-gel sample containing AgNO3

  17. Silica aerogel: An intrinsically low dielectric constant material

    SciTech Connect

    Hrubesh, L.W.

    1995-04-01

    Silica aerogels are highly porous solids having unique morphologies in wavelength of visible which both the pores and particles have sizes less than the wavelength of visible light. This fine nanostructure modifies the normal transport mechanisms within aerogels and endows them with a variety of exceptional physical properties. For example, aerogels have the lowest measured thermal conductivity and dielectric constant for any solid material. The intrinsically low dielectric properties of silica aerogels are the direct result of the extremely high achievable porosities, which are controllable over a range from 75% to more than 99.8 %, and which result in measured dielectric constants from 2.0 to less than 1.01. This paper discusses the synthesis of silica aerogels, processing them as thin films, and characterizing their dielectric properties. Existing data and other physical characteristics of bulk aerogels (e.g., thermal stablity, thermal expansion, moisture adsorption, modulus, dielectric strength, etc.), which are useful for evaluating them as potential dielectrics for microelectronics, are also given.

  18. Synthesis of mesoporous silica materials from municipal solid waste incinerator bottom ash.

    PubMed

    Liu, Zhen-Shu; Li, Wen-Kai; Huang, Chun-Yi

    2014-05-01

    Incinerator bottom ash contains a large amount of silica and can hence be used as a silica source for the synthesis of mesoporous silica materials. In this study, the conditions for alkaline fusion to extract silica from incinerator bottom ash were investigated, and the resulting supernatant solution was used as the silica source for synthesizing mesoporous silica materials. The physical and chemical characteristics of the mesoporous silica materials were analyzed using BET, XRD, FTIR, SEM, and solid-state NMR. The results indicated that the BET surface area and pore size distribution of the synthesized silica materials were 992 m2/g and 2-3.8 nm, respectively. The XRD patterns showed that the synthesized materials exhibited a hexagonal pore structure with a smaller order. The NMR spectra of the synthesized materials exhibited three peaks, corresponding to Q(2) [Si(OSi)2(OH)2], Q(3) [Si(OSi)3(OH)], and Q(4) [Si(OSi)4]. The FTIR spectra confirmed the existence of a surface hydroxyl group and the occurrence of symmetric Si-O stretching. Thus, mesoporous silica was successfully synthesized from incinerator bottom ash. Finally, the effectiveness of the synthesized silica in removing heavy metals (Pb2+, Cu2+, Cd2+, and Cr2+) from aqueous solutions was also determined. The results showed that the silica materials synthesized from incinerator bottom ash have potential for use as an adsorbent for the removal of heavy metals from aqueous solutions. PMID:24656468

  19. Metal binding to the HIV nucleocapsid peptide.

    PubMed

    McLendon, G; Hull, H; Larkin, K; Chang, W

    1999-04-01

    Co(II) and Zn(II) binding constants have been measured for binding to the HIV-1 nucleocapsid N-terminal metal binding domain (residues 1-18), using competition titration methods and monitoring Co(II) binding by visible absorbance spectroscopy. Enthalpies for binding were directly measured by isothermal titration colorimetry. The results are compared with recent studies of related systems, including a study of Zn(II) binding by the full length protein.

  20. Mesoporous silica as carrier of antioxidant for food packaging materials

    NASA Astrophysics Data System (ADS)

    Buonocore, Giovanna Giuliana; Gargiulo, Nicola; Verdolotti, Letizia; Liguori, Barbara; Lavorgna, Marino; Caputo, Domenico

    2014-05-01

    Mesoporous silicas have been long recognized as very promising materials for the preparation of drug delivery systems. In this work SBA-15 mesoporous silica has been functionalized with amino-silane to be used as carrier of antioxidant compound in the preparation of active food packaging materials exhibiting tailored release properties. Active films have been prepared by loading the antioxidant tocopherol, the purely siliceous SBA-15 and the aminofunctionalized SBA-15 loaded with tocopherol into LDPE matrix trough a two-step process (mixing+extrusion). The aim of the present work is the study of the effect of the pore size and of the chemical functionality of the internal walls of the mesophase on the migration of tocopherol from active LDPE polymer films. Moreover, it has been proved that the addition of the active compound do not worsen the properties of the film such as optical characteristic and water vapor permeability, thus leading to the development of a material which could be favorably used mainly, but not exclusively, in the sector of food packaging.

  1. Characterization of silica quartz as raw material in photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Boussaa, S. Anas; Kheloufi, A.; Zaourar, N. Boutarek; Kefaifi, A.; Kerkar, F.

    2016-07-01

    Raw materials are essential for the functioning of modern societies, and access to these raw materials is vital to the world economy. Sustainable development, both globally level, raises important new challenges associated with access and efficient use of raw materials. High purity quartz, is consider as a critical raw material and it is a rare commodity that only forms under geological conditions where a narrow set of chemical and physical parameters is fulfilled. When identified and following special beneficiation techniques, high purity quartz obtains very attractive prices and is applied in high technology sectors that currently are under rapid expansion such as photovoltaic solar cells, silicon metal - oxide wafers in the semiconductor industry and long distance optical fibers that are used in communication networks. Crystalline silicon remains the principal material for photovoltaic technology. Metallurgical silicon is produced industrially by the reduction of silica with carbon in an electric arc furnace at temperatures higher than 2000 °C in the hottest parts, by a reaction that can be written ideally as: SiO2 + 2C = Si + 2CO. The aim of this study has been to test experimental methods for investigating the various physical and chemical proprieties of Hoggar quartz with different techniques: X Ray Fluorescence, infra-red spectroscopy, Scanning Electron Microscopy, Optic Microscopy, Carbon Analyzer and Vickers Hardness. The results show finally that the quartz has got good result in purity but need enrichment for the photovoltaic application.

  2. Chemical Processing and Characterization of Fiber Reinforced Nanocomposite Silica Materials

    NASA Astrophysics Data System (ADS)

    Burnett, Steven Shannon

    Ultrasound techniques, acoustic and electroacoustic spectroscopy, are used to investigate and characterize concentrated fluid phase nanocomposites. In particular, the data obtained from ultrasound methods are used as tools to improve the understanding of the fundamental process chemistry of concentrated, multicomponent, nanomaterial dispersions. Silicon nitride nanofibers embedded in silica are particularly interesting for lightweight nanocomposites, because silicon nitride is isostructural to carbon nitride, a super hard material. However, the major challenge with processing these composites is retarding particle-particle aggregation, to maintain highly dispersed systems. Therefore, a systematic approach was developed to evaluate the affect of process parameters on particle-particle aggregation, and improving the chemical kinetics for gelation. From the acoustic analysis of the nanofibers, this thesis was able to deduce that changes in aspect ratio affects the ultrasound propagation. In particular, higher aspect ratio fibers attenuate the ultrasound wave greater than lower aspect fibers of the same material. Furthermore, our results confirm that changes in attenuation depend on the hydrodynamical interactions between particles, the aspect ratio, and the morphology of the dispersant. The results indicate that the attenuation is greater for fumed silica due to its elastic nature and its size, when compared to silica Ludox. Namely, the larger the size, the greater the attenuation. This attenuation is mostly the result of scattering loss in the higher frequency range. In addition, the silica nanofibers exhibit greater attenuation than their nanoparticle counterparts because of their aspect ratio influences their interaction with the ultrasound wave. In addition, this study observed how 3M NH 4 Cl's acoustic properties changes during the gelation process, and during that change, the frequency dependency deviates from the expected squared of the frequency, until the

  3. Silica scintillating materials prepared by sol-gel methods

    SciTech Connect

    Werst, D.W.; Sauer, M.C. Jr.; Cromack, K.R.; Lin, Y.; Tartakovsky, E.A.; Trifunac, A.D.

    1993-12-31

    Silica was investigated as a rad-hard alternative to organic polymer hosts for organic scintillators. Silica sol-gels were prepared by hydrolysis of tetramethoxysilane in alcohol solutions. organic dyes were incorporated into the gels by dissolving in methanol at the sol stage of gel formation. The silica sol-gel matrix is very rad-hard. The radiation stability of silica scintillators prepared by this method is dye-limited. Transient radioluminescence was measured following excitation with 30 ps pulses of 20 MeV electrons.

  4. Polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials and their chromatographic applications.

    PubMed

    Qiu, Hongdeng; Jiang, Shengxiang; Takafuji, Makoto; Ihara, Hirotaka

    2013-03-25

    New polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials were designed based on the preparation of a new polymerizable azobenzene anionic monomer and either its cation-exchange with alkylimidazolium after grafting or the formation of an ionic liquid monomer pair before grafting onto silica. PMID:23417018

  5. Synthesis of mesoporous silica materials from municipal solid waste incinerator bottom ash

    SciTech Connect

    Liu, Zhen-Shu Li, Wen-Kai; Huang, Chun-Yi

    2014-05-01

    Highlights: • The optimal alkaline agent for the extraction of silica from bottom ash was Na{sub 2}CO{sub 3}. • The pore sizes for the mesoporous silica synthesized from bottom ash were 2–3.8 nm. • The synthesized materials exhibited a hexagonal pore structure with a smaller order. • The materials have potential for the removal of heavy metals from aqueous solutions. - Abstract: Incinerator bottom ash contains a large amount of silica and can hence be used as a silica source for the synthesis of mesoporous silica materials. In this study, the conditions for alkaline fusion to extract silica from incinerator bottom ash were investigated, and the resulting supernatant solution was used as the silica source for synthesizing mesoporous silica materials. The physical and chemical characteristics of the mesoporous silica materials were analyzed using BET, XRD, FTIR, SEM, and solid-state NMR. The results indicated that the BET surface area and pore size distribution of the synthesized silica materials were 992 m{sup 2}/g and 2–3.8 nm, respectively. The XRD patterns showed that the synthesized materials exhibited a hexagonal pore structure with a smaller order. The NMR spectra of the synthesized materials exhibited three peaks, corresponding to Q{sup 2} [Si(OSi){sub 2}(OH){sub 2}], Q{sup 3} [Si(OSi){sub 3}(OH)], and Q{sup 4} [Si(OSi){sub 4}]. The FTIR spectra confirmed the existence of a surface hydroxyl group and the occurrence of symmetric Si–O stretching. Thus, mesoporous silica was successfully synthesized from incinerator bottom ash. Finally, the effectiveness of the synthesized silica in removing heavy metals (Pb{sup 2+}, Cu{sup 2+}, Cd{sup 2+}, and Cr{sup 2+}) from aqueous solutions was also determined. The results showed that the silica materials synthesized from incinerator bottom ash have potential for use as an adsorbent for the removal of heavy metals from aqueous solutions.

  6. Metal Binding to Bipyridine-Modified PNA

    SciTech Connect

    Franzini,R.; Watson, R.; Patra, G.; Breece, R.; Tierney, D.; Hendrich, M.; Achim, C.

    2006-01-01

    Substitution of natural nucleobases in PNA oligomers with ligands is a strategy for directing metal ion incorporation to specific locations within a PNA duplex. In this study, we have synthesized PNA oligomers that contain up to three adjacent bipyridine ligands and examined the interaction with Ni{sup 2+} and Cu{sup 2+} of these oligomers and of duplexes formed from them. Variable-temperature UV spectroscopy showed that duplexes containing one terminal pair of bipyridine ligands are more stable upon metal binding than their nonmodified counterparts. While binding of one metal ion to duplexes that contain two adjacent bipyridine pairs makes the duplexes more stable, additional metal ions lower the duplex stability, with electrostatic repulsions being, most likely, an important contributor to the destabilization. UV titrations showed that the presence of several bipyridine ligands in close proximity of each other in PNA oligomers exerts a chelate effect. A supramolecular chelate effect occurs when several bipyridines are brought next to each other by hybridization of PNA duplexes. EPR spectroscopy studies indicate that even when two Cu{sup 2+} ions coordinate to a PNA duplex in which two bipyridine pairs are next to each other, the two metal-ligand complexes that form in the duplex are far enough from each other that the dipolar coupling is very weak. EXAFS and XANES show that the Ni{sup 2+}-bipyridine bond lengths are typical for [Ni(bipy){sub 2}]{sup 2+} and [Ni(bipy){sub 3}]{sup 2+} complexes.

  7. Metal binding components in human amniotic fluid

    SciTech Connect

    Paterson, P.G.; Zlotkin, S.H.; Sarkar, B. )

    1990-02-26

    Amniotic fluid is a potential source of both nutritionally essential and toxic metals for the fetus. As the binding pattern of these metals in amniotic fluid may be one of the determining factors in their availability to the fetus, the objective of this study was to investigate metal binding in vitro. The binding of six trace metals, Mn(II), Ni(II), Zn(II), Cu(II), Cd(II), and Fe(III), to components of human amniotic fluid was studied by Sephadex G-100 gel filtration at physiological pH, using radioisotopes as tracers and 50 mM TRIS/HCl as the elution buffer. The amniotic fluid was collected at 16-16.5 weeks gestation by amniocentesis and pooled for analysis. Extensive amounts of Fe, Cu, Zn, and Cd and small amounts of Mn and Ni were bound to high molecular weight proteins with elution patterns similar to those seen for the binding of these metals in serum. In addition, large amounts of Fe, Mn, Ni and Cd and small amounts of Zn and Cu were associated with low molecular weight component(s). The identity of these latter components is unknown, but they play an important biological role in amniotic fluid.

  8. Impact of pore characteristics of silica materials on loading capacity and release behavior of ibuprofen.

    PubMed

    Numpilai, Thanapha; Muenmee, Suthaporn; Witoon, Thongthai

    2016-02-01

    Impact of pore characteristics of porous silica supports on loading capacity and release behavior of ibuprofen was investigated. The porous silica materials and ibuprofen-loaded porous silica materials were thoroughly characterized by N2-sorption, thermal gravimetric and derivative weight analyses (TG-DTW), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM) to determine the physical properties of materials, amount of ibuprofen adsorbed and position of ibuprofen. The detailed characterization reveals that the ibuprofen molecules adsorbed inside the mesopores. Increasing the mesopore size from 5nm to 10nm increased the ibuprofen loading from 0.74 to 0.85mmol/g, respectively. Incorporation of macropore into the structure of porous silica materials enhanced the ibuprofen loading capacity of 11.8-20.3%. The ibuprofen-loaded bimodal meso-macroporous silica materials exhibited the highest dissolution of 92wt.% within an hour. The ibuprofen particles deposited on the external surface of the porous silica materials showed a lower dissolution rate than the ibuprofen adsorbed inside the mesopores due to the formation of ibuprofen crystalline.

  9. Impact of pore characteristics of silica materials on loading capacity and release behavior of ibuprofen.

    PubMed

    Numpilai, Thanapha; Muenmee, Suthaporn; Witoon, Thongthai

    2016-02-01

    Impact of pore characteristics of porous silica supports on loading capacity and release behavior of ibuprofen was investigated. The porous silica materials and ibuprofen-loaded porous silica materials were thoroughly characterized by N2-sorption, thermal gravimetric and derivative weight analyses (TG-DTW), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM) to determine the physical properties of materials, amount of ibuprofen adsorbed and position of ibuprofen. The detailed characterization reveals that the ibuprofen molecules adsorbed inside the mesopores. Increasing the mesopore size from 5nm to 10nm increased the ibuprofen loading from 0.74 to 0.85mmol/g, respectively. Incorporation of macropore into the structure of porous silica materials enhanced the ibuprofen loading capacity of 11.8-20.3%. The ibuprofen-loaded bimodal meso-macroporous silica materials exhibited the highest dissolution of 92wt.% within an hour. The ibuprofen particles deposited on the external surface of the porous silica materials showed a lower dissolution rate than the ibuprofen adsorbed inside the mesopores due to the formation of ibuprofen crystalline. PMID:26652347

  10. Bio-templated synthesis of highly ordered macro-mesoporous silica material for sustained drug delivery

    NASA Astrophysics Data System (ADS)

    Qu, Fengyu; Lin, Huiming; Wu, Xiang; Li, Xiaofeng; Qiu, Shilun; Zhu, Guangshan

    2010-05-01

    The bimodal porous structured silica materials consisting of macropores with the diameter of 5-20 μm and framework-like mesopores with the diameter of 4.7-6.0 nm were prepared using natural Manchurian ash and mango linin as macropored hard templates and P123 as mesopore soft templates, respectively. The macroporous structures of Manchurian ash and mango linin were replicated with the walls containing highly ordered mesoporous silica as well. As-synthesized dual porous silica was characterized by scanning electron microscope (SEM), powder X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption/desorption, fourier transform IR (FTIR) spectroscopy, and thermo-gravimetric analyzer (TGA). Ibuprofen (Ibu) was employed as a model drug and the release profiles showed that the dual porous material had a sustained drug delivery capability. And such highly ordered dual pore silica materials may have potential applications for bimolecular adsorption/separation and tissue repairing.

  11. Hierarchical mesoporous silica nanoparticles as superb light scattering materials.

    PubMed

    Ryu, Jaehoon; Yun, Juyoung; Lee, Jungsup; Lee, Kisu; Jang, Jyongsik

    2016-02-01

    A novel approach to enhance the light scattering effect was explored by applying hierarchical silica nanoparticles in DSSCs as scattering layers. The WSN-incorporated cells showed a PCE value of 9.53% and a PCE enhancement of 30.19% compared with those of the reference cells. PMID:26699659

  12. Reversible assembly of tunable nanoporous materials from "hairy" silica nanoparticles.

    PubMed

    Khabibullin, Amir; Fullwood, Emily; Kolbay, Patrick; Zharov, Ilya

    2014-10-01

    Membranes with 1-100 nm nanopores are widely used in water purification and in biotechnology, but are prone to blockage and fouling. Reversibly assembled nanoporous membranes may be advantageous due to recyclability, cleaning, and retentate recovery, as well as the ability to tune the pore size. We report the preparation and characterization of size-selective nanoporous membranes with controlled thickness, area, and pore size via reversible assembly of polymer brush-grafted ("hairy") silica nanoparticles. We describe membranes reversibly assembled from silica particles grafted with (1) polymer brushes carrying acidic and basic groups, and (2) polymer brushes carrying neutral groups. The former are stable in most organic solvents and easily disassemble in water, whereas the latter are water-stable and disassemble in organic solvents.

  13. Metal-binding proteins as metal pollution indicators

    SciTech Connect

    Hennig, H.F.

    1986-03-01

    The fact that metal-binding proteins are a consequence of elevated metal concentration in organisms is well known. What has been overlooked is that the presence of these proteins provides a unique opportunity to reformulate the criteria of metal pollution. The detoxification effect of metal-binding proteins in animals from polluted areas has been cited, but there have been only very few studies relating metal-binding proteins to pollution. This lack is due partly to the design of most experiments, which were aimed at isolation of metal-binding proteins and hence were of too short duration to allow for correlation to adverse physiological effects on the organism. In this study metal-binding proteins were isolated and characterized from five different marine animals (rock lobster, Jasus lalandii; hermit crab, Diogenes brevirostris; sandshrimp, Palaemon pacificus; black mussel, Choromytilus meridionalis; and limpet, Patella granularis). These animals were kept under identical metal-enriched conditions, hence eliminating differences in method and seasons. The study animals belonged to different phyla; varied in size, mass, age, behavior, food requirements and life stages; and accumulated metals at different rates. It is possible to link unseasonal moulting in crustacea, a known physiological effect due to a metal-enriched environment, to the production of the metal-binding protein without evidence of obvious metal body burden. Thus a new concept of pollution is defined: the presence of metal-binding proteins confirms toxic metal pollution. This concept was then tested under field conditions in the whelk Bullia digitalis and in metal-enriched grass.

  14. Optically active silica and polymeric materials for microcavity lasers and sensors

    NASA Astrophysics Data System (ADS)

    Armani, A. M.; Deka, N.; Mehrabani, S.; Shi, C.; Maker, A.; Lee, M.; Kovach, A.; Gungor, E.; Kuo, K.; Diep, V.

    2015-03-01

    Silica and silica-doped high quality factor (Q) optical resonators have demonstrated ultra-low threshold lasers based on numerous mechanisms (eg rare earth dopants, Raman). To date, the key focus has been on maintaining a high Q, as that determines the lasing threshold and linewidth. However, equally important criteria are lasing efficiency and wavelength. These parameters are governed by the material, not the cavity Q. Therefore, to fully address this challenge, it is necessary to develop new materials. We have synthesized a suite of silica and polymeric materials with nanoparticle and rare-earth dopants to enable the development of microcavity lasers with emission from the near-IR to the UV. Additionally, the efficiencies and thresholds of many of these devices surpass the previous work. Specifically, the silica sol-gel lasers are co- and tri-doped with metal nanoparticles (eg Ti, Al) and rare-earth materials (eg Yb, Nb, Tm) and are fabricated using conventional micro/nanofabrication methods. The intercalation of the metal in the silica matrix reduces the clustering of the rare-earth ions and reduces the phonon energy of the glass, improving efficiency and overall device performance. Additionally, the silica Raman gain coefficient is enhanced due to the inclusion of the metal nanoparticles, which results in a lower threshold and a higher efficiency silica Raman laser. Finally, we have synthesized several polymer films doped with metal (eg Au, Ag) nanoparticles and deposited them on the surface of our microcavity devices. By pumping on the plasmonic resonant wavelength of the particle, we are able to achieve plasmonic-enhanced upconversion lasing.

  15. Metal binding stoichiometry and isotherm choice in biosorption

    SciTech Connect

    Schiewer, S.; Wong, M.H.

    1999-11-01

    Seaweeds that possess a high metal binding capacity may be used as biosorbents for the removal of toxic heavy metals from wastewater. The binding of Cu and Ni by three brown algae (Sargassum, Colpomenia, Petalonia) and one green alga (Ulva) was investigated at pH 4.0 and pH 3.0. The greater binding strength of Cu is reflected in a binding constant that is about 10 times as high as that of Ni. The extent of metal binding followed the order Petalonia {approximately} Sargassum > Colpomenia > Ulva. This was caused by a decreasing number of binding sites and by much lower metal binding constants for Ulva as compared to the brown algae. Three different stoichiometric assumptions are compared for describing the metal binding, which assume either that each metal ion M binds to one binding site B forming a BM complex or that a divalent metal ion M binds to two monovalent sites B forming BM{sub 0.5} or B{sub 2}M complexes, respectively. Stoichiometry plots are proposed as tools to discern the relevant binding stoichiometry. The pH effect in metal binding and the change in proton binding were well predicted for the B{sub 2}M or BM{sub 0.5} stoichiometries with the former being better for Cu and the latter preferable for Ni. Overall, the BM{sub 0.5} model is recommended because it avoids iterations.

  16. NiO-silica based nanostructured materials obtained by microemulsion assisted sol-gel procedure

    SciTech Connect

    Mihaly, M.; Comanescu, A.F.; Rogozea, A.E.; Vasile, E.; Meghea, A.

    2011-10-15

    Graphical abstract: TEM micrograph of NiO/SiO{sub 2} nanoparticles. Highlights: {yields} Microemulsion assisted sol-gel procedure for NiO silica nanomaterials synthesis. {yields} Controlling the size and shape of nanoparticles and avoiding their aggregation. {yields} Narrow band-gap semiconductors (energies <3 eV) absorbing VIS or near-UV light biologically and chemically inert semiconductors entrapping/coating in silica network. {yields} Low cost as the microemulsion is firstly used in water metallic cation extraction. -- Abstract: NiO-silica based materials have been synthesized by microemulsion assisted sol-gel procedure. The versatility of these soft nanotechnology techniques has been exploited in order to obtain different types of nanostructures, such as NiO nanoparticles, NiO silica coated nanoparticles and NiO embedded in silica matrix. These materials have been characterized by adequate structural and morphology techniques: DLS, HR-TEM/SAED, BET, AFM. Optical and semiconducting properties (band-gap values) of the synthesized materials have been quantified by means of VIS-NIR diffuse reflectance spectra, thus demonstrating their applicative potential in various electron transfer phenomena such as photocatalysis, electrochromic thin films, solid oxide fuel cells.

  17. Development of construction materials using nano-silica and aggregates recycled from construction and demolition waste.

    PubMed

    Mukharjee, Bibhuti Bhusan; Barai, Sudhirkumar V

    2015-06-01

    The present work addresses the development of novel construction materials utilising commercial grade nano-silica and recycled aggregates retrieved from construction and demolition waste. For this, experimental work has been carried out to examine the influence of nano-silica and recycled aggregates on compressive strength, modulus of elasticity, water absorption, density and volume of voids of concrete. Fully natural and recycled aggregate concrete mixes are designed by replacing cement with three levels (0.75%, 1.5% and 3%) of nano-silica. The results of the present investigation depict that improvement in early days compressive strength is achieved with the incorporation of nano-silica in addition to the restoration of reduction in compressive strength of recycled aggregate concrete mixes caused owing to the replacement of natural aggregates by recycled aggregates. Moreover, the increase in water absorption and volume of voids with a reduction of bulk density was detected with the incorporation of recycled aggregates in place of natural aggregates. However, enhancement in density and reduction in water absorption and volume of voids of recycled aggregate concrete resulted from the addition of nano-silica. In addition, the results of the study reveal that nano-silica has no significant effect on elastic modulus of concrete. PMID:25986048

  18. Development of construction materials using nano-silica and aggregates recycled from construction and demolition waste.

    PubMed

    Mukharjee, Bibhuti Bhusan; Barai, Sudhirkumar V

    2015-06-01

    The present work addresses the development of novel construction materials utilising commercial grade nano-silica and recycled aggregates retrieved from construction and demolition waste. For this, experimental work has been carried out to examine the influence of nano-silica and recycled aggregates on compressive strength, modulus of elasticity, water absorption, density and volume of voids of concrete. Fully natural and recycled aggregate concrete mixes are designed by replacing cement with three levels (0.75%, 1.5% and 3%) of nano-silica. The results of the present investigation depict that improvement in early days compressive strength is achieved with the incorporation of nano-silica in addition to the restoration of reduction in compressive strength of recycled aggregate concrete mixes caused owing to the replacement of natural aggregates by recycled aggregates. Moreover, the increase in water absorption and volume of voids with a reduction of bulk density was detected with the incorporation of recycled aggregates in place of natural aggregates. However, enhancement in density and reduction in water absorption and volume of voids of recycled aggregate concrete resulted from the addition of nano-silica. In addition, the results of the study reveal that nano-silica has no significant effect on elastic modulus of concrete.

  19. Mixed surfactants-directed the mesoporous silica materials with various morphologies and structures

    SciTech Connect

    Lin Huiming; Qu Fengyu; Wu Xiang; Xue Ming; Zhu Guangshan; Qiu Shilun

    2011-06-15

    A new mixed surfactants system using alkyl carboxylic acids and quaternized poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl] urea] (PEPU) as the co-template was used to synthesize mesoporous silica materials with various morphologies and structures, including flakes, regular spheres, nanoparticles, and tube-spheres. The cationic polymer connected the anionic surfactant micelle to the anionic polysilicate species to induce the synthesis of the mesoporous silica materials. The structure and property of the surfactant and the cationic polymer determined the formation of mesoporous silica, and also had a signification influence on the morphology and structure of the final materials. To further explore the possible formation mechanism of these mesoporous materials, zeta potential was utilized to evaluate the interaction between the anionic surfactant and the cationic co-template. In addition, the structure, morphology, and porosity of these materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N{sub 2} adsorption-desorption measurements. - Graphical abstract: A new mixed surfactants system using alkyl carboxylic acids and PEPU as the co-template was used to synthesize mesoporous silica materials with various morphologies and structures. Highlights: {yields}A new mixed surfactants system induced the mesoporous silica materials with various morphologies and structure. > It is a development of the type S{sup -}N{sup +}I{sup -} route of the mesoporous formation. > Zeta potential was utilized to evaluate the interaction between the anionic surfactant and the cationic co-template. > The property and amount of surfactant and polymer determined the formation of the mesoporous materials.

  20. Efficient method for recycling silica materials from waste powder of the photonic industry.

    PubMed

    Lin, Liang-Yi; Bai, Hsunling

    2013-05-01

    An efficient and economic approach is proposed for the fast and direct recovery of silica materials from photonic waste powder. Unlike the conventional alkaline fusion method for the extraction of silica from waste materials, this method possesses advantages of a rapid and low-energy-consumed process with total recovery yield. The obtained mesoporous silica material, denoted as MCM-41(DU)-F, was recovered directly from photonic waste powder at room temperature with the assistance of cationic surfactant, hydrofluoric acid, and ammonia hydroxide. The recycled MCM-41(DU)-F with a high specific surface area (788 m(2)/g), ordered mesoporous structure (4.5 nm), and large pore volume (1.1 cm(3)/g) was used as support of tetraethylenepentamine (TEPA) for the capture of CO2 from a flue gas stream. The results demonstrated that TEPA-impregnated MCM-41(DU)-F had an adsorption capacity of 120 mg of CO2/g of adsorbent. This is higher than the amount adsorbed by TEPA-MCM-41(NaSi) made from pure chemicals (113 mg of CO2/g of adsorbent) and TEPA-MCM-41(AF) made from alkaline fusion (112 mg of CO2/g of adsorbent) under the same testing conditions. This novel recycling process, which can improve cost effectiveness for the mass production of valuable mesoporous silica materials from cheap and abundant resources through convenient preparation steps, is surely beneficial from the viewpoint of economical use of photonic industrial waste powder.

  1. Evaluation of the metal binding sites in a recombinant coagulation factor VIII identifies two sites with unique metal binding properties.

    PubMed

    Svensson, Lars Anders; Thim, Lars; Olsen, Ole Hvilsted; Nicolaisen, Else Marie

    2013-06-01

    Coagulation factor VIII is a glycosylated, non-covalent heterodimer consisting of a heavy chain (A1-A2-B domains) and a light chain (A3-C1-C2 domains). The association of the chains, and the stability and function of the dimer depend on the presence of metal ions. We applied X-ray fluorescence, X-ray crystallographic structure determination with anomalous signals at different wavelengths, and colorimetric measurements to evaluate the metal binding sites in a recombinant factor VIII molecule, turoctocog alfa. We identified a metal binding site in domain A3 dominated by Cu(+) binding and a site in domain A1 dominated by Zn(2+) binding.

  2. Use of ground clay brick as a pozzolanic material to reduce the alkali-silica reaction

    SciTech Connect

    Turanli, L.; Bektas, F.; Monteiro, P.J.M

    2003-10-01

    The objective of this experimental study was to use ground clay brick (GCB) as a pozzolanic material to minimize the alkali-silica reaction expansion. Two different types of clay bricks were finely ground and their activity indices were determined. ASTM accelerated mortar bar tests were performed to investigate the effect of GCB when used to replace cement mass. The microstructure of the mortar was investigated using scanning electron microscopy (SEM). The results showed that the GCBs meet the strength activity requirements of ASTM. In addition, the GCBs were found to be effective in suppressing the alkali-silica reaction expansion. The expansion decreased as the amount of GCBs in the mortar increased.

  3. Fabrication and testing of engineered forms of self-assembled monolayers on mesoporous silica (SAMMS) material

    SciTech Connect

    Mattigod, S.V.; Liu, J.; Fryxell, G.E.; Baskaran, S.; Gong, M.; Nie, Z.; Feng, X.; Klasson, K.T.

    1998-09-01

    A number of engineered forms such as flexible extrudates, beads, and rods were fabricated using thiol-SAMMS (Self-Assembled Monolayers on Mesoporous Silica) and tested for their mercury adsorption capacities. The flexible extrudate form had a mercury adsorption capacity of 340 mg/g but was found to be structurally unstable. A structurally sound bead form of thiol-SAMMS was fabricated with 5, 10, 25, and 40% by weight clay binder (attapulgite) and successfully functionalized. A structurally stable but non-optimized rod form of thiol-SAMMS was also fabricated. Bench-scale processes were developed to silanize and functionalize mesoporous silica beads made with attapulgite clay binder. Contact angle measurements were conducted to assess the degree of surface coverage by functional groups on mesoporous silica materials.

  4. Molecular Dynamics Study on the Particle Dispersion Mechanism of Polyamide-imide/Silica Nano-composite Materials

    NASA Astrophysics Data System (ADS)

    Kikuchi, Hideyuki; Iwasaki, Tomio; Hanawa, Hidehito; Honda, Yuki

    We studied the particle dispersion mechanism of polyamide-imide/silica nano-composite material by using molecular-dynamics simulation technique based on Newtonian dynamics and quantum mechanics. In simulations, adhesive fracture energies at the interfaces between silica and solvents were calculated, and Brownian motions of silica particles were simulated to clarify dispersion properties. The simulation results showed that the colloidal state of silica was maintained by covering the silica surface with a new low hygroscopicity solvent and that the chemical structure of polymer contributed to the dispersion of silica. It is found that the results obtained from molecular dynamics agree well with those obtained by experiments, and that molecular-dynamics simulation technique will become very useful for the development of nano-composite materials in the future.

  5. Evaluation of the acid properties of porous zirconium-doped and undoped silica materials

    SciTech Connect

    Fuentes-Perujo, D.; Santamaria-Gonzalez, J.; Merida-Robles, J.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Maireles-Torres, P. . E-mail: maireles@uma.es; Moreno-Tost, R.

    2006-07-15

    A series of porous silica and Zr-doped silica molecular sieves, belonging to the MCM-41 and MSU families, were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N{sub 2} adsorption at 77 K. Their acid properties have been evaluated by NH{sub 3}-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FT-IR spectroscopy and the catalytic tests of isopropanol decomposition and isomerization of 1-butene. The acidity of purely siliceous solids were, in all cases, very low, while the incorporation of Zr(IV) into the siliceous framework produced an enhancement of the acidity. The adsorption of basic probe molecules and the catalytic behaviour revealed that Zr-doped MSU-type silica was more acidic than the analogous Zr-MCM-41 solid, with a similar Zr content. This high acidity observed in the case of Zr-doped silica samples is due to the presence of surface zirconium atoms with a low coordination, mainly creating Lewis acid sites. - Graphical abstract: The adsorption of basic probe molecules and the catalytic behaviour have revealed that MSU-type materials are more acidic than the analogous MCM-41 solids, mainly after the incorporation of zirconium into the silica framework.

  6. Pure Silica Zeolite Beta Membrane: A Potential Low Dielectric Constant Material For Microprocessor Application

    NASA Astrophysics Data System (ADS)

    Fong, Yeong Yin; Bhatia, Subhash

    The semiconductor industry needs low dielectric constant (low k-value) materials for more advance microprocessor and chips by reducing the size of the device features. In fabricating these contents, a new material with lower k-value than conventional silica (k = 3.9-4.2) is needed in order to improve the circuit performance. The choice of the inorganic zeolite membrane is an attractive option for low k material and suitable for microprocessor applications. A pure silica zeolite beta membrane was synthesized and coated on non-porous stainless steel support using insitu crystallization in the presence of tetraethylammonium hydroxide, TEA (OH), as structure directing agent, fumed silica, HF and deionized water at pH value of 9. The crystallization was carried out for the duration of 14 days under hydrothermal conditions at 130°C. The membrane was characterized by thermogravimetric analysis (TGA), nitrogen adsorption and Scanning Electron Microscope (SEM). SEM results show a highly crystalline; with a truncated square bipyramidal morphology of pure silica zeolite beta membrane strongly adhered on the non-porous stainless steel support. In the present work, the k-value of the membrane was measured as 2.64 which make it suitable for the microprocessor applications.

  7. Kraft lignin/silica-AgNPs as a functional material with antibacterial activity.

    PubMed

    Klapiszewski, Łukasz; Rzemieniecki, Tomasz; Krawczyk, Magdalena; Malina, Dagmara; Norman, Małgorzata; Zdarta, Jakub; Majchrzak, Izabela; Dobrowolska, Anna; Czaczyk, Katarzyna; Jesionowski, Teofil

    2015-10-01

    Advanced functional silica/lignin hybrid materials, modified with nanosilver, were obtained. The commercial silica Syloid 244 was used, modified with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane to increase its chemical affinity to lignin. Similarly, kraft lignin was oxidized using a solution of sodium periodate to activate appropriate functional groups on its surface. Silver nanoparticles were grafted onto the resulting silica/lignin hybrids. The systems obtained were comprehensively tested using available techniques and methods, including transmission electron microscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, elemental analysis and atomic absorption spectroscopy. An evaluation was also made of the electrokinetic stability of the systems with and without silver nanoparticles. Conclusions were drawn concerning the chemical nature of the bonds between the precursors and the effectiveness of the method of binding nanosilver to the hybrid materials. The antimicrobial activity of the studied materials was tested against five species of Gram-positive and Gram-negative bacteria. The addition of silver nanoparticles to the silica/lignin hybrids led to inhibition of the growth of the analyzed bacteria. The best results were obtained against Pseudomonas aeruginosa, a dangerous human pathogen.

  8. A silica sol-gel design strategy for nanostructured metallic materials.

    PubMed

    Warren, Scott C; Perkins, Matthew R; Adams, Ashley M; Kamperman, Marleen; Burns, Andrew A; Arora, Hitesh; Herz, Erik; Suteewong, Teeraporn; Sai, Hiroaki; Li, Zihui; Werner, Jörg; Song, Juho; Werner-Zwanziger, Ulrike; Zwanziger, Josef W; Grätzel, Michael; DiSalvo, Francis J; Wiesner, Ulrich

    2012-03-18

    Batteries, fuel cells and solar cells, among many other high-current-density devices, could benefit from the precise meso- to macroscopic structure control afforded by the silica sol-gel process. The porous materials made by silica sol-gel chemistry are typically insulators, however, which has restricted their application. Here we present a simple, yet highly versatile silica sol-gel process built around a multifunctional sol-gel precursor that is derived from the following: amino acids, hydroxy acids or peptides; a silicon alkoxide; and a metal acetate. This approach allows a wide range of biological functionalities and metals--including noble metals--to be combined into a library of sol-gel materials with a high degree of control over composition and structure. We demonstrate that the sol-gel process based on these precursors is compatible with block-copolymer self-assembly, colloidal crystal templating and the Stöber process. As a result of the exceptionally high metal content, these materials can be thermally processed to make porous nanocomposites with metallic percolation networks that have an electrical conductivity of over 1,000 S cm(-1). This improves the electrical conductivity of porous silica sol-gel nanocomposites by three orders of magnitude over existing approaches, opening applications to high-current-density devices.

  9. Application of mesoporous silica materials for the immobilization of polyphenol oxidase.

    PubMed

    Corell Escuin, Paula; García-Bennett, Alfonso; Ros-Lis, Jose Vicente; Argüelles Foix, Angel; Andrés, Ana

    2017-02-15

    The ability of a number of mesoporous silica materials (SBA-15, SBA-3, and MCM-48) to immobilize polyphenol oxidase (PPO) at different pH has been tested. Pore size and volume are the structural characteristics with higher influence on the PPO immobilization. Mesoropous material SBA-15 adsorbs a larger quantity of PPO at pH 4.00 and offers an inhibition of enzymatic activity close the 50% in apple extracts. PMID:27664646

  10. Application of mesoporous silica materials for the immobilization of polyphenol oxidase.

    PubMed

    Corell Escuin, Paula; García-Bennett, Alfonso; Ros-Lis, Jose Vicente; Argüelles Foix, Angel; Andrés, Ana

    2017-02-15

    The ability of a number of mesoporous silica materials (SBA-15, SBA-3, and MCM-48) to immobilize polyphenol oxidase (PPO) at different pH has been tested. Pore size and volume are the structural characteristics with higher influence on the PPO immobilization. Mesoropous material SBA-15 adsorbs a larger quantity of PPO at pH 4.00 and offers an inhibition of enzymatic activity close the 50% in apple extracts.

  11. High-performance light-emitting diodes encapsulated with silica-filled epoxy materials.

    PubMed

    Li, Tian; Zhang, Jie; Wang, Huiping; Hu, Zhongnan; Yu, Yingfeng

    2013-09-25

    Packaging materials have a great impact on the performance and reliability of light-emitting diodes (LEDs). In this study, we have prepared high performance LED devices through encapsulating LEDs by epoxy materials incorporated with filler powders. A set of evaluation methods have also been established to characterize the reliability of LED devices. No delamination or internal cracking between packaging materials and lead frames has been found for the encapsulated high performance LED devices after the package saturation with moisture and subsequent exposure to high-temperature solder reflow and thermal cycling. Four kinds of inorganic silica fillers, namely, quartz, fused silica, cristobalite, and spherical silica, and one kind of organic filler, that is, spherical silicone powder, were incorporated into the epoxy packaging materials to compare their effects on performance of LED devices. The properties of epoxy packaging materials and LED devices were studied by differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), dynamic mechanical analysis (DMA), thermomechanical analyzer (TMA), ultravioletvisible spectrophotometer (UV-vis), scanning acoustic microscopy (SAM), and scanning electron microscopy (SEM). Except the spherical silicone powder filled epoxy materials, all the other filled systems showed lower equilibrium water sorption content and smaller water diffusion coefficient in both water sorption and moisture sorption tests. The coefficient of thermal expansion (CTE) values were also decreased with the addition of fillers, and the systems filled with quartz, fused, and filled with spherical silica gave the best performance, which exhibited the reduced CTE values both below and above Tg. The results of TGA essentially showed no difference between filled and unfilled systems. The glass transition temperature changed little for all the filled systems, except the one incorporated with spherical silicone. The modulus at room temperature

  12. Microwave material characterization of alkali-silica reaction (ASR) gel in cementitious materials

    NASA Astrophysics Data System (ADS)

    Hashemi, Ashkan

    Since alkali-silica reaction (ASR) was recognized as a durability challenge in cement-based materials over 70 years ago, numerous methods have been utilized to prevent, detect, and mitigate this issue. However, quantifying the amount of produced ASR byproducts (i.e., ASR gel) in-service is still of great interest in the infrastructure industry. The overarching objective of this dissertation is to bring a new understanding to the fundamentals of ASR formation from a microwave dielectric property characterization point-of-view, and more importantly, to investigate the potential for devising a microwave nondestructive testing approach for ASR gel detection and evaluation. To this end, a comprehensive dielectric mixing model was developed with the potential for predicting the effective dielectric constant of mortar samples with and without the presence of ASR gel. To provide pertinent inputs to the model, critical factors on the influence of ASR gel formation on dielectric and reflection properties of several mortar samples were investigated at R, S, and X-band. Effects of humidity, alkali content, and long-term curing conditions on ASR-prone mortars were also investigated. Additionally, dielectric properties of chemically different synthetic ASR gel were also determined. All of these, collectively, served as critical inputs to the mixing model. The resulting developed dielectric mixing model has the potential to be further utilized to quantify the amount of produced ASR gel in cement-based materials. This methodology, once becomes more mature, will bring new insight to the ASR reaction, allowing for advancements in design, detection and mitigation of ASR, and eventually has the potential to become a method-of-choice for in-situ infrastructure health-monitoring of existing structures.

  13. Preparation of bicontinuous mesoporous silica and organosilica materials containing gold nanoparticles by co-synthesis method

    SciTech Connect

    Lee, Byunghwan; Zhu, Haoguo; Zhang, Zongtao; Overbury, Steven {Steve} H; Dai, Sheng

    2004-01-01

    Catalytic activities of gold strongly depend on its particle size. It is necessary to have homogeneous distributions of small gold nanoparticles with diameters between 2 and 5 nm for excellent catalytic activities. In this study, gold-containing mesoporous silica materials were prepared by a co-synthesis method. The essence of this sol-gel co-synthesis method is to combine together neutral surfactant template synthesis of mesoporous silica materials with the introduction of metal ions via bifunctional silane ligands, so that the formation of mesostructures and metal-ion doping occur simultaneously. The formation of gold nanoparticles with size less than 5 nm inside mesoporous materials (HMS, MSU, and PMO) has been achieved by this co-synthesis sol-gel process. In addition, the effects of post-treatments, such as calcination and reduction, on pore structures and nanoparticle size distributions were also investigated.

  14. Molecular Simulation Study of the Early Stages of Formation of Bioinspired Mesoporous Silica Materials.

    PubMed

    Centi, Alessia; Jorge, Miguel

    2016-07-19

    The use of bioinspired templates, such as polyamines and polypeptides, could lead to significant improvements in the synthesis conditions under which mesoporous materials are traditionally produced, removing the need for strong pH as well as high temperature or pressure. In this work, we perform atomistic molecular dynamics simulations of 1,12-diaminododecane surfactants, in water and in the presence of silica monomers, to investigate the early stages of synthesis of one of the first examples of bioinspired silica materials. Different surfactant concentrations and pH were considered, clarifying the influence of the charge state of the molecules on the self-assembly process. We show that the amphiphilic amines form stable lamellar structures at equilibrium in the range from intermediate to high pH values. In a later stage, when silica species are added to the system, our results reveal that, in the same range of pH, silicates strongly adsorb around these aggregates at the interface with water. This causes a considerable modification of the curvature of the layer, which suggests a tendency for the system to evolve from a lamellar phase to the formation of vesicle structures. Furthermore, we show that silica monomers are able to penetrate the layer spontaneously when defects are created as a result of surfactants' head-to-head repulsion. These findings are in agreement with experimental observations and support the pillaring mechanism postulated for this class of materials. However, our simulations indicate that the aggregation process is driven by charge matching between surfactant heads and silica monomers rather than by hydrogen bond interactions between neutral species, as had been previously hypothesized. PMID:27340948

  15. Adsorption of Methyl Blue on Mesoporous Materials Using Rice Husk Ash as Silica Source.

    PubMed

    Nguyen, Nhat Thien; Chen, Shiao-shing; Nguyen, Nguyen Cong; Nguyen, Hau Thi; Tsai, Hsiao Hsin; Chang, Chang Tang

    2016-04-01

    It is recognized that recycling and reuse of waste can result in significant savings in materials and energy. In this research, the adsorption of methyl blue (MB) using waste rice husk ash (Rha) and mesoporous silica materials made from Rha (R-MCM) were analyzed. Mesoporous silica materials were synthesized using cetyltrimethyl ammonium bromide (CTAB) as a cationic surfactant and Rha as the silica source. The prepared samples were characterized by Brunnaur-Emmet-Teller (BET) adsorption isotherm analyzer and transmission electron microscope (TEM) analysis. The results showed the surface area of R-MCM materials was 1347 m2g-1 and the pore volume was 0.906 cm3g-1. TEM analysis showed that the mesoporous materials generally exhibited ordered hexagonal arrays of mesopores with a uniform pore size. The effects on adsorption performance under different initial dye concentrations, different pH values and different dosages of adsorbent were also studied. Both Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. The results show that the maximum removal efficiency of MB more than 99%. PMID:27451772

  16. Shear bond strengths of an indirect composite layering material to a tribochemically silica-coated zirconia framework material.

    PubMed

    Iwasaki, Taro; Komine, Futoshi; Fushiki, Ryosuke; Kubochi, Kei; Shinohara, Mitsuyo; Matsumura, Hideo

    2016-01-01

    This study evaluated shear bond strengths of a layering indirect composite material to a zirconia framework material treated with tribochemical silica coating. Zirconia disks were divided into two groups: ZR-PRE (airborne-particle abrasion) and ZR-PLU (tribochemical silica coating). Indirect composite was bonded to zirconia treated with one of the following primers: Clearfil Ceramic Primer (CCP), Clearfil Mega Bond Primer with Clearfil Porcelain Bond Activator (MGP+Act), ESPE-Sil (SIL), Estenia Opaque Primer, MR. Bond, Super-Bond PZ Primer Liquid A with Liquid B (PZA+PZB), and Super-Bond PZ Primer Liquid B (PZB), or no treatment. Shear bond testing was performed at 0 and 20,000 thermocycles. Post-thermocycling shear bond strengths of ZR-PLU were higher than those of ZR-PRE in CCP, MGP+Act, SIL, PZA+PZB, and PZB groups. Application of silane yielded better durable bond strengths of a layering indirect composite material to a tribochemically silica-coated zirconia framework material. PMID:27252003

  17. Pharmacological activity of metal binding agents that alter copper bioavailability

    PubMed Central

    Helsel, Marian E.

    2015-01-01

    Iron, copper and zinc are required nutrients for many organisms but also potent toxins if misappropriated. An overload of any of these metals can be cytotoxic and ultimately lead to organ failure, whereas deficiencies can result in anemia, weakened immune system function, and other medical conditions. Cellular metal imbalances have been implicated in neurodegenerative diseases, cancer and infection. It is therefore critical for living organisms to maintain careful control of both the total levels and subcellular distributions of these metals to maintain healthy function. This perspective explores several strategies envisioned to alter the bioavailability of metal ions by using synthetic metal-binding agents targeted for diseases where misappropriated metal ions are suspected of exacerbating cellular damage. Specifically, we discuss chemical properties that influence the pharmacological outcome of a subset of metal-binding agents known as ionophores, and review several examples that have shown multiple pharmacological activities in metal-related diseases, with a specific focus on copper. PMID:25797044

  18. Macrocyclization of the ATCUN Motif Controls Metal Binding and Catalysis

    PubMed Central

    Neupane, Kosh P.; Aldous, Amanda R.; Kritzer, Joshua A.

    2013-01-01

    We report the design, synthesis and characterization of macrocyclic analogs of the amino-terminal copper and nickel binding (ATCUN) motif. These macrocycles have altered pH transitions for metal binding, and unlike linear ATCUN motifs, the optimal cyclic peptide 1 binds Cu(II) selectively over Ni(II) at physiological pH. UV-vis and EPR spectroscopy showed that cyclic peptide 1 can coordinate Cu(II) or Ni(II) in a square planar geometry. Metal binding titration and ESI-MS data revealed a 1:1 binding stoichiometry. Macrocyclization allows for coordination of Cu(II) or Ni(II) as in linear ATCUN motifs, but with enhanced DNA cleavage by the Cu(II)-1 complex relative to linear analogs. The Cu(II)-1 complex was also capable of producing diffusible hydroxyl radicals, which is unique among ATCUN motifs and most other common copper(II) chelators. PMID:23421754

  19. Development of vapor deposited silica sol-gel particles for use as a bioactive materials system.

    PubMed

    Snyder, Katherine L; Holmes, Hallie R; VanWagner, Michael J; Hartman, Natalie J; Rajachar, Rupak M

    2013-06-01

    Silica-based sol-gel and bioglass materials are used in a variety of biomedical applications including the surface modification of orthopedic implants and tissue engineering scaffolds. In this work, a simple system for vapor depositing silica sol-gel nano- and micro-particles onto substrates using nebulizer technology has been developed and characterized. Particle morphology, size distribution, and degradation can easily be controlled through key formulation and manufacturing parameters including water:alkoxide molar ratio, pH, deposition time, and substrate character. These particles can be used as a means to rapidly modify substrate surface properties, including surface hydrophobicity (contact angle changes >15°) and roughness (RMS roughness changes of up to 300 nm), creating unique surface topography. Ions (calcium and phosphate) were successfully incorporated into particles, and induced apatitie-like mineral formation upon exposure to simulated body fluid Preosteoblasts (MC3T3) cultured with these particles showed up to twice the adhesivity within 48 h when compared to controls, potentially indicating an increase in cell proliferation, with the effect likely due to both the modified substrate properties as well as the release of silica ions. This novel method has the potential to be used with implants and tissue engineering materials to influence cell behavior including attachment, proliferation, and differentiation via cell-material interactions to promote osteogenesis.

  20. A novel composite material based on antimony(III) oxide and amorphous silica

    SciTech Connect

    Zemnukhova, Ludmila A.; Panasenko, Alexander E.

    2013-05-01

    The composite material nSb₂O₃·mSiO₂·xH₂O was prepared by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. It has been shown that the composition of the material is influenced by the ratio of the initial components and the acidity of the reaction medium. The morphology of the material particles and its specific surface area have been determined. The thermal and optic properties were also investigated. - Graphical abstract: Novel composite material containing amorphous silica and crystal antimony(III) oxide has been synthesized by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. Highlights: • The composite material nSb₂O₃·mSiO₂·xH₂O was prepared in an aqueous medium. • The composition of the material is controllable by a synthesis conditions. • The morphology of the material and its optic properties have been determined.

  1. Silica reusable surface insulation

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Smith, M.; Leiser, D. B. (Inventor)

    1976-01-01

    A reusable silica surface insulation material is provided by bonding amorphous silica fibers with colloidal silica at an elevated temperature. The surface insulation is ordinarily manufactured in the form of blocks (i.e., tiles).

  2. Sol-gel derived silica/siloxane composite materials: The effect of loading level and catalyst activity on silica domain formation

    SciTech Connect

    Black, E.P.; Ulibarri, T.A.; Beaucage, G.; Schaefer, D.W.; Assink, R.A.; Bergstrom, D.F.; Giwa-Agbomeirele, P.A.; Burns, G.T.

    1993-11-01

    Currently, the production of in situ reinforcement in polymeric systems by sol-gel methods is undergoing rapid development. However, understanding of synthesis/structure/property relationships is still lacking. In order to produce sol-gel derived composite materials with sufficient mechanical properties for commercial applications, this deficit of information must be addressed. We have completed a detailed investigation of in situ silica growth in polydimethylsiloxane (PDMS)/tetraethylorthosilicate (TEOS) systems. Factors which affect the domain growth, such as catalyst activity and silica loading, have been examined by solid state {sup 29}Si NMR, SEM, mechanical testing and small angle neutron scattering.

  3. Effect of silica fume on the characterization of the geopolymer materials

    NASA Astrophysics Data System (ADS)

    Khater, Hisham M.

    2013-12-01

    The influence of silica fume (SF) addition on properties of geopolymer materials produced from alkaline activation of alumino-silicates metakaolin and waste concrete produced from demolition works has been studied through the measurement of compressive strength, Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy (SEM) analysis. Alumino-silicate materials are coarse aggregate included waste concrete and fired kaolin (metakaolin) at 800°C for 3 h, both passing a sieve of 90 μm. Mix specimens containing silica fume were prepared at water/binder ratios in a range of 0.30 under water curing. The used activators are an equal mix of sodium hydroxide and silicate in the ratio of 3:3 wt.%. The control geopolymer mix is composed of metakaolin and waste concrete in an equal mix (50:50, wt.%). Waste concrete was partially replaced by silica fume by 1 to 10 wt.%. The results indicated that compressive strengths of geopolymer mixes incorporating SF increased up to 7% substitution and then decreased up to 10% but still higher than that of the control mix. Results indicated that compressive strengths of geopolymer mixes incorporating SF increases up to 7% substitution and then decreases up to 10% but still higher than the control mix, where 7% SF-digested calcium hydroxide (CH) crystals, decreased the orientation of CH crystals, reduced the crystal size of CH gathered at the interface, and improved the interface more effectively.

  4. Preparation of resveratrol-loaded nanoporous silica materials with different structures

    SciTech Connect

    Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

    2014-11-15

    Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.

  5. Silica Polyamine Composites: New Supramolecular Materials for Cation and Anion Recovery and Remediation

    SciTech Connect

    Hughes, Mark; Miranda, Paul; Nielsen, Daniel J.; Rosenberg, Edward; Gobetto, Roberto; Viale, Alessandra; Burton, Sarah D.

    2006-03-01

    The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by 29Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solid state CPMAS-13C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader 13C NMR resonances than the linear polymers poly(allylamine) (PAA) and poly(vinylamine) (PVA). These results are understood in terms of the low energy conformations calculated from molecular modeling studies. Three new applications of the technology are also presented: (1) separation of lanthanides as a group from ferric ion and all other divalent ions; (2) a multi step process for recovering and concentrating the valuable metals in acid mine drainage; (3) a process for removing low level arsenic and selenium in the presence of sulfate using immobilized cations on the composite materials.

  6. [Dust and silica exposure on metallurgical furnace maintenance using refractory materials].

    PubMed

    Garattini, S; Barbieri, P G; Bottone, F; Brunelli, E; Carminati, F; Chiari, R; Sarnico, M

    2012-01-01

    In the metallurgical industries the silica risk has long been known, particularly for the refractoryes maintenance workers. The maintenance of furnaces, ladles and tundisches refractory linings, on the current organization of production, is provided by companies under contract. The information available about the characterization of risk for this group of workers are at present inadequate. The study investigates the exposure to dust, also containing free crystalline silica (SLC), through the analysis of samples of commercial products used in the reconstruction of refractory linings of furnaces, ladles and tundisches, materials from the demolition of refractory articles and dust from work areas. It also presents the results of an environmental investigation conducted during the demolition and reconstruction of the refractory in three steel mills. The Authors, by the numerous inspections and the systematic survey of working conditions, have formulated a SLC risk profile and some proposals for prevention.

  7. Preparation of resveratrol-loaded nanoporous silica materials with different structures

    NASA Astrophysics Data System (ADS)

    Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

    2014-11-01

    Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound.

  8. Power scaling analysis of fiber lasers and amplifiers based on non-silica materials

    SciTech Connect

    Dawson, J W; Messerly, M J; Heebner, J E; Pax, P H; Sridharan, A K; Bullington, A L; Beach, R J; Siders, C W; Barty, C P; Dubinskii, M

    2010-03-30

    A developed formalism for analyzing the power scaling of diffraction limited fiber lasers and amplifiers is applied to a wider range of materials. Limits considered include thermal rupture, thermal lensing, melting of the core, stimulated Raman scattering, stimulated Brillouin scattering, optical damage, bend induced limits on core diameter and limits to coupling of pump diode light into the fiber. For conventional fiber lasers based upon silica, the single aperture, diffraction limited power limit was found to be 36.6kW. This is a hard upper limit that results from an interaction of the stimulated Raman scattering with thermal lensing. This result is dependent only upon physical constants of the material and is independent of the core diameter or fiber length. Other materials will have different results both in terms of ultimate power out and which of the many limits is the determining factor in the results. Materials considered include silica doped with Tm and Er, YAG and YAG based ceramics and Yb doped phosphate glass. Pros and cons of the various materials and their current state of development will be assessed. In particular the impact of excess background loss on laser efficiency is discussed.

  9. Power scaling analysis of fiber lasers and amplifiers based on non-silica materials

    NASA Astrophysics Data System (ADS)

    Dawson, Jay W.; Messerly, Michael J.; Heebner, John E.; Pax, Paul H.; Sridharan, Arun K.; Bullington, Amber L.; Beach, Raymond J.; Siders, Craig W.; Barty, C. P. J.; Dubinskii, Mark

    2010-04-01

    A developed formalism1 for analyzing the power scaling of diffraction limited fiber lasers and amplifiers is applied to a wider range of materials. Limits considered include thermal rupture, thermal lensing, melting of the core, stimulated Raman scattering, stimulated Brillouin scattering, optical damage, bend induced limits on core diameter and limits to coupling of pump diode light into the fiber. For conventional fiber lasers based upon silica, the single aperture, diffraction limited power limit was found to be 36.6kW. This is a hard upper limit that results from an interaction of the stimulated Raman scattering with thermal lensing. This result is dependent only upon physical constants of the material and is independent of the core diameter or fiber length. Other materials will have different results both in terms of ultimate power out and which of the many limits is the determining factor in the results. Materials considered include silica doped with Tm and Er, YAG and YAG based ceramics and Yb doped phosphate glass. Pros and cons of the various materials and their current state of development will be assessed. In particular the impact of excess background loss on laser efficiency is discussed.

  10. SOD1 exhibits allosteric frustration to facilitate metal binding affinity.

    PubMed

    Das, Atanu; Plotkin, Steven S

    2013-03-01

    Superoxide dismutase-1 (SOD1) is a ubiquitous, Cu and Zn binding, free-radical defense enzyme whose misfolding and aggregation play a potential key role in amyotrophic lateral sclerosis, an invariably fatal neurodegenerative disease. Over 150 mutations in SOD1 have been identified with a familial form of the disease, but it is presently not clear what unifying features, if any, these mutants share to make them pathogenic. Here, we develop several unique computational assays for probing the thermo-mechanical properties of both ALS-associated and rationally designed SOD1 variants. Allosteric interaction-free energies between residues and metals are calculated, and a series of atomic force microscopy experiments are simulated with variable tether positions to quantify mechanical rigidity "fingerprints" for SOD1 variants. Mechanical fingerprinting studies of a series of C-terminally truncated mutants, along with an analysis of equilibrium dynamic fluctuations while varying native constraints, potential energy change upon mutation, frustratometer analysis, and analysis of the coupling between local frustration and metal binding interactions for a glycine scan of 90 residues together, reveal that the apo protein is internally frustrated, that these internal stresses are partially relieved by mutation but at the expense of metal-binding affinity, and that the frustration of a residue is directly related to its role in binding metals. This evidence points to apo SOD1 as a strained intermediate with "self-allostery" for high metal-binding affinity. Thus, the prerequisites for the function of SOD1 as an antioxidant compete with apo state thermo-mechanical stability, increasing the susceptibility of the protein to misfold in the apo state.

  11. Asymmetric bioreduction of acetophenones by Baker's yeast and its cell-free extract encapsulated in sol-gel silica materials

    NASA Astrophysics Data System (ADS)

    Kato, Katsuya; Nakamura, Hitomi; Nakanishi, Kazuma

    2014-02-01

    Baker's yeast (BY) encapsulated in silica materials was synthesized using a yeast cell suspension and its cell-free extract during a sol-gel reaction of tetramethoxysilane with nitric acid as a catalyst. The synthesized samples were fully characterized using various methods, such as scanning electron microscopy, nitrogen adsorption-desorption, Fourier transform infrared spectroscopy, thermogravimetry, and differential thermal analysis. The BY cells were easily encapsulated inside silica-gel networks, and the ratio of the cells in the silica gel was approximately 75 wt%, which indicated that a large volume of BY was trapped with a small amount of silica. The enzyme activity (asymmetric reduction of prochiral ketones) of BY and its cell-free extract encapsulated in silica gel was investigated in detail. The activities and enantioselectivities of free and encapsulated BY were similar to those of acetophenone and its fluorine derivatives, which indicated that the conformation structure of BY enzymes inside silica-gel networks did not change. In addition, the encapsulated BY exhibited considerably better solvent (methanol) stability and recyclability compared to free BY solution. We expect that the development of BY encapsulated in sol-gel silica materials will significantly impact the industrial-scale advancement of high-efficiency and low-cost biocatalysts for the synthesis of valuable chiral alcohols.

  12. Simple Synthesis of Hierarchically Ordered Mesocellular Mesoporous Silica Materials Hosting Crosslinked Enzyme Aggregates

    SciTech Connect

    Lee, Jinwoo; Kim, Jungbae; Kim, Jaeyun; Jia, Hongfei; Kim, Moon Il; Kwak, Ja Hun; Jin, Sunmi; Dohnalkova, Alice; Park, Hyun-Gyu; Chang, Ho Nam; Wang, Ping; Grate, Jay W.; Hyeon, Taeghwan

    2005-07-01

    : Hierarchically ordered mesocellular mesoporous silica materials (MMS) were synthesized using a single structure directing agent under neutral conditions for the first time. The mesocellular pores are synthesized without adding any pore expander, and the walls of cellular pores in MMS are composed of SBA-15 type mesopores. The small-angle X-ray scattering (SAXS) pattern of MMS revealed the presence of ordered pore structures with two different length scales. The current MMS possesses four different pore systems; complementary micro/mesopores, main 13 nm mesopores, 40 nm mesocellular spherical pores, and textural inter-particle macropores. Nanometer-scale enzyme reactors (NER) were developed in mesocellular mesoporous silica (MMS) via a ship-in-a-bottle approach, which employs adsorption of enzymes followed by cross-linking using glutaraldehyde (GA) treatment. The resulting NER show an impressive stability and activity with an extremely high loading of enzymes. For example, NER containing α-chymotrypsin (NER-CT) could hold 0.5 g CT in 1 g of silica, but the specific activity of NER-CT was 10.4 times higher than that of the adsorbed CT with a lower loading (0.07 g CT per 1 g of silica), which was further decreased by a continuous leaching of adsorbed CT. NER-CT showed excellent stability without any leaching, i.e. no activity decrease at all in a rigorously-shaking condition for two weeks (a half-life with 3.8 years), while the conventional adsorption method resulted in a half-life of 3.6 days in the same condition.

  13. Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

    SciTech Connect

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-08-11

    Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

  14. Spherical β-cyclodextrin-silica hybrid materials for multifunctional chiral stationary phases.

    PubMed

    Wang, Litao; Dong, Shuqing; Han, Feng; Zhao, Yingwei; Zhang, Xia; Zhang, Xiaoli; Qiu, Hongdeng; Zhao, Liang

    2015-02-27

    Spherical β-CD-silica hybrid materials have been prepared successfully by simple one-pot polymerization, which provide a new strategy to construct new type of HPLC chiral stationary phases. Various β-CD, ethane, triazinyl and 3,5-dimethylphenyl functional groups that can provide multiple interactions were introduced into the pore channels and pore wall framework of mesoporous materials, respectively. The materials towards some chiral, acidic, anilines and phenols compounds showed multiple chromatographic separation functions including racemic resolution, anion exchange and achiral separations with a typical feature of normal/reversed phase chromatography. Multi-tasking including racemic resolution and achiral separations for selected compounds were performed simultaneously on a chiral chromatographic column. The multifunctional character of materials arises from the multiple interactions including hydrophobic interaction, π-π interaction, anion exchange, inclusion interaction and hydrogen bonding interaction. PMID:25637012

  15. Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

    SciTech Connect

    Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

    2015-07-14

    Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

  16. A new method for synthesizing fluid inclusions in fused silica capillaries containing organic and inorganic material

    USGS Publications Warehouse

    Chou, I.-Ming; Song, Y.; Burruss, R.C.

    2008-01-01

    Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 ?? 0.3 mm with 0.05 ?? 0.05 mm or 0.1 ?? 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 ??C) and temperature (T; about 500 ??C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 ??C). The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 ??C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress. When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3

  17. Dimensional stability of fused silica, Invar, and several ultralow thermal expansion materials

    NASA Technical Reports Server (NTRS)

    Berthold, J. W., III; Jacobs, S. F.; Norton, M. A.

    1976-01-01

    A method is developed for testing the long-term dimensional stability of an iodine-stabilized He-Ne laser, using a technique whereby thermal expansion coefficients are measured by forming a Fabry-Perot etalon from the sample and monitoring the optical resonant frequencies with tunable sidebands impressed on a laser beam from a frequency-stabilized He-Ne laser. A change of 1 ppm over a 3-yr period on the part of fused silica dimensions and the differential thermal expansion of Invar LR-35 and Super Invar materials are noted. The method is of interest for the metrology of extremely stable structures such as telescopes and optical resonators.

  18. The metal-binding sites of glycose phosphates.

    PubMed

    Gilg, Kathrin; Mayer, Tobias; Ghaschghaie, Natascha; Klüfers, Peter

    2009-10-14

    In aqueous solution, the reducing sugar phosphates D-arabinose 5-phosphate, D-ribose 5-phosphate, D-fructose 1,6-bisphosphate, D-fructose 6-phosphate, D-glucose 6-phosphate and D-mannose 6-phosphate provide metal-binding sites at their glycose core on reaction with Pd(II)(en) or M(III)(tacn) residues (M = Ga, Co; en = ethylenediamine, tacn = 1,4,7-triazacyclononane). The individual species were detected by one- and two-dimensional NMR spectroscopy. The coordination patterns are related to the metal-binding modes of the respective parent glycoses. In detail, ribo- and arabinofuranose phosphate favour kappaO(1,3) coordination, whereas the ketofuranose core of fructose phosphate and fructose bisphosphate provides the kappaO(2,3) chelator thus maintaining the configuration of the respective major solution anomer. On palladium excess, D-fructose 6-phosphate is metallated twice in a unique kappaO(1,3):kappaO(2,4) metallation pattern. Dimetallation is also found for the aldohexose phosphates. A mixed glycose-core-phosphate chelation was detected for Pd(II)(en) and M(III)(tacn) residues with M = Al, Ga in the pH range just above the physiological pH for the D-fructose 1,6-bisphosphate ligand. The results are discussed in relation to D-fructose-1,6-bisphosphate-metabolism in class-II aldolases. PMID:19771356

  19. Reflectance Spectra Diversity of Silica-Rich Materials: Sensitivity to Environment and Implications for Detections on Mars

    NASA Technical Reports Server (NTRS)

    Rice, M. S.; Cloutis, E. A.; Bell, J. F., III; Bish, D. L.; Horgan, B. H.; Mertzman, S. A.; Craig, M. A.; Renault, R. W.; Gautason, B.; Mountain, B.

    2013-01-01

    Hydrated silica-rich materials have recently been discovered on the surface of Mars by the Mars Exploration Rover (MER) Spirit, the Mars Reconnaissance Orbiter (MRO) Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), and the Mars Express Observatoire pour la Mineralogie, l'Eau, les Glaces, et l'Activite'(OMEGA) in several locations. Having been interpreted as hydrothermal deposits and aqueous alteration products, these materials have important implications for the history of water on the martian surface. Spectral detections of these materials in visible to near infrared (Vis NIR) wavelengths have been based on a H2O absorption feature in the 934-1009 nm region seen with Spirit s Pancam instrument, and on SiOH absorption features in the 2.21-2.26 micron range seen with CRISM. Our work aims to determine how the spectral reflectance properties of silica-rich materials in Vis NIR wavelengths vary as a function of environmental conditions and formation. Here we present laboratory reflectance spectra of a diverse suite of silica-rich materials (chert, opal, quartz, natural sinters and synthetic silica) under a range of grain sizes and temperature, pressure, and humidity conditions. We find that the H2O content and form of H2O/OH present in silica-rich materials can have significant effects on their Vis NIR spectra. Our main findings are that the position of the approx.1.4 microns OH feature and the symmetry of the approx.1.9 microns feature can be used to discern between various forms of silica-rich materials, and that the ratio of the approx.2.2 microns (SiOH) and approx.1.9 microns (H2O) band depths can aid in distinguishing between silica phases (opal-A vs. opal-CT) and formation conditions (low vs. high temperature). In a case study of hydrated silica outcrops in Valles Marineris, we show that careful application of a modified version of these spectral parameters to orbital near-infrared spectra (e.g., from CRISM and OMEGA) can aid in characterizing the

  20. Fumed silica nanoparticle mediated biomimicry for optimal cell-material interactions for artificial organ development.

    PubMed

    de Mel, Achala; Ramesh, Bala; Scurr, David J; Alexander, Morgan R; Hamilton, George; Birchall, Martin; Seifalian, Alexander M

    2014-03-01

    Replacement of irreversibly damaged organs due to chronic disease, with suitable tissue engineered implants is now a familiar area of interest to clinicians and multidisciplinary scientists. Ideal tissue engineering approaches require scaffolds to be tailor made to mimic physiological environments of interest with specific surface topographical and biological properties for optimal cell-material interactions. This study demonstrates a single-step procedure for inducing biomimicry in a novel nanocomposite base material scaffold, to re-create the extracellular matrix, which is required for stem cell integration and differentiation to mature cells. Fumed silica nanoparticle mediated procedure of scaffold functionalization, can be potentially adapted with multiple bioactive molecules to induce cellular biomimicry, in the development human organs. The proposed nanocomposite materials already in patients for number of implants, including world first synthetic trachea, tear ducts and vascular bypass graft.

  1. Fumed silica nanoparticle mediated biomimicry for optimal cell-material interactions for artificial organ development.

    PubMed

    de Mel, Achala; Ramesh, Bala; Scurr, David J; Alexander, Morgan R; Hamilton, George; Birchall, Martin; Seifalian, Alexander M

    2014-03-01

    Replacement of irreversibly damaged organs due to chronic disease, with suitable tissue engineered implants is now a familiar area of interest to clinicians and multidisciplinary scientists. Ideal tissue engineering approaches require scaffolds to be tailor made to mimic physiological environments of interest with specific surface topographical and biological properties for optimal cell-material interactions. This study demonstrates a single-step procedure for inducing biomimicry in a novel nanocomposite base material scaffold, to re-create the extracellular matrix, which is required for stem cell integration and differentiation to mature cells. Fumed silica nanoparticle mediated procedure of scaffold functionalization, can be potentially adapted with multiple bioactive molecules to induce cellular biomimicry, in the development human organs. The proposed nanocomposite materials already in patients for number of implants, including world first synthetic trachea, tear ducts and vascular bypass graft. PMID:24243739

  2. Structural and dynamical properties of guest molecules confined in mesoporous silica materials revealed by NMR.

    PubMed

    Buntkowsky, Gerd; Breitzke, Hergen; Adamczyk, Anna; Roelofs, Frank; Emmler, Thomas; Gedat, Egbert; Grünberg, Bob; Xu, Yeping; Limbach, Hans-Heinrich; Shenderovich, Ilja; Vyalikh, Anastasia; Findenegg, Gerhard

    2007-09-21

    In the last fifteen years several novel porous silica materials, which are periodically structured on the mesoscopic length scale, have been synthesized. They are of broad interest for fundamental studies of surface-substrate interactions, for studies of the dynamics of guest molecules in confinement and for studies of the effect of confinement on the structural and thermophysical properties of fluids. Examples of such confinement effects include the change of the freezing and melting points or glass transitions of the confined liquids. These effects are studied by combinations of several NMR techniques, such as (15)N- and (2)H-solid-state NMR line shape analysis, MAS NMR and NMR diffusometry with physico-chemical characterization techniques such as nitrogen adsorption and small angle diffraction of neutrons or X-rays. This combination does not require crystalline samples or special clean and well defined surfaces such as conventional surface science techniques, but can work with typical ill-defined real world systems. The review discusses, after a short introduction, the salient features of these materials and the applied NMR experiments to give the reader a basic knowledge of the systems and the experiments. The rest of the review then focuses on the structural and dynamical properties of guest molecules confined in the mesoporous silica. It is shown that the confinement into the pores leads to fascinating new features of the guests, which are often not known for their bulk phases. These features depend strongly on the interplay of the their interactions with the silica surface and their mutual interactions. PMID:17912415

  3. Influence of geometry on mechanical properties of bio-inspired silica-based hierarchical materials.

    PubMed

    Dimas, Leon S; Buehler, Markus J

    2012-09-01

    Diatoms, bone, nacre and deep-sea sponges are mineralized natural structures found abundantly in nature. They exhibit mechanical properties on par with advanced engineering materials, yet their fundamental building blocks are brittle and weak. An intriguing characteristic of these structures is their heterogeneous distribution of mechanical properties. Specifically, diatoms exhibit nanoscale porosity in specific geometrical configurations to create regions with distinct stress strain responses, notably based on a single and simple building block, silica. The study reported here, using models derived from first principles based full atomistic studies with the ReaxFF reactive force field, focuses on the mechanics and deformation mechanisms of silica-based nanocomposites inspired by mineralized structures. We examine single edged notched tensile specimens and analyze stress and strain fields under varied sample size in order to gain fundamental insights into the deformation mechanisms of structures with distinct ordered arrangements of soft and stiff phases. We find that hierarchical arrangements of silica nanostructures markedly change the stress and strain transfer in the samples. The combined action of strain transfer in the deformable phase, and stress transfer in the strong phase, acts synergistically to reduce the intensity of stress concentrations around a crack tip, and renders the resulting composites less sensitive to the presence of flaws, for certain geometrical configurations it even leads to stable crack propagation. A systematic study allows us to identify composite structures with superior fracture mechanical properties relative to their constituents, akin to many natural biomineralized materials that turn the weaknesses of building blocks into a strength of the overall system. PMID:22740585

  4. Structural investigation of nonionic fluorinated micelles by SANS in relation to mesoporous silica materials.

    PubMed

    Michaux, Florentin; Blin, Jean-Luc; Teixeira, José; Stébé, Marie José

    2012-01-12

    In an attempt to answer the question if there is dependence between the pore ordering of the mesoporous silica, obtained through the cooperative template mechanism, and the shape of the micellar aggregates of the surfactant solutions, the micellar structures of two nonionic fluorinated surfactant based-systems are studied by SANS. By fitting the experimental spectra with theoretical models, the structural evolution of the molecular aggregates can be described, and some important parameters can be obtained, such as the water and eventually oil penetration into the surfactant film, the aggregation number, the area per polar head of the surfactant, and the surfactant chain conformations. We have shown that for the C(8)F(17)C(2)H(4)(OC(2)H(4))(9)OH system, the micelles are prolate spheroids. The increase of the surfactant concentration in water does not change the characteristics of the interfacial film, but the aggregation number raises and the particles become more elongated. By contrast, the experimental curves of C(7)F(15)C(2)H(4)(OC(2)H(4))(8)OH cannot be fitted considering a small particle model. However, progressive incorporation of fluorocarbon induces a change of size and shape of the globules, which become smaller and more and more spherical. Regarding the material mesopore ordering, it appears that the micelles that lead to hexagonal mesoporous silica materials are described with a model of quasi-spherical globules. On the contrary, when large micelles are found, only wormhole-like structures are obtained.

  5. Rational Catalyst Design of Titanium-Silica Materials Aided by Site-Specific Titration Tools

    NASA Astrophysics Data System (ADS)

    Eaton, Todd Robert

    Silica-supported titanium materials are widely used for thermocatalytic applications such as hydroxylation of alkanes and aromatics, oxidation of alcohols and ethers, ammoximation of carbonyls, and sulfoxidations, while Ti-based materials are widely studied for photocatalytic applications such as photo-oxidation of organic substrates and photo-reduction of CO 2. However, the underlying phenomena of how to synthesize, identify, and control the active structures in these materials is not well understood because of the narrow scope of previous work. Studies of titanium-based catalysts typically focus on materials where the metal is present as either highly-dispersed Ti cations or in bulk crystalline TiO2 form, neglecting the numerous and potentially useful intermediate structures. Furthermore, these works typically focus on a single synthesis technique and rely upon bulk characterization techniques to understand the materials. Here rigorous titanium-silica synthesis-structure-function relationships are established by examining several different synthetic method and utilizing characterization techniques that enable an atomic-level understanding of the materials. The materials studied span the range from isolated Ti cations to clustered TiOx domains, polymeric TiO x domains, anatase-like 2D TiO2 domains, and 3D crystalline TiO2. Tools to quantify accessible TiO x and tetrahedral Ti sites are developed, utilizing the selective titration of titanium with phenylphosphonic acid (PPA). Catalytic properties are probed with the photocatalytic oxidation of benzyl alcohol and the thermocatalytic epoxidation of cis-cyclooctene with H2O2 . PPA titration data indicate that the rate of benzyl alcohol photo-oxidation is independent of titanium coordination, while the rate of alkene epoxidation with H2O2 is proportional to the number of tetrahedral titanium sites on the catalyst. PPA titration data also enables the estimation of TiO2 particle size and reveals an important distinction

  6. Collagen-silica hybrid materials: sodium silicate and sodium chloride effects on type I collagen fibrillogenesis.

    PubMed

    Eglin, David; Coradin, Thibaud; Giraud Guille, Marie M; Helary, Christophe; Livage, Jacques

    2005-01-01

    Collagen-silica hybrid materials have been considered for potential biomedical applications. Understanding of the collagen-silica interactions is the key to control hybrids structure and properties. For this purpose, the effect of sodium silicate and sodium chloride addition at two concentrations, 0.83 and 10 mM, on the kinetic of the type I collagen fibrillogenesis at 20 degrees C, and pH 7.4 were studied. Absorbance profiles of fibrillogenesis experiments were collected together with measures of silicic acid concentration and transmission electron microscopy analysis. The specific effect of silica addition on the collagen fibrils self-assembly mechanisms was demonstrated by comparison with the sodium chloride. Sodium silicate at 10 mM inhibited the collagen fibrillogenesis. At the same concentration, the sodium chloride decreased the rate of the collagen fibril assembly. Collagen fibrillogenesis kinetic was not significantly disturbed by the presence of 0.83 mM of sodium chloride. However, the same concentration of sodium silicate modified the collagen fibrillogenesis kinetic. Transmission electron microscopy indicated for experiment with 0.83 mM of sodium silicate, the formation of longer and wider fibrils than for the equivalent collagen fibrillogenesis experiment with sodium chloride. The effect of sodium chloride is explained in terms of osmotic exclusion and influence on electrostatic interactions between collagen fibrils. The specific involvement of silicic acid in collagen helices hydrogen-bond interactions is suggested. Finally, the results of this study are discussed regarding the preparation of composites by co-gelation of type I collagen and sodium silicate, for potential application as bone repair device.

  7. Metal binding proteins, recombinant host cells and methods

    DOEpatents

    Summers, Anne O.; Caguiat, Jonathan J.

    2004-06-15

    The present disclosure provides artificial heavy metal binding proteins termed chelons by the inventors. These chelons bind cadmium and/or mercuric ions with relatively high affinity. Also disclosed are coding sequences, recombinant DNA molecules and recombinant host cells comprising those recombinant DNA molecules for expression of the chelon proteins. In the recombinant host cells or transgenic plants, the chelons can be used to bind heavy metals taken up from contaminated soil, groundwater or irrigation water and to concentrate and sequester those ions. Recombinant enteric bacteria can be used within the gastrointestinal tracts of animals or humans exposed to toxic metal ions such as mercury and/or cadmium, where the chelon recombinantly expressed in chosen in accordance with the ion to be rededicated. Alternatively, the chelons can be immobilized to solid supports to bind and concentrate heavy metals from a contaminated aqueous medium including biological fluids.

  8. Multinuclear metal-binding ability of a carotene

    PubMed Central

    Horiuchi, Shinnosuke; Tachibana, Yuki; Yamashita, Mitsuki; Yamamoto, Koji; Masai, Kohei; Takase, Kohei; Matsutani, Teruo; Kawamata, Shiori; Kurashige, Yuki; Yanai, Takeshi; Murahashi, Tetsuro

    2015-01-01

    Carotenes are naturally abundant unsaturated hydrocarbon pigments, and their fascinating physical and chemical properties have been studied intensively not only for better understanding of the roles in biological processes but also for the use in artificial chemical systems. However, their metal-binding ability has been virtually unexplored. Here we report that β-carotene has the ability to assemble and align ten metal atoms to afford decanuclear homo- and heterometal chain complexes. The metallo–carotenoid framework shows reversible metalation–demetalation reactivity with multiple metals, which allows us to control the size of metal chains as well as the heterobimetallic composition and arrangement of the carotene-supported metal chains. PMID:25857402

  9. Biosynthetic regulation of phytochelatins, heavy metal-binding peptides.

    PubMed

    Hirata, Kazumasa; Tsuji, Naoki; Miyamoto, Kazuhisa

    2005-12-01

    Phytochelatins (PCs) are heavy metal-binding peptides that play important roles in the detoxification of toxic heavy metals and the regulation of intracellular concentrations of essential metals in eukaryotes, including higher plants, fungi, and microalgae. Recently, PC synthase genes in higher plants and fission yeast have been identified and characterized, enabling molecular biological studies to unravel the mechanisms underlying PC synthesis. Moreover, recent routine database searches have unexpectedly identified genes that are similar to plant PC synthase genes in the genomes of worms and some prokaryotes. In this review, we introduce these recent advances in our understanding of the molecular mechanisms for PC biosynthesis and functions in order to supply basic information about the unique and attractive peptides applicable to various fields.

  10. Thermal expansion coefficient prediction of fuel-cell seal materials from silica sand

    NASA Astrophysics Data System (ADS)

    Hidayat, Nurul; Triwikantoro, Baqiya, Malik A.; Pratapa, Suminar

    2013-09-01

    This study is focused on the prediction of coefficient of thermal expansion (CTE) of silica-sand-based fuel-cell seal materials (FcSMs) which in principle require a CTE value in the range of 9.5-12 ppm/°C. A semi-quantitative theoretical method to predict the CTE value is proposed by applying the analyzed phase compositions from XRD data and characterized density-porosity behavior. A typical silica sand was milled at 150 rpm for 1 hour followed by heating at 1000 °C for another hour. The sand and heated samples were characterized by means of XRD to perceive the phase composition correlation between them. Rietveld refinement was executed to investigate the weight fraction of the phase contained in the samples, and then converted to volume fraction for composite CTE calculations. The result was applied to predict their potential physical properties for FcSM. Porosity was taken into account in the calculation after which it was directly measured by the Archimedes method.

  11. Evaluation and optimization of the metal-binding properties of a complex ligand for immobilized metal affinity chromatography.

    PubMed

    Chen, Bin; Li, Rong; Li, Shiyu; Chen, Xiaoli; Yang, Kaidi; Chen, Guoliang; Ma, Xiaoxun

    2016-02-01

    The simultaneous determination of two binding parameters for metal ions on an immobilized metal affinity chromatography column was performed by frontal chromatography. In this study, the binding parameters of Cu(2+) to l-glutamic acid were measured, the metal ion-binding characteristics of the complex ligand were evaluated. The linear correlation coefficients were all greater than 99%, and the relative standard deviations of two binding parameters were 0.58 and 0.059%, respectively. The experiments proved that the frontal chromatography method was accurate, reproducible, and could be used to determine the metal-binding parameters of the affinity column. The effects of buffer pH, type, and concentration on binding parameters were explored by uniform design experiment. Regression, matching and residual analyses of the models were performed. Meanwhile, the optimum-binding conditions of Cu(2+) on the l-glutamic acid-silica column were obtained. Under these binding conditions, observations and regression values of two parameters were similar, and the observation values were the best. The results demonstrated that high intensity metal affinity column could be effectively prepared by measuring and evaluating binding parameters using frontal chromatography combined with a uniform design experiment. The present work provided a new mode for evaluating and preparing immobilized metal affinity column with good metal-binding behaviors. PMID:26632098

  12. A novel silica alumina-based backfill material composed of coal refuse and fly ash.

    PubMed

    Yao, Yuan; Sun, Henghu

    2012-04-30

    In this paper, a systematic study was conducted to investigate a novel silica alumina-based backfill material composed of coal refuse and fly ash. The coal refuse and fly ash had different properties under various thermal activation temperatures (20 °C, 150 °C, 350 °C, 550 °C, 750 °C and 950 °C). It is known that a thermal activation temperature ranging from 20 °C to 950 °C significantly increases the flowability and pozzolanic properties of the coal refuse; however, the flowability of fly ash decreases when the activation temperature is higher than 550 °C because of a severe agglomeration phenomenon on its surface. An optimal design for this backfill material was determined to include an activated portion composed of 5% coal refuse at 750 °C and 15% fly ash at 20 °C. This combination yields the best performance with excellent flowability, a high compressive strength and a low bleeding rate. The microanalysis results corresponded well with the performance tests at different activation conditions. In the coal refuse, kaolinite peaks began to decrease because of their transformation into metakaolin at 550 °C. Chlorite peaks disappeared at 750 °C. Muscovite peaks decreased at 750 °C and disappeared at 950 °C. During this process, muscovite 2M(1) gradually dehydroxylated to muscovite HT. Furthermore, this paper examined the environmental acceptance and economic feasibility of this technology and found that this silica alumina-based backfill material composed of coal refuse and fly ash not only meets EPA requirements but also has several advantages in industry feasibility when compared with hydraulic backfill, rock backfill and paste backfill.

  13. Entrapping quercetin in silica/polyethylene glycol hybrid materials: Chemical characterization and biocompatibility.

    PubMed

    Catauro, Michelina; Bollino, Flavia; Nocera, Paola; Piccolella, Simona; Pacifico, Severina

    2016-11-01

    Sol-gel synthesis was exploited to entrap quercetin, a natural occurring antioxidant polyphenol, in silica-based hybrid materials, which differed in their polyethylene glycol (PEG) content (6, 12, 24 and 50wt%). The materials obtained, whose nano-composite nature was ascertained by Scanning Electron Microscopy (SEM), were chemically characterized by Fourier Transform InfraRed (FT-IR) and UV-Vis spectroscopies. The results prove that a reaction between the polymer and the drug occurred. Bioactivity tests showed their ability to induce hydroxyapatite nucleation on the sample surfaces. The direct contact method was applied to screen the cytotoxicity of the synthetized materials towards fibroblast NIH 3T3 cells, commonly used for in vitro biocompatibility studies, and three nervous system cell lines (neuroblastoma SH-SY5Y, glioma U251, and pheochromocytoma PC12 cell lines), adopted as models in oxidative stress related studies. Using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay NIH 3T3 proliferation was assessed and the morphology was not compromised by direct exposure to the materials. Analogously, PC-12, and U-251 cell lines were not affected by new materials. SH-SY5Y appeared to be the most sensitive cell line with cytotoxic effects of 20-35%.

  14. Entrapping quercetin in silica/polyethylene glycol hybrid materials: Chemical characterization and biocompatibility.

    PubMed

    Catauro, Michelina; Bollino, Flavia; Nocera, Paola; Piccolella, Simona; Pacifico, Severina

    2016-11-01

    Sol-gel synthesis was exploited to entrap quercetin, a natural occurring antioxidant polyphenol, in silica-based hybrid materials, which differed in their polyethylene glycol (PEG) content (6, 12, 24 and 50wt%). The materials obtained, whose nano-composite nature was ascertained by Scanning Electron Microscopy (SEM), were chemically characterized by Fourier Transform InfraRed (FT-IR) and UV-Vis spectroscopies. The results prove that a reaction between the polymer and the drug occurred. Bioactivity tests showed their ability to induce hydroxyapatite nucleation on the sample surfaces. The direct contact method was applied to screen the cytotoxicity of the synthetized materials towards fibroblast NIH 3T3 cells, commonly used for in vitro biocompatibility studies, and three nervous system cell lines (neuroblastoma SH-SY5Y, glioma U251, and pheochromocytoma PC12 cell lines), adopted as models in oxidative stress related studies. Using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay NIH 3T3 proliferation was assessed and the morphology was not compromised by direct exposure to the materials. Analogously, PC-12, and U-251 cell lines were not affected by new materials. SH-SY5Y appeared to be the most sensitive cell line with cytotoxic effects of 20-35%. PMID:27524014

  15. Material removal and surface figure during pad polishing of fused silica

    SciTech Connect

    Suratwala, T I; Feit, M D; Steele, W A

    2009-05-04

    The material removal and surface figure after ceria pad polishing of fused silica glass have been measured and analyzed as a function of kinematics, loading conditions, and polishing time. Also, the friction at the workpiece/lap interface, the slope of the workpiece relative to the lap plane, and lap viscoelastic properties have been measured and correlated to material removal. The results show that the relative velocity between the workpiece & lap (determined by the kinematics) and the pressure distribution determine the spatial and temporal material removal and hence the final surface figure of the workpiece. In the case where the applied loading and relative velocity distribution over the workpiece are spatially uniform, a significant non-uniform spatial material removal from the workpiece surface is observed. This is due to a non-uniform pressure distribution resulting from: (1) a moment caused by a pivot point and interface friction forces; (2) viscoelastic relaxation of the polyurethane lap; and (3) a physical workpiece/lap interface mismatch. Both the kinematics and these contributions to the pressure distribution are quantitatively described, and then combined to form a spatial and temporal Preston model & code for material removal (called Surface Figure or SurF{copyright}). The surface figure simulations are consistent with the experiment for a wide variety of polishing conditions. This study is an important step towards deterministic full-aperture polishing, which would allow optical glass fabrication to be performed in a more repeatable, less iterative, and hence more economical manner.

  16. Silica hollow nanospheres as new nanoscaffold materials to enhance hydrogen releasing from ammonia borane.

    PubMed

    Zhang, Tianran; Yang, Xiaojing; Yang, Siqi; Li, Daixin; Cheng, Fangyi; Tao, Zhanliang; Chen, Jun

    2011-11-01

    Silica hollow nanospheres (SHNS) are used as new nanoscaffold materials to confine ammonia borane (NH(3)BH(3), AB) for enhancing the dehydrogenation process. Different loading levels of AB in SHNS are considered and AB/4SHNS (with AB content of approximately 20 wt%) shows the best result. The onset temperature of the dehydrogenation of AB in SHNS is as low as 70 °C with the peak temperature at 99 °C and no other gases such as borazine and ammonia are detected. Furthermore, within 60 min at 85 °C, 0.53 equivalent of hydrogen is released and the activation energy is 97.6 kJ mol(-1). Through FT-IR, Raman spectrum and density functional theory (DFT) calculation, it is found that nanoconfinement effect combined with SiO-HH-B interaction is essential for the enhancement of hydrogen releasing. PMID:21947307

  17. Photovoltaic's silica-rich waste sludge as supplementary cementitious material (SCM)

    SciTech Connect

    Quercia, G.; Putten, J.J.G. van der; Hüsken, G.; Brouwers, H.J.H.

    2013-12-15

    Waste sludge, a solid recovered from wastewater of photovoltaic-industries, composes of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. This sludge deflocculates in aqueous solutions into nano-particles smaller than 1 μm. Thus, this sludge constitutes a potentially hazardous waste when it is improperly disposed. Due to its high content of amorphous SiO{sub 2}, this sludge has a potential use as supplementary cementitious material (SCM) in concrete. In this study the main properties of three different samples of photovoltaic's silica-rich waste sludge (nSS) were physically and chemically characterized. The characterization techniques included: scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), nitrogen physical adsorption isotherm (BET method), density by Helium pycnometry, particle size distribution determined by laser light scattering (LLS) and zeta-potential measurements by dynamic light scattering (DLS). In addition, a dispersability study was performed to design stable slurries to be used as liquid additives for the concrete production on site. The effects on the hydration kinetics of cement pastes by the incorporation of nSS in the designed slurries were determined using an isothermal calorimeter. A compressive strength test of standard mortars with 7% of cement replacement was performed to determine the pozzolanic activity of the waste nano-silica sludge. Finally, the hardened system was fully characterized to determine the phase composition. The results demonstrate that the nSS can be utilized as SCM to replace portion of cement in mortars, thereby decreasing the CO{sub 2} footprint and the environmental impact of concrete. -- Highlights: •Three different samples of PV nano-silica sludge (nSS) were fully characterized. •nSS is composed of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. •Dispersability studies demonstrated that nSS agglomerates are broken to nano

  18. Monodisperse hollow silica nanospheres for nano insulation materials: synthesis, characterization, and life cycle assessment.

    PubMed

    Gao, Tao; Jelle, Bjørn Petter; Sandberg, Linn Ingunn C; Gustavsen, Arild

    2013-02-01

    The application of manufactured nanomaterials provides not only advantages resulting from their unique properties but also disadvantages derived from the high energy use and CO(2) burden related to their manufacture, operation, and disposal. It is therefore important to understand the trade-offs of process economics of nanomaterial production and their associated environmental footprints in order to strengthen the existing advantages while counteracting disadvantages. This work reports the synthesis, characterization, and life cycle assessment (LCA) of a new type of superinsulating materials, nano insulation materials (NIMs), which are made of hollow silica nanospheres (HSNSs) and have great flexibility in modifying their properties by tuning the corresponding structural parameters. The as-prepared HSNSs in this work have a typical inner pore diameter of about 150 nm and a shell thickness of about 10-15 nm and exhibit a reduced thermal conductivity of about 0.02 W/(m K) because of their size-dependent thermal conduction at the nanometer scale. The energy and raw material consumption related to the synthesis of HSNSs have been analyzed by the LCA method. The results indicate that the recycle of chemicals, up-scaling production, and use of environmentally friendly materials can greatly affect the process of environmental footprints. New synthesis routes for NIMs with improved thermal performance and energy and environmental features are also recommended on the basis of the LCA study.

  19. Identification and characterization of a novel high affinity metal-binding site in the hammerhead ribozyme.

    PubMed Central

    Hansen, M R; Simorre, J P; Hanson, P; Mokler, V; Bellon, L; Beigelman, L; Pardi, A

    1999-01-01

    A novel metal-binding site has been identified in the hammerhead ribozyme by 31P NMR. The metal-binding site is associated with the A13 phosphate in the catalytic core of the hammerhead ribozyme and is distinct from any previously identified metal-binding sites. 31P NMR spectroscopy was used to measure the metal-binding affinity for this site and leads to an apparent dissociation constant of 250-570 microM at 25 degrees C for binding of a single Mg2+ ion. The NMR data also show evidence of a structural change at this site upon metal binding and these results are compared with previous data on metal-induced structural changes in the core of the hammerhead ribozyme. These NMR data were combined with the X-ray structure of the hammerhead ribozyme (Pley HW, Flaherty KM, McKay DB. 1994. Nature 372:68-74) to model RNA ligands involved in binding the metal at this A13 site. In this model, the A13 metal-binding site is structurally similar to the previously identified A(g) metal-binding site and illustrates the symmetrical nature of the tandem G x A base pairs in domain 2 of the hammerhead ribozyme. These results demonstrate that 31P NMR represents an important method for both identification and characterization of metal-binding sites in nucleic acids. PMID:10445883

  20. Imaging the early material response associated with exit surface damage in fused silica

    SciTech Connect

    Demos, S G; Raman, R N; Negres, R A

    2010-11-05

    The processes involved at the onset of damage initiation on the surface of fused silica have been a topic of extensive discussion and thought for more than four decades. Limited experimental results have helped develop models covering specific aspects of the process. In this work we present the results of an experimental study aiming at imaging the material response from the onset of the observation of material modification during exposure to the laser pulse through the time point at which material ejection begins. The system involves damage initiation using a 355 nm pulse, 7.8 ns FWHM in duration and imaging of the affected material volume with spatial resolution on the order of 1 {micro}m using as strobe light a 150 ps laser pulse that is appropriately timed with respect to the pump pulse. The observations reveal that the onset of material modification is associated with regions of increased absorption, i.e., formation of an electronic excitation, leading to a reduction in the probe transmission to only a few percent within a time interval of about 1 ns. This area is subsequently rapidly expanding with a speed of about 1.2 {micro}m/ns and is accompanied by the formation and propagation of radial cracks. These cracks appear to initiate about 2 ns after the start of the expansion of the modified region. The damage sites continue to grow for about 25 ns but the mechanism of expansion after the termination of the laser pulse is via formation and propagation of lateral cracks. During this time, the affected area of the surface appears to expand forming a bulge of about 40 {micro}m in height. The first clear observation of material cluster ejection is noted at about 50 ns delay.

  1. QM/MM Molecular Dynamics Studies of Metal Binding Proteins

    PubMed Central

    Vidossich, Pietro; Magistrato, Alessandra

    2014-01-01

    Mixed quantum-classical (quantum mechanical/molecular mechanical (QM/MM)) simulations have strongly contributed to providing insights into the understanding of several structural and mechanistic aspects of biological molecules. They played a particularly important role in metal binding proteins, where the electronic effects of transition metals have to be explicitly taken into account for the correct representation of the underlying biochemical process. In this review, after a brief description of the basic concepts of the QM/MM method, we provide an overview of its capabilities using selected examples taken from our work. Specifically, we will focus on heme peroxidases, metallo-β-lactamases, α-synuclein and ligase ribozymes to show how this approach is capable of describing the catalytic and/or structural role played by transition (Fe, Zn or Cu) and main group (Mg) metals. Applications will reveal how metal ions influence the formation and reduction of high redox intermediates in catalytic cycles and enhance drug metabolism, amyloidogenic aggregate formation and nucleic acid synthesis. In turn, it will become manifest that the protein frame directs and modulates the properties and reactivity of the metal ions. PMID:25006697

  2. Metals and Neuronal Metal Binding Proteins Implicated in Alzheimer's Disease

    PubMed Central

    2016-01-01

    Alzheimer's disease (AD) is the most prevalent age-related dementia affecting millions of people worldwide. Its main pathological hallmark feature is the formation of insoluble protein deposits of amyloid-β and hyperphosphorylated tau protein into extracellular plaques and intracellular neurofibrillary tangles, respectively. Many of the mechanistic details of this process remain unknown, but a well-established consequence of protein aggregation is synapse dysfunction and neuronal loss in the AD brain. Different pathways including mitochondrial dysfunction, oxidative stress, inflammation, and metal metabolism have been suggested to be implicated in this process. In particular, a body of evidence suggests that neuronal metal ions such as copper, zinc, and iron play important roles in brain function in health and disease states and altered homeostasis and distribution as a common feature across different neurodegenerative diseases and aging. In this focused review, we overview neuronal proteins that are involved in AD and whose metal binding properties may underlie important biochemical and regulatory processes occurring in the brain during the AD pathophysiological process. PMID:26881049

  3. Ground, sieved, and C18 modified monolithic silica particles for packing material of microcolumn high-performance liquid chromatography.

    PubMed

    Ko, Joung Ho; Baik, Yoon Suk; Park, Seong Tae; Cheong, Won Jo

    2007-03-16

    We here report a new type of stationary phase for microcolumns. C18 modified silica monolith particles were prepared by grinding and sieving the silica monolith followed by C18 modification and end-capping, and were used as packing material. Ground silica monolith particles were not spherical but irregular with some residual monolithic network structure. The separation efficiency of the stationary phase made of sieved monolith particles (5-10 microm) was better than that of the stationary phase made of unsieved particles. The microcolumn packed with the sieved C18 ground monolith particles (5-10 microm) showed quite good separation efficiency (height equivalent to theoretical plate, HETP, as low as 15 microm) and it was even superior to the microcolumn packed with a commercial spherical 5 microm C18 stationary phase. The column pressure drop of C18 monolith particles was about two-third of that of the commercial spherical C18 phase. The preparation method of C18 stationary phase with ground and sieved silica monolith particles presumably suggests advantages of simplicity and convenience in modification and washing procedures compared to bulk silica monolith. It also showed both improved separation efficiency and low back pressure. PMID:17289065

  4. Multifunctional mesoporous silica catalyst

    DOEpatents

    Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

    2015-03-31

    The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

  5. What Is Crystalline Silica?

    MedlinePlus

    ... silica, and requires a repirator protection program until engineering controls are implemented. Additionally, OSHA has a National ... silica materials with safer substitutes, whenever possible. ■ Provide engineering or administrative controls, where feasible, such as local ...

  6. FUNCTIONALIZED SILICA AEROGELS: ADVANCED MATERIALS TO CAPTURE AND IMMOBILIZE RADIOACTIVE IODINE

    SciTech Connect

    Matyas, Josef; Fryxell, Glen E.; Busche, Brad J.; Wallace, Krys; Fifield, Leonard S.

    2011-11-16

    To support the future expansion of nuclear energy, an effective method is needed to capture and safely store radiological iodine-129 released during reprocessing of spent nuclear fuel. Various materials have been investigated to capture and immobilize iodine. In most cases, however, the materials that are effective for capturing iodine cannot subsequently be sintered/densified to create a stable composite that could be a viable waste form. We have developed chemically modified, highly porous, silica aerogels that show sorption capacities higher than 440 mg of I2 per gram at 150 C. An iodine uptake test in dry air containing 4.2 ppm of iodine demonstrated no breakthrough after 3.5 h and indicated a decontamination factor in excess of 310. Preliminary densification tests showed that the I2-loaded aerogels retained more than 92 wt% of I2 after thermal sintering with pressure assistance at 1200 C for 30 min. These high capture and retention efficiencies for I2 can be further improved by optimizing the functionalization process and the chemistry as well as the sintering conditions.

  7. Fluorescent chelates for monitoring metal binding with macromolecules.

    PubMed

    Islam, M; Khanin, M; Sadik, O A

    2003-01-01

    Metals and radionuclides are usually coupled with proteins together with suitable ligands for therapeutic, tumor-imaging, pharmaceuticals, and biocompatibility applications. Several ligands that can strongly coordinate a given nuclide in a specific valency are already known. However, the demand for bifunctionality has limited the applications of these ligands. We hereby report the molecular design of a receptor system based on the linkage of protein to monoazo ligands. By use of basic coordination chemistry, 4-(3-quinolinoazo)hydroxybenzoic acid (QABA) and derivatives were successfully conjugated to ovalbumin, bovine serum albumin, and alkaline phosphatase at a site that was distinct from the metal binding site. The presence of carboxylic acid linkage in the QABA served as a convenient bridge for protein conjugation and may allow the generic application of these ligands for bioconjugate synthesis while ensuring a high in vivo stability. The ligand-protein conjugates were characterized using UV-vis spectroscopy, Fourier transform infrared spectroscopy, thin layer chromatography, NMR, and surface-enhanced laser desorption ionization time-of-flight mass spectrometry. The conjugate was tested for the ability to recognize nonradioactive Ga(3+) at a physiological pH, and a binding constant of 1 x 10(20) was recorded. Also, the in vitro testing results indicated that the fluorescent conjugates exhibited significant selectivity for gallium compared to Pb(2+), Hg(2+), Zn(2+), Cu(2+), Fe(3+), and Co(2+) while no responses were obtained for alkaline and alkaline earth metals. These attributes could allow these conjugates to be used as a model for imaging sensors and for metal detection. PMID:12523855

  8. Silica-Ceria Hybrid Nanostructures

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Baer, Donald R.; Thevuthasan, Suntharampillai

    2012-04-25

    A new hybrid material system that consists of ceria attached silica nanoparticles has been developed. Because of the versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and versatile properties of silica and antioxidant properties of ceria nanoparticles, this material system is ideally suited for biomedical applications. The silica particles of size ~50nm were synthesized by the Stöber synthesis method and ceria nanoparticles of size ~2-3nm was attached to the silica surface using a hetrocoagulation method. The presence of silanol groups on the surface of silica particles mediated homogenous nucleation of ceria which were attached to silica surface by Si-O-Ce bonding. The formations of silica-ceria hybrid nanostructures were characterized by X-photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). The HRTEM image confirms the formation of individual crystallites of ceria nanoparticles attached to the silica surface. The XPS analysis indicates that ceria nanoparticles are chemically bonded to surface of silica and possess mixture of +3 and +4 chemical states.

  9. Silica/quercetin sol-gel hybrids as antioxidant dental implant materials

    NASA Astrophysics Data System (ADS)

    Catauro, Michelina; Papale, Ferdinando; Bollino, Flavia; Piccolella, Simona; Marciano, Sabina; Nocera, Paola; Pacifico, Severina

    2015-06-01

    The development of biomaterials with intrinsic antioxidant properties could represent a valuable strategy for preventing the onset of peri-implant diseases. In this context, quercetin, a naturally occurring flavonoid, has been entrapped at different weight percentages in a silica-based inorganic material by a sol-gel route. The establishment of hydrogen bond interactions between the flavonol and the solid matrix was ascertained by Fourier transform infrared spectroscopy. This technique also evidenced changes in the stretching frequencies of the quercetin dienonic moiety, suggesting that the formation of a secondary product occurs. Scanning electron microscopy was applied to detect the morphology of the synthesized materials. Their bioactivity was shown by the formation of a hydroxyapatite layer on sample surface soaked in a fluid that simulates the composition of human blood plasma. When the potential release of flavonol was determined by liquid chromatography coupled with ultraviolet and electrospray ionization tandem mass spectrometry techniques, the eluates displayed a retention time that was 0.5 min less than quercetin. Collision-activated dissociation mass spectrometry and untraviolet-visible spectroscopy were in accordance with the release of a quercetin derivative. The antiradical properties of the investigated systems were evaluated by DPPH and ABTS methods, whereas the 2,7-dichlorofluorescein diacetate assay highlighted their ability to inhibit the H2O2-induced intracellular production of reactive oxygen species in NIH-3T3 mouse fibroblast cells. Data obtained, along with data gathered from the MTT cytotoxicity test, revealed that the materials that entrapped the highest amount of quercetin showed notable antioxidant effectiveness.

  10. Quercetin conjugated silica particles as novel biofunctional hybrid materials for biological applications.

    PubMed

    Vergara-Castañeda, Hayde; Hernandez-Martinez, Angel R; Estevez, Miriam; Mendoza, Sandra; Luna-Barcenas, Gabriel; Pool, Héctor

    2016-03-15

    The aim of this work is to formulate biofunctional hybrid materials (HMs) with quercetin (QC) and silica particles (SiPs) by simple methods such as sol-gel and QC conjugation. Physicochemical characterization included particle size, zeta potential (ζ), FTIR and SEM imaging. Spherical particles with ca. 115 nm in diameter were produced, ζ and FTIR demonstrated that QC conjugation was successfully achieved. Electrochemical analyses performed by cyclic voltammetry (CV) suggested that potential binding sites between QC and SiPs may be at functional groups from A ring or C ring, affecting the transfer electron of resorcinol moiety. Iron chelating activity and lipid peroxidation assays showed that after conjugation to SiPs, QC decreased its metal chelating activity, but anti-radical properties is maintained. Our results demonstrated that our proposed method is simple and effective to obtain bio-functional HMs. Our findings prove to be useful in the design of protective approaches against lipid oxidation in food, pharmaceutical, and cosmetics fields. PMID:26704475

  11. Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Fabrizio, Eve F.; Ilhan, Faysal; Dass, Amala; Zhang, Guo-Hui; Vassilaras, Plousia; Johnston, J. Chris; Leventis, Nicholas

    2005-01-01

    The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

  12. Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution.

    PubMed

    Prarat, Panida; Ngamcharussrivichai, Chawalit; Khaodhiar, Sutha; Punyapalakul, Patiparn

    2011-09-15

    The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS. PMID:21752539

  13. Propagation in atmosphere of ablated material from femtosecond laser machining of fused silica

    NASA Astrophysics Data System (ADS)

    Bowman, Trevor; Canfield, Brian; Davis, Lloyd

    2014-03-01

    Femtosecond laser pulses provide a means to machine structures with small heat-affected areas through highly non-linear mechanisms that enable direct writing of nanoscale features, which can be applied for fabricating a range of devices, including micro-optics and micro-fluidics. A single, tightly focused ultrashort pulse induces extreme conditions on sub-picosecond time-scales and forms a region of expanding plasma beyond the focal region. This plasma, which typically limits the depth of the nanoscale features to create shallow craters, results in the ejection of micro/nano-particles. The generation and use of these particles have a large range of applications in nanotechnology. We have studied the propagation, in atmosphere, of micro/nano particles ejected using single pulses from a 100 fs, 800 nm laser tightly focused with either a line or spot profile near the back surface of a fused silica substrate. The substrate was translated such that a fresh portion was ablated with each pulse. Time-gated images of the ejected material were taken using an intensified charged coupled device camera with additional illumination along the axial direction. Physical mechanisms and experimental results to date will be discussed.

  14. A New Phase Change Material Based on Potassium Nitrate with Silica and Alumina Nanoparticles for Thermal Energy Storage

    NASA Astrophysics Data System (ADS)

    Chieruzzi, Manila; Miliozzi, Adio; Crescenzi, Tommaso; Torre, Luigi; Kenny, José M.

    2015-06-01

    In this study different nanofluids with phase change behavior were developed by mixing a molten salt base fluid (KNO3 selected as phase change material) with nanoparticles using the direct synthesis method. The thermal properties of the nanofluids obtained were investigated. Following the improvement in the specific heat achieved, these nanofluids can be used in concentrating solar plants with a reduction of storage material. The nanoparticles used (1.0 wt.%) were silica (SiO2), alumina (Al2O3), and a mix of silica-alumina (SiO2-Al2O3) with an average diameter of 7, 13, and 2-200 nm respectively. Each nanofluid was prepared in water solution, sonicated, and evaporated. Measurements of the thermophysical properties were performed by DSC analysis, and the dispersion of the nanoparticles was analyzed by SEM microscopy. The results obtained show that the addition of 1.0 wt.% of nanoparticles to the base salt increases the specific heat of about 5-10 % in solid phase and of 6 % in liquid phase. In particular, this research shows that the addition of silica nanoparticles has significant potential for enhancing the thermal storage characteristics of KNO3. The phase-change temperature of potassium nitrate was lowered up to 3 °C, and the latent heat was increased to 12 % with the addition of silica nanoparticles. These results deviated from the predictions of theoretical simple mixing model used. The stored heat as a function of temperature was evaluated for the base salt, and the nanofluids and the maximum values obtained were 229, 234, 242, and 266 J/g respectively. The maximum total gain (16 %) due to the introduction of the nanoparticles (calculated as the ratio between the total stored heat of the nanofluids and the base salt in the range of temperatures 260-390 °C) was also recorded with the introduction of silica. SEM and EDX analysis showed the presence of aggregates in all nanofluids: with silica nanoparticles they were homogenously present while with alumina and

  15. A New Phase Change Material Based on Potassium Nitrate with Silica and Alumina Nanoparticles for Thermal Energy Storage.

    PubMed

    Chieruzzi, Manila; Miliozzi, Adio; Crescenzi, Tommaso; Torre, Luigi; Kenny, José M

    2015-12-01

    In this study different nanofluids with phase change behavior were developed by mixing a molten salt base fluid (KNO3 selected as phase change material) with nanoparticles using the direct synthesis method. The thermal properties of the nanofluids obtained were investigated. Following the improvement in the specific heat achieved, these nanofluids can be used in concentrating solar plants with a reduction of storage material. The nanoparticles used (1.0 wt.%) were silica (SiO2), alumina (Al2O3), and a mix of silica-alumina (SiO2-Al2O3) with an average diameter of 7, 13, and 2-200 nm respectively. Each nanofluid was prepared in water solution, sonicated, and evaporated. Measurements of the thermophysical properties were performed by DSC analysis, and the dispersion of the nanoparticles was analyzed by SEM microscopy. The results obtained show that the addition of 1.0 wt.% of nanoparticles to the base salt increases the specific heat of about 5-10 % in solid phase and of 6 % in liquid phase. In particular, this research shows that the addition of silica nanoparticles has significant potential for enhancing the thermal storage characteristics of KNO3. The phase-change temperature of potassium nitrate was lowered up to 3 °C, and the latent heat was increased to 12 % with the addition of silica nanoparticles. These results deviated from the predictions of theoretical simple mixing model used. The stored heat as a function of temperature was evaluated for the base salt, and the nanofluids and the maximum values obtained were 229, 234, 242, and 266 J/g respectively. The maximum total gain (16 %) due to the introduction of the nanoparticles (calculated as the ratio between the total stored heat of the nanofluids and the base salt in the range of temperatures 260-390 °C) was also recorded with the introduction of silica. SEM and EDX analysis showed the presence of aggregates in all nanofluids: with silica nanoparticles they were homogenously present while with

  16. A New Phase Change Material Based on Potassium Nitrate with Silica and Alumina Nanoparticles for Thermal Energy Storage.

    PubMed

    Chieruzzi, Manila; Miliozzi, Adio; Crescenzi, Tommaso; Torre, Luigi; Kenny, José M

    2015-12-01

    In this study different nanofluids with phase change behavior were developed by mixing a molten salt base fluid (KNO3 selected as phase change material) with nanoparticles using the direct synthesis method. The thermal properties of the nanofluids obtained were investigated. Following the improvement in the specific heat achieved, these nanofluids can be used in concentrating solar plants with a reduction of storage material. The nanoparticles used (1.0 wt.%) were silica (SiO2), alumina (Al2O3), and a mix of silica-alumina (SiO2-Al2O3) with an average diameter of 7, 13, and 2-200 nm respectively. Each nanofluid was prepared in water solution, sonicated, and evaporated. Measurements of the thermophysical properties were performed by DSC analysis, and the dispersion of the nanoparticles was analyzed by SEM microscopy. The results obtained show that the addition of 1.0 wt.% of nanoparticles to the base salt increases the specific heat of about 5-10 % in solid phase and of 6 % in liquid phase. In particular, this research shows that the addition of silica nanoparticles has significant potential for enhancing the thermal storage characteristics of KNO3. The phase-change temperature of potassium nitrate was lowered up to 3 °C, and the latent heat was increased to 12 % with the addition of silica nanoparticles. These results deviated from the predictions of theoretical simple mixing model used. The stored heat as a function of temperature was evaluated for the base salt, and the nanofluids and the maximum values obtained were 229, 234, 242, and 266 J/g respectively. The maximum total gain (16 %) due to the introduction of the nanoparticles (calculated as the ratio between the total stored heat of the nanofluids and the base salt in the range of temperatures 260-390 °C) was also recorded with the introduction of silica. SEM and EDX analysis showed the presence of aggregates in all nanofluids: with silica nanoparticles they were homogenously present while with

  17. Probing local pH-based precipitation processes in self-assembled silica-carbonate hybrid materials.

    PubMed

    Opel, Julian; Hecht, Mandy; Rurack, Knut; Eiblmeier, Josef; Kunz, Werner; Cölfen, Helmut; Kellermeier, Matthias

    2015-11-01

    Crystallisation of barium carbonate in the presence of silica can lead to the spontaneous assembly of highly complex superstructures, consisting of uniform and largely co-oriented BaCO3 nanocrystals that are interspersed by a matrix of amorphous silica. The formation of these biomimetic architectures (so-called silica biomorphs) is thought to be driven by a dynamic interplay between the components, in which subtle changes of conditions trigger ordered mineralisation at the nanoscale. In particular, it has been proposed that local pH gradients at growing fronts play a crucial role in the process of morphogenesis. In the present work, we have used a special pH-sensitive fluorescent dye to directly trace these presumed local fluctuations by means of confocal laser scanning microscopy. Our data demonstrate the existence of an active region near the growth front, where the pH is locally decreased with respect to the alkaline bulk solution on a length scale of few microns. This observation provides fundamental and, for the first time, direct experimental support for the current picture of the mechanism underlying the formation of these peculiar materials. On the other hand, the absence of any temporal oscillations in the local pH - another key feature of the envisaged mechanism - challenges the notion of autocatalytic phenomena in such systems and raises new questions about the actual role of silica as an additive in the crystallisation process. PMID:26439927

  18. Photophysical properties of some fluorescent materials containing 3-methoxy-7H-benzo[de]anthracen-7-one embedded in sol-gel silica hybrids

    NASA Astrophysics Data System (ADS)

    Raditoiu, Alina; Raditoiu, Valentin; Culita, Daniela Cristina; Baran, Adriana; Anghel, Dan Florin; Spataru, Catalin Ilie; Amariutei, Viorica; Nicolae, Cristian Andi; Wagner, Luminita Eugenia

    2015-07-01

    Several fluorescent materials were prepared by embedding 3-methoxy-7H-benzo[de]anthracen-7-one in transparent sol-gel silica hybrids, in acid catalysis and at room temperature. The photophysical properties of the materials are studied in relationship with the structure and based on interactions established between the fluorophore, which display high sensitivity to minor changes in the local environments, and hybrid silica networks. Colored materials show marked differences in absorption and fluorescence spectra due to the environments around the dyestuff molecules created in the host matrices by grafting different organic moieties onto silica surface. The fluorescence emission spectrum of the obtained materials reveals a positive solvatochromism due to the intramolecular charge transfer character of the excited states and changes in the fluorophore dipole moment. Variations recorded in the fluorescence parameters of the hybrid materials confirm that some interactions are established between the fluorescent dyestuff and hybrid silica network.

  19. Potential uses of silica-bonded macrocyclic ligands for separation of metal ions from nuclear waste

    SciTech Connect

    Bruening, R.L.; Camaioni, D.M.; Colton, N.G.; Morrey, J.R.

    1991-11-01

    This paper explores the potential of a relatively new separation material that is obtained by covalently binding macrocyclic ligands to silica gel. Fortunately, neutral macrocyclic ligands can be bound to silica gel such that metal binding constants do not differ significantly from the binding constants of the free ligands so that selectivities of free macrocyclic ligands can be used in designing silica-bound materials with appropriate selectivities. Accordingly, macrocyclic ligands known to have selectivities for Pd{sup +2}, Ag{sup +}, Ru{sup +3}, Sr{sup +2}, and Cs{sup +} were covalently bound to silica gel. These materials were then tested for their ability to separate these ions from a synthetic test solution representative of a nuclear process waste stream. Cs{sup +} and Sr{sup +2} are of interest because their radioactive isotopes are major radioactive constituents of defense nuclear wastes accumulated at the Hanford site. Removal of precious metals such as Pd{sup +2}, Ag{sup +} and Ru{sup +3} present in nuclear defense waste are of interest not just because of their obvious economic value, but also because these metals may hinder the waste vitrification process for confining radionuclides.

  20. The effects of surface chemistry of mesoporous silica materials and solution pH on kinetics of molsidomine adsorption

    SciTech Connect

    Dolinina, E.S.; Parfenyuk, E.V.

    2014-01-15

    Adsorption kinetics of molsidomine on mesoporous silica material (UMS), the phenyl- (PhMS) and mercaptopropyl-functionalized (MMS) derivatives from solution with different pH and 298 K was studied. The adsorption kinetics was found to follow the pseudo-second-order kinetic model for all studied silica materials and pH. Effects of surface functional groups and pH on adsorption efficiency and kinetic adsorption parameters were investigated. At all studied pH, the highest molsidomine amount is adsorbed on PhMS due to π–π interactions and hydrogen bonding between surface groups of PhMS and molsidomine molecules. An increase of pH results in a decrease of the amounts of adsorbed molsidomine onto the silica materials. Furthermore, the highest adsorption rate kinetically evaluated using a pseudo-second-order model, is observed onto UMS and it strongly depends on pH. The mechanism of the adsorption process was determined from the intraparticle diffusion and Boyd kinetic film–diffusion models. The results showed that the molsidomine adsorption on the silica materials is controlled by film diffusion. Effect of pH on the diffusion parameters is discussed. - Graphical abstract: The kinetic study showed that the k{sub 2} value, the rate constant of pseudo-second order kinetic model, is the highest for molsidomine adsorption on UMS and strongly depends on pH because it is determined by availability and accessibility of the reaction sites of the adsorbents molsidomine binding. Display Omitted - Highlights: • The adsorption capacities of UMS, PhMS and MMS were dependent on the pH. • At all studied pH, the highest molsidomine amount is adsorbed on PhMS. • The highest adsorption rate, k{sub 2}, is observed onto UMS and strongly depends on pH. • Film diffusion was the likely rate-limiting step in the adsorption process.

  1. Combination of porous silica monolith and gold thin films for electrode material of supercapacitor

    NASA Astrophysics Data System (ADS)

    Pastre, A.; Cristini-Robbe, O.; Boé, A.; Raulin, K.; Branzea, D.; El Hamzaoui, H.; Kinowski, C.; Rolland, N.; Bernard, R.

    2015-12-01

    An all-solid electrical double layer supercapacitor was prepared, starting from a porous silica matrix coated with a gold thin-film. The metallization of the silica xerogel was performed by an original wet chemical process, based on the controlled growth of gold nanoparticles on two opposite faces of the silica monolith as a seed layer, followed by an electroless deposition of a continuous gold thin film. The thickness of the metallic thin film was assessed to be 700 nm. The silica plays two major roles: (1) it is used as a porous matrix for the gold electrode, creating a large specific surface area, and (2) it acts as a separator (non-metallized part of the silica). The silica monolith was soaked in a polyvinyl alcohol and phosphoric acid mixture which is used as polymer electrolyte. Capacitance effect was demonstrated by cyclic voltammetry experiments. The specific capacitance was found to be equal to 0.95 mF cm- 2 (9.5 F g-1). No major degradation occurs within more than 3000 cycles.

  2. Influence of Environmental Factors on the Adsorption Capacity and Thermal Conductivity of Silica Nano-Porous Materials.

    PubMed

    Zhang, Hu; Gu, Wei; Li, Ming-Jia; Fang, Wen-Zhen; Li, Zeng-Yao; Tao, Wen-Quan

    2015-04-01

    In this work, the influence of temperature and humidity environment on the water vapor adsorption capacity and effective thermal conductivity of silica nano-porous material is conducted within a relative humidity range from 15% to 90% at 25 °C, 40 °C and 55 °C, respectively. The experiment results show that both the temperature and relative humidity have significant influence on the adsorption capacity and effective thermal conductivity of silica nano-porous materials. The adsorption capacity and effective thermal conductivity increase with humidity because of the increases of water vapor concentration. The effective thermal conductivity increases linearly with adsorption saturation capacity at constant temperature. Because adsorption process is exothermic reaction, the increasing temperature is not conducive to the adsorption. But the effective thermal conductivity increases with the increment of temperature at the same water uptake because of the increment of water thermal conductivity with temperature Geometric models and unit cell structure are adopted to predict the effective thermal conductivity and comparisons with the experimental result are made, and for the case of moist silica nano-porous materials with high porosity no quantitative agreement is found. It is believed that the adsorbed water will fill in the nano-pores and gap and form lots of short cuts, leading to a significant reduction of the thermal resistance.

  3. Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

    USGS Publications Warehouse

    Leenheer, J.A.; Brown, G.K.; MacCarthy, P.; Cabaniss, S.E.

    1998-01-01

    Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that

  4. Development of UHPC Mixtures Utilizing Natural and Industrial Waste Materials as Partial Replacements of Silica Fume and Sand

    PubMed Central

    2014-01-01

    In the exploratory study presented in this paper, an attempt was made to develop different mixtures of ultrahigh performance concrete (UHPC) using various locally available natural and industrial waste materials as partial replacements of silica fume and sand. Materials such as natural pozzolana (NP), fly ash (FA), limestone powder (LSP), cement kiln dust (CKD), and pulverized steel slag (PSS), all of which are abundantly available in Saudi Arabia at little or no cost, were employed in the development of the UHPC mixtures. A base mixture of UHPC without replacement of silica fume or sand was selected and a total of 24 trial mixtures of UHPC were prepared using different percentages of NP, FA, LSP, CKD, and PSS, partially replacing the silica fume and sand. Flow and 28-d compressive strength of each UHPC mixture were determined to finally select those mixtures, which satisfied the minimum flow and strength criteria of UHPC. The test results showed that the utilization of NP, FA, LSP, CKD, and PSS in production of UHPC is possible with acceptable flow and strength. A total of 10 UHPC mixtures were identified with flow and strength equal to or more than the minimum required. PMID:25197709

  5. Development of UHPC mixtures utilizing natural and industrial waste materials as partial replacements of silica fume and sand.

    PubMed

    Ahmad, Shamsad; Hakeem, Ibrahim; Maslehuddin, Mohammed

    2014-01-01

    In the exploratory study presented in this paper, an attempt was made to develop different mixtures of ultrahigh performance concrete (UHPC) using various locally available natural and industrial waste materials as partial replacements of silica fume and sand. Materials such as natural pozzolana (NP), fly ash (FA), limestone powder (LSP), cement kiln dust (CKD), and pulverized steel slag (PSS), all of which are abundantly available in Saudi Arabia at little or no cost, were employed in the development of the UHPC mixtures. A base mixture of UHPC without replacement of silica fume or sand was selected and a total of 24 trial mixtures of UHPC were prepared using different percentages of NP, FA, LSP, CKD, and PSS, partially replacing the silica fume and sand. Flow and 28-d compressive strength of each UHPC mixture were determined to finally select those mixtures, which satisfied the minimum flow and strength criteria of UHPC. The test results showed that the utilization of NP, FA, LSP, CKD, and PSS in production of UHPC is possible with acceptable flow and strength. A total of 10 UHPC mixtures were identified with flow and strength equal to or more than the minimum required. PMID:25197709

  6. Effects of quenching, irradiation, and annealing processes on the radiation hardness of silica fiber cladding materials (I)

    NASA Astrophysics Data System (ADS)

    Wen, Jianxiang; Gong, Renxiang; Xiao, Zhongyin; Luo, Wenyun; Wu, Wenkai; Luo, Yanhua; Peng, Gang-ding; Pang, Fufei; Chen, Zhenyi; Wang, Tingyun

    2016-07-01

    Silica optical fiber cladding materials were experimentally treated by a series of processes. The treatments involved quenching, irradiation, followed by annealing and subsequent re-irradiation, and they were conducted in order to improve the radiation hardness. The microstructural properties of the treated materials were subsequently investigated. Following the treatment of the optical fiber cladding materials, the results from the electron spin resonance (ESR) analysis demonstrated that there was a significant decrease in the radiation-induced defect structures. The ESR signals became significantly weaker when the samples were annealed at 1000 °C in combination with re-irradiation. In addition, the microstructure changes within the silica optical fiber cladding material were also analyzed using Raman spectroscopy. The experimental results demonstrate that the Sisbnd Osbnd Si bending vibrations at ω3 = 800-820 cm-1 and ω4 = 1000-1200 cm-1 (with longitudinal optical (LO) and transverse optical (TO) splitting bands) were relatively unaffected by the quenching, irradiation, and annealing treatments. In particular, the annealing process resulted in the disappearance of the defect centers; however, the LO and TO modes at the ω3 and ω4 bands were relatively unchanged. With the additional support of the ESR test results, we can conclude that the combined treatment processes can significantly enhance the radiation hardness properties of the optical fiber cladding materials.

  7. Preparation of antibacterial composite material of natural rubber particles coated with silica and titania

    NASA Astrophysics Data System (ADS)

    Wisutiratanamanee, Apisit; Poompradub, Sirilux; Poochinda, Kunakorn

    2014-06-01

    Silica coating, followed by titania coating, was performed over spray-dried natural rubber (NR) compound for physical and anti-bacterial characterizations. Titania has a strong photo-oxidative catalytic property, which can disinfect bacteria, but may degrade NR. Therefore, silica coating was intended to form a barrier between NR and titania. First, NR particles were prepared by spray-drying of NR compound latex, formulated for household glove products, mixed with sodium dodecyl sulfate (SDS) to reduce particle agglomeration. The factorial experimental design was employed to investigate the effects of nozzle flow rate (500-700 Lh-1), inlet air temperature (110-150 °C), SDS content (35-55 phr) and mass flow rate (1.2-1.7 g rubber/min) on NR yield and moisture content. Then, the NR compound particles prepared at the optimum condition were coated with silica, using tetraethoxysilane (TEOS) as the precursor, by chemical vapor deposition (CVD) at 60 °C for 2-48 hours. Next, the particles were coated with titania using titanium tetrafluoride (TiF4) by liquid phase deposition (LPD) at 60 ºC for 4-8 hours. The NR composites were characterized for surface morphology by SEM, silica and titania content by TGA and EDX. The NR composites were found to cause more than 99% reduction of Escherichia coli and Staphylococcus aureus under 1-hour exposure to natural light.

  8. Synthesis of Silica-Carbon Nanotube Composite Materials and Their Application for Laser Systems

    NASA Astrophysics Data System (ADS)

    Pilipavicius, J.; Sakalauskas, D.; Beganskiene, A.; Kareiva, A.

    2012-08-01

    Currently, fabrication of CNT and polymer composites for saturable absorbers is very popular. But due to nature of organic polymer matrix, these composites are unstable on higher temperatures or in high energy light exposition. Therefore a sol-gel process for the fabrication for inorganic (i.e. silica) or semi-organic (organic-modified silica) matrix can be a promising way to produce photo-chemically and thermally stable CNT composites. In this work we investigated SWCNT's solubility in ethanol using different surfactants - Triton, polyvinylpyrrolidone, and Poly(4-vinylpyridine). Most stable colloidal solution was obtained using a P4VP as surfactant - solutions were stable up to 6 weeks. Therefore this surfactant was used for the fabrication of SWCNT/Silica composite coatings. SWCNT's was directly dispensed in a colloidal silica sol and coatings made by spin-coating technique. Samples were investigated under optical, atomic force microscopy methods, and optical non-linearity was measured. Thermal stability was investigated using Raman spectroscopy.

  9. Validating metal binding sites in macromolecule structures using the CheckMyMetal web server

    PubMed Central

    Zheng, Heping; Chordia, Mahendra D.; Cooper, David R.; Chruszcz, Maksymilian; Müller, Peter; Sheldrick, George M.

    2015-01-01

    Metals play vital roles in both the mechanism and architecture of biological macromolecules. Yet structures of metal-containing macromolecules where metals are misidentified and/or suboptimally modeled are abundant in the Protein Data Bank (PDB). This shows the need for a diagnostic tool to identify and correct such modeling problems with metal binding environments. The "CheckMyMetal" (CMM) web server (http://csgid.org/csgid/metal_sites/) is a sophisticated, user-friendly web-based method to evaluate metal binding sites in macromolecular structures in respect to 7350 metal binding sites observed in a benchmark dataset of 2304 high resolution crystal structures. The protocol outlines how the CMM server can be used to detect geometric and other irregularities in the structures of metal binding sites and alert researchers to potential errors in metal assignment. The protocol also gives practical guidelines for correcting problematic sites by modifying the metal binding environment and/or redefining metal identity in the PDB file. Several examples where this has led to meaningful results are described in the anticipated results section. CMM was designed for a broad audience—biomedical researchers studying metal-containing proteins and nucleic acids—but is equally well suited for structural biologists to validate new structures during modeling or refinement. The CMM server takes the coordinates of a metal-containing macromolecule structure in the PDB format as input and responds within a few seconds for a typical protein structure modeled with a few hundred amino acids. PMID:24356774

  10. Metal-binding sites are designed to achieve optimal mechanical and signaling properties.

    PubMed

    Dutta, Anindita; Bahar, Ivet

    2010-09-01

    Many proteins require bound metals to achieve their function. We take advantage of increasing structural data on metal-binding proteins to elucidate three properties: the involvement of metal-binding sites in the global dynamics of the protein, predicted by elastic network models, their exposure/burial to solvent, and their signal-processing properties indicated by Markovian stochastics analysis. Systematic analysis of a data set of 145 structures reveals that the residues that coordinate metal ions enjoy remarkably efficient and precise signal transduction properties. These properties are rationalized in terms of their physical properties: participation in hinge sites that control the softest modes collectively accessible to the protein and occupancy of central positions minimally exposed to solvent. Our observations suggest that metal-binding sites may have been evolutionary selected to achieve optimum allosteric communication. They also provide insights into basic principles for designing metal-binding sites, which are verified to be met by recently designed de novo metal-binding proteins.

  11. Naphthopyran-Based Silica Nanoparticles as New High-Performance Photoresponsive Materials.

    PubMed

    Pinto, Tânia V; Costa, Paula; Sousa, Céu M; Sousa, Carlos A D; Monteiro, Andreia; Pereira, Clara; Soares, Olívia Salomé G P; Silva, Carla S M; Pereira, Manuel Fernando R; Coelho, Paulo J; Freire, Cristina

    2016-03-23

    Hybrid nanomaterials based on the covalent grafting of silylated naphthopyrans (NPTs) onto silica nanoparticles (SiO2 NPs) were successfully prepared and studied as new photochromic materials. They were prepared by a two-step protocol consisting of (i) NPTs (derivatives from 2H-naphtho[1,2-b]pyran (2H-NPT) and 3H-naphtho[2,1-b]pyran (3H-NPT)) silylation by a microwave-assisted reaction between hydroxyl-substituted NPTs and 3-(triethoxysilyl)propyl isocyanate, followed by (ii) covalent post-grafting onto SiO2 NPs. In order to study the role of the silylation step, the analogous non-silylated nanomaterials were also prepared by direct adsorption of NPTs. The characterization techniques confirmed the successful NPTs silylation and subsequent grafting to SiO2 NPs. All SiO2-based nanomaterials revealed photoswitching behavior, following a biexponential decay. The SiO2 NPs functionalized with silylated 3H-NPTs (SiO2@S3 and SiO2@S4) presented the most promising photochromic properties, showing fast coloration/decoloration kinetics (coloring in 1 min under UV irradiation and fading in only 2 min) and high values of total color difference (ΔE*ab = 30-50). Also, the 2H-NPTs-based SiO2 NPs (SiO2@S1 and SiO2@S2) presented fast coloration and good color contrasts (ΔE*ab = 54), but slower fading kinetic rates, taking more than 2 h to return to their initial color. In contrast, the SiO2 NPs functionalized with non-silylated NPTs (SiO2@1 and SiO2@3) showed weaker color contrasts (ΔE*ab = 6-10) and slower fading kinetics, proving that the NPT silylation step was crucial to enhance the photochromic behavior of SiO2 NPs based on NPTs. Furthermore, the silylated-based nanomaterials showed good photostability upon prolonged UV light exposure, keeping their photochromic performance unchanged for at least 12 successive UV/dark cycles, anticipating interesting technological applications in several areas. PMID:26926033

  12. Naphthopyran-Based Silica Nanoparticles as New High-Performance Photoresponsive Materials.

    PubMed

    Pinto, Tânia V; Costa, Paula; Sousa, Céu M; Sousa, Carlos A D; Monteiro, Andreia; Pereira, Clara; Soares, Olívia Salomé G P; Silva, Carla S M; Pereira, Manuel Fernando R; Coelho, Paulo J; Freire, Cristina

    2016-03-23

    Hybrid nanomaterials based on the covalent grafting of silylated naphthopyrans (NPTs) onto silica nanoparticles (SiO2 NPs) were successfully prepared and studied as new photochromic materials. They were prepared by a two-step protocol consisting of (i) NPTs (derivatives from 2H-naphtho[1,2-b]pyran (2H-NPT) and 3H-naphtho[2,1-b]pyran (3H-NPT)) silylation by a microwave-assisted reaction between hydroxyl-substituted NPTs and 3-(triethoxysilyl)propyl isocyanate, followed by (ii) covalent post-grafting onto SiO2 NPs. In order to study the role of the silylation step, the analogous non-silylated nanomaterials were also prepared by direct adsorption of NPTs. The characterization techniques confirmed the successful NPTs silylation and subsequent grafting to SiO2 NPs. All SiO2-based nanomaterials revealed photoswitching behavior, following a biexponential decay. The SiO2 NPs functionalized with silylated 3H-NPTs (SiO2@S3 and SiO2@S4) presented the most promising photochromic properties, showing fast coloration/decoloration kinetics (coloring in 1 min under UV irradiation and fading in only 2 min) and high values of total color difference (ΔE*ab = 30-50). Also, the 2H-NPTs-based SiO2 NPs (SiO2@S1 and SiO2@S2) presented fast coloration and good color contrasts (ΔE*ab = 54), but slower fading kinetic rates, taking more than 2 h to return to their initial color. In contrast, the SiO2 NPs functionalized with non-silylated NPTs (SiO2@1 and SiO2@3) showed weaker color contrasts (ΔE*ab = 6-10) and slower fading kinetics, proving that the NPT silylation step was crucial to enhance the photochromic behavior of SiO2 NPs based on NPTs. Furthermore, the silylated-based nanomaterials showed good photostability upon prolonged UV light exposure, keeping their photochromic performance unchanged for at least 12 successive UV/dark cycles, anticipating interesting technological applications in several areas.

  13. Probing local pH-based precipitation processes in self-assembled silica-carbonate hybrid materials

    NASA Astrophysics Data System (ADS)

    Opel, Julian; Hecht, Mandy; Rurack, Knut; Eiblmeier, Josef; Kunz, Werner; Cölfen, Helmut; Kellermeier, Matthias

    2015-10-01

    Crystallisation of barium carbonate in the presence of silica can lead to the spontaneous assembly of highly complex superstructures, consisting of uniform and largely co-oriented BaCO3 nanocrystals that are interspersed by a matrix of amorphous silica. The formation of these biomimetic architectures (so-called silica biomorphs) is thought to be driven by a dynamic interplay between the components, in which subtle changes of conditions trigger ordered mineralisation at the nanoscale. In particular, it has been proposed that local pH gradients at growing fronts play a crucial role in the process of morphogenesis. In the present work, we have used a special pH-sensitive fluorescent dye to directly trace these presumed local fluctuations by means of confocal laser scanning microscopy. Our data demonstrate the existence of an active region near the growth front, where the pH is locally decreased with respect to the alkaline bulk solution on a length scale of few microns. This observation provides fundamental and, for the first time, direct experimental support for the current picture of the mechanism underlying the formation of these peculiar materials. On the other hand, the absence of any temporal oscillations in the local pH - another key feature of the envisaged mechanism - challenges the notion of autocatalytic phenomena in such systems and raises new questions about the actual role of silica as an additive in the crystallisation process.Crystallisation of barium carbonate in the presence of silica can lead to the spontaneous assembly of highly complex superstructures, consisting of uniform and largely co-oriented BaCO3 nanocrystals that are interspersed by a matrix of amorphous silica. The formation of these biomimetic architectures (so-called silica biomorphs) is thought to be driven by a dynamic interplay between the components, in which subtle changes of conditions trigger ordered mineralisation at the nanoscale. In particular, it has been proposed that local

  14. Development and characterization of silica and titania based nano structured materials for the removal of indoor and outdoor air pollutants

    NASA Astrophysics Data System (ADS)

    Peiris, Thelge Manindu Nirasha

    Solar energy driven catalytic systems have gained popularity in environmental remediation recently. Various photocatalytic systems have been reported in this regard and most of the photocatalysts are based on well-known semiconducting material, Titanium Dioxide, while some are based on other materials such as Silicon Dioxide and various Zeolites. However, in titania based photocatalysts, titania is actively involved in the catalytic mechanism by absorbing light and generating exitons. Because of this vast popularity of titania in the field of photocatalysis it is believed that photocatalysis mainly occurs via non-localized mechanisms and semiconductors are extremely important. Even though it is still rare, photocatalysis could be localized and possible without use of a semiconductor as well. Thus, to support localized photocatalytic systems, and to compare the activity to titania based systems, degradation of organic air pollutants by nanostructured silica, titania and mixed silica titania systems were studied. New materials were prepared using two different approaches, precipitation technique (xerogel) and aerogel preparation technique. The prepared xerogel samples were doped with both metal (silver) and non-metals (carbon and sulfur) and aerogel samples were loaded with Chromium, Cobalt and Vanadium separately, in order to achieve visible light photocatalytic activity. Characterization studies of the materials were carried out using Nova BET analysis, DR UV-vis spectrometry, powder X-ray diffraction, X-ray photoelectron Spectroscopy, FT-IR spectroscopy, Transmission Electron Microscopy, etc. Kinetics of the catalytic activities was studied using a Shimadzu GCMS-QP 5000 instrument using a closed glass reactor. All the experiments were carried out in gaseous phase using acetaldehyde as the model pollutant. Kinetic results suggest that chromium doped silica systems are good UV and visible light active photocatalysts. This is a good example for a localized

  15. Raspberry-like PS/CdTe/Silica Microspheres for Fluorescent Superhydrophobic Materials.

    PubMed

    Chang, Jinghui; Zang, Linlin; Wang, Cheng; Sun, Liguo; Chang, Qing

    2016-12-01

    Superhydrophobic particulate films were fabricated via deposition of raspberry-like fluorescent PS/CdTe/silica microspheres on clean glass substrates and surface modification. Particularly, the fluorescent microspheres were prepared by a kind of modified strategy, namely introducing poly (acrylic acid)-functionalized polystyrene microspheres and thiol-stabilized CdTe quantum dots into a hydrolysis reaction of tetraethoxysilane simultaneously. And through adjusting the reaction parameters, the polystyrene spheres with two particle sizes and three colors of CdTe quantum dots aqueous solution were obtained. Consequently, raspberry-like microspheres consist of polystyrene cores and the composite shells of CdTe quantum dots and silica. These microspheres possess a fluorescent characteristic and form a hierarchical dual roughness which was conductive to superhydrophobicity, and the hydrophobic tests also showed the contact angles of water droplets on the surface of the raspberry-like microspheres which were over 160° at room temperature.

  16. Raspberry-like PS/CdTe/Silica Microspheres for Fluorescent Superhydrophobic Materials

    NASA Astrophysics Data System (ADS)

    Chang, Jinghui; Zang, Linlin; Wang, Cheng; Sun, Liguo; Chang, Qing

    2016-02-01

    Superhydrophobic particulate films were fabricated via deposition of raspberry-like fluorescent PS/CdTe/silica microspheres on clean glass substrates and surface modification. Particularly, the fluorescent microspheres were prepared by a kind of modified strategy, namely introducing poly (acrylic acid)-functionalized polystyrene microspheres and thiol-stabilized CdTe quantum dots into a hydrolysis reaction of tetraethoxysilane simultaneously. And through adjusting the reaction parameters, the polystyrene spheres with two particle sizes and three colors of CdTe quantum dots aqueous solution were obtained. Consequently, raspberry-like microspheres consist of polystyrene cores and the composite shells of CdTe quantum dots and silica. These microspheres possess a fluorescent characteristic and form a hierarchical dual roughness which was conductive to superhydrophobicity, and the hydrophobic tests also showed the contact angles of water droplets on the surface of the raspberry-like microspheres which were over 160° at room temperature.

  17. Shock-wave compression of silica gel as a model material for comets

    NASA Astrophysics Data System (ADS)

    Arasuna, Akane; Okuno, Masayuki; Chen, Liliang; Mashimo, Tsutomu; Okudera, Hiroki; Mizukami, Tomoyuki; Arai, Shoji

    2016-07-01

    A shock-wave compression experiment using synthesized silica gel was investigated as a model for a comet impact event on the Earth's surface. The sample shocked at 20.7 GPa showed considerable structural changes, a release of water molecules, and the dehydration of silanol (Si-OH) that led to the formation of a new Si-O-Si network structure containing larger rings (e.g., six-membered ring of SiO4 tetrahedra). The high aftershock temperature at 20.7 GPa, which could be close to 800 °C, influenced the sample structure. However, some silanols, which were presumed to be the mutually hydrogen-bonded silanol group, remained at pressures >20.7 GPa. This type of silanol along with a small number of water molecules may remain even after shock compression at 30.9 GPa, although the intermediate structure of the sample recovered was similar to that of silica glass.

  18. Synthesis and physicochemical study of ZSM-5 high-silica zeolite from natural raw materials

    NASA Astrophysics Data System (ADS)

    Aliev, A. M.; Mamedova, U. A.; Samedov, Kh. R.; Sarydzhanov, A. A.; Agaeva, R. Yu.

    2011-02-01

    ZSM-5 high-silica zeolite was obtained from metakaolinite, Dzhenranchel'sk volcanic ash, and silica gel at T = 150-220°C, pH 9-13, and τ = 48-240 h with the use of an organic structure-forming additive, butanediol-1,4, in an alkaline solution. Optimum conditions for the synthesis of ZSM-5 zeolite were found ( T = 200°C, pH 10, τ = 144 h). The catalytic properties of its H-form in vapor-phase esterification of acetic acid ( I) with ethanol ( II) were studied at 140-180°C and a I: II molar ratio from 1 to 2. Synthesized HZSM-5 showed high activity and selectivity in this reaction.

  19. Electrospun Ultrafine Fiber Composites Containing Fumed Silica: From Solution Rheology to Materials with Tunable Wetting.

    PubMed

    Dufficy, Martin K; Geiger, Mackenzie T; Bonino, Christopher A; Khan, Saad A

    2015-11-17

    Fumed silica (FS) particles with hydrophobic (R805) or hydrophilic (A150) surface functionalities are incorporated in polyacrylonitrile (PAN) fibers by electrospinning to produce mats with controlled wettability. Rheological measurements are conducted to elucidate the particle-polymer interactions and characterize the system while microscopic and analytic tools are used to examine FS location within both fibers and films to aid in the fundamental understanding of wetting behavior. Unlike traditional polymers, we find these systems to be gel-like, yet electrospinnable; the fumed silica networks break down into smaller aggregates during the electrospinning process and disperse both within and on the surface of the fibers. Composite nanofiber mats containing R805 FS exhibit an apparent contact angle over 130° and remain hydrophobic over 30 min, while similar mats with A150 display rapid surface-wetting with a static contact angle of ∼30°. Wicking experiments reveal that the water absorption properties can be further manipulated, with R805 FS-impregnated mats taking up only 8% water relative to mat weight in 15 min. In contrast, PAN fibers containing A150 FS absorb 425% of water in the same period, even more than the pure PAN fiber (371%). The vastly different responses to water demonstrate the versatility of FS in surface modification, especially for submicron fibrous mats. The role of fumed silica in controlling wettability is discussed in terms of their surface functionality, placement on nanofibers and induced surface roughness. PMID:26477547

  20. Electrospun Ultrafine Fiber Composites Containing Fumed Silica: From Solution Rheology to Materials with Tunable Wetting.

    PubMed

    Dufficy, Martin K; Geiger, Mackenzie T; Bonino, Christopher A; Khan, Saad A

    2015-11-17

    Fumed silica (FS) particles with hydrophobic (R805) or hydrophilic (A150) surface functionalities are incorporated in polyacrylonitrile (PAN) fibers by electrospinning to produce mats with controlled wettability. Rheological measurements are conducted to elucidate the particle-polymer interactions and characterize the system while microscopic and analytic tools are used to examine FS location within both fibers and films to aid in the fundamental understanding of wetting behavior. Unlike traditional polymers, we find these systems to be gel-like, yet electrospinnable; the fumed silica networks break down into smaller aggregates during the electrospinning process and disperse both within and on the surface of the fibers. Composite nanofiber mats containing R805 FS exhibit an apparent contact angle over 130° and remain hydrophobic over 30 min, while similar mats with A150 display rapid surface-wetting with a static contact angle of ∼30°. Wicking experiments reveal that the water absorption properties can be further manipulated, with R805 FS-impregnated mats taking up only 8% water relative to mat weight in 15 min. In contrast, PAN fibers containing A150 FS absorb 425% of water in the same period, even more than the pure PAN fiber (371%). The vastly different responses to water demonstrate the versatility of FS in surface modification, especially for submicron fibrous mats. The role of fumed silica in controlling wettability is discussed in terms of their surface functionality, placement on nanofibers and induced surface roughness.

  1. A sulfonic-azobenzene-grafted silica amphiphilic material: a versatile stationary phase for mixed-mode chromatography.

    PubMed

    Qiu, Hongdeng; Zhang, Mingliang; Gu, Tongnian; Takafuji, Makoto; Ihara, Hirotaka

    2013-12-23

    A novel sulfonic-azobenzene-functionalized amphiphilic silica material was synthesized through the preparation of a new sulfonic azobenzene monomer and its grafting on mercaptopropyl-modified silica by a surface-initiated radical chain-transfer reaction. The synthesis was confirmed by infrared spectra, elemental analysis, and thermogravimetric analysis. This new material was successfully applied as a new kind of mixed-mode stationary phase in liquid chromatography. This allows an exceptionally flexible adjustment of retention and selectivity by tuning the experimental conditions. The distinct separation mechanisms were outlined by selected examples of chromatographic separations in the different modes. In reversed-phase liquid chromatography, this new stationary phase presented specific chromatographic performance when evaluated using a Tanaka test mixture. Seven dinitro aromatic isomers, four steroids, and seven flavonoids were separated successfully in simple reversed-phase mode. This stationary phase can also be used in hydrophilic interaction chromatography because of the existing polar functional groups; for this, nucleosides and their bases were used as a test mixture. Interestingly, the same nucleosides and bases can also be separated in per aqueous liquid chromatography using the same stationary phase. Three ginsenosides including Rg1, Re, and Rb1 were successfully separated in hydrophilic mode. There is the potential for more applications to benefit from this useful column. PMID:24353082

  2. Chemical modifications and metal binding studies of Datura innoxia

    SciTech Connect

    Drake, L.R.; Rayson, G.D.; Lin, S.; Jackson, P.J.

    1996-01-01

    The esterification of carboxylate functionalities present in the cell walls of Datura innoxia results in a decrease in metal uptake by as much as 40%, depending on the metal studied. These findings suggest that carboxylate groups are important in metal ion adsorption to this biomaterial. Base hydrolysis of the native plant material resulted in a slight increase in metal ion uptake for Cu{sup 2+} and Sr{sup 2+} and a decrease in uptake for Cd{sup 2+}. These results are attributed to the hydrolysis of esters native to the plant material, which increases the carboxylate content but also results in conformational changes in the macromolecules that comprise the cell fragments. Both the esterified product and the hydrolyzed material were examined via infrared spectroscopy. A peak occurring at 1735 cm{sup -1} (attributed to the carbonyl stretch) confirmed the esterification process. The infrared spectra of the hydrolyzed samples indicate further ionization of carboxylate groups or hydrolysis of esters native to D. innoxia. 29 refs., 5 figs.

  3. Adsorption of transition metal ions from aqueous solutions onto a novel silica gel matrix inorganic-organic composite material.

    PubMed

    Yin, Ping; Xu, Qiang; Qu, Rongjun; Zhao, Guifang; Sun, Yanzhi

    2010-01-15

    A novel inorganic-organic composite material silica gel microspheres encapsulated by imidazole functionalized polystyrene (SG-PS-azo-IM) has been synthesized and characterized. This composite material was used to investigate the adsorption of Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II), Hg(II), Pb(II), Pd(II), Pt(II), Ag(I), and Au(III) from aqueous solutions, and the research results displayed that SG-PS-azo-IM has the highest adsorption capacity for Au(III). Langmuir and Freundlich isotherm models were applied to analyze the experimental data, the best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Au(III) is 1.700 mmol/g. The adsorption selectivity, the dynamic adsorption and desorption properties of SG-PS-azo-IM for Au(III) have also been studied. The results showed that SG-PS-azo-IM had excellent adsorption for Au(III) in four binary ions system, especially in the systems of Au(III)-Zn(II) and Au(III)-Cu(II), and almost Au(III) could be desorbed with the eluent solution of 0.5% thiourea in 1 mol/L HCl. Moreover, this novel composite material was used to preconcentrate Au(III) before its determination by flame atomic adsorption spectrometry. In the initial concentration range of 0.10-0.20 microg/mL, multiple of enrichment could reach 5.28. Thus, silica gel encapsulated by polystyrene coupling with imidazole (SG-PS-azo-IM) is favorable and useful for the removal of transition metal ions, and the high adsorption capacity makes it a good promising candidate material for Au(III) removal.

  4. Application of Hectorite-Coated Silica Gel Particles as a Packing Material for Chromatographic Resolution.

    PubMed

    Okada, Tomohiko; Kumasaki, Aisaku; Shimizu, Kei; Yamagishi, Akihiko; Sato, Hisako

    2016-08-01

    A new type of clay column particles was prepared, in which a hectorite layer (∼0.1 µm thickness) covered uniformly the surface of amorphous silica particles with an average radius of 5 µm (ref. Okada et al., The Journal of Physical Chemistry C, 116, 21864-21869 (2012)). The hectorite layer was fully ion-exchanged with Δ-[Ru(phen)3](2+) (phen = 1,10-phenanthroline) ions by being immersed in a methanol solution of Δ-[Ru(phen)3](ClO4)2 (1 mM). The modified silica gel particles thus prepared were packed into a stainless steel tube (4 mm (i.d.) × 25 cm) as a high-performance liquid chromatography column. Optical resolution was achieved when the racemic mixtures of several metal complexes or organic molecules were eluted with methanol. In the case of tris(acetylacetonato)ruthenium(III) ([Ru(acac)3]), for example, the Λ- and Δ-enantiomers gave an elution volume of 2.6 and 3.0 mL, respectively, with the separation factor of 1.2. The total elution volume (5 mL) was nearly one-tenth for the previously reported column of the same size (RU-1 (Shiseido Co., Ltd.)) packed with the spray-dried particles of synthetic hectorite (average radius 5 µm) ion-exchanged by the same Ru(II) complexes. PMID:27130880

  5. Application of Hectorite-Coated Silica Gel Particles as a Packing Material for Chromatographic Resolution.

    PubMed

    Okada, Tomohiko; Kumasaki, Aisaku; Shimizu, Kei; Yamagishi, Akihiko; Sato, Hisako

    2016-08-01

    A new type of clay column particles was prepared, in which a hectorite layer (∼0.1 µm thickness) covered uniformly the surface of amorphous silica particles with an average radius of 5 µm (ref. Okada et al., The Journal of Physical Chemistry C, 116, 21864-21869 (2012)). The hectorite layer was fully ion-exchanged with Δ-[Ru(phen)3](2+) (phen = 1,10-phenanthroline) ions by being immersed in a methanol solution of Δ-[Ru(phen)3](ClO4)2 (1 mM). The modified silica gel particles thus prepared were packed into a stainless steel tube (4 mm (i.d.) × 25 cm) as a high-performance liquid chromatography column. Optical resolution was achieved when the racemic mixtures of several metal complexes or organic molecules were eluted with methanol. In the case of tris(acetylacetonato)ruthenium(III) ([Ru(acac)3]), for example, the Λ- and Δ-enantiomers gave an elution volume of 2.6 and 3.0 mL, respectively, with the separation factor of 1.2. The total elution volume (5 mL) was nearly one-tenth for the previously reported column of the same size (RU-1 (Shiseido Co., Ltd.)) packed with the spray-dried particles of synthetic hectorite (average radius 5 µm) ion-exchanged by the same Ru(II) complexes.

  6. Time-Resolved Imaging of Material Response Following Laser-Induced Breakdown in the Bulk and Surface of Fused Silica

    SciTech Connect

    Raman, R N; Negres, R A; DeMange, P; Demos, S G

    2010-02-04

    Optical components within high energy laser systems are susceptible to laser-induced material modification when the breakdown threshold is exceeded or damage is initiated by pre-existing impurities or defects. These modifications are the result of exposure to extreme conditions involving the generation of high temperatures and pressures and occur on a volumetric scale of the order of a few cubic microns. The response of the material following localized energy deposition, including the timeline of events and the individual processes involved during this timeline, is still largely unknown. In this work, we investigate the events taking place during the entire timeline in both bulk and surface damage in fused silica using a set of time-resolved microscopy systems. These microscope systems offer up to 1 micron spatial resolution when imaging static or dynamic effects, allowing for imaging of the entire process with adequate temporal and spatial resolution. These systems incorporate various pump-probe geometries designed to optimize the sensitivity for detecting individual aspects of the process such as the propagation of shock waves, near-surface material motion, the speed of ejecta, and material transformations. The experimental results indicate that the material response can be separated into distinct phases, some terminating within a few tens of nanoseconds but some extending up to about 100 microseconds. Overall the results demonstrate that the final characteristics of the modified region depend on the material response to the energy deposition and not on the laser parameters.

  7. New nanostructured silica incorporated with isolated Ti material for the photocatalytic conversion of CO2 to fuels

    PubMed Central

    2014-01-01

    In this work, new nanoporous silica (Korea Advanced Institute of Science and Technology-6 (KIT-6)-dried or KIT-6-calcined) incorporated with isolated Ti materials with different Si/Ti ratios (Si/Ti = 200, 100, and 50) has been synthesized and investigated to establish photocatalytic reduction of CO2 in the presence of H2O vapors. The properties of the materials have been characterized through N2 adsorption/desorption, UV-vis, TEM, FT-IR, and XPS analysis techniques. The intermediate amount of the isolated Ti (Si/Ti = 100) has resulted to be more uniformly distributed on the surface and within the three-dimensional pore structure of the KIT-6 material, without its structure collapsing, than the other two ratios (Si/Ti = 200 and 50). However, titania agglomerates have been observed to have formed due to the increased Ti content (Si/Ti = 50). The Ti-KIT-6 (calcined) materials in the reaction showed higher activity than the Ti-KIT-6 (dried) materials, which produced CH4, H2, CO, and CH3OH (vapors) as fuel products. The Ti-KIT-6 (Si/Ti = 100) material also showed more OH groups, which are useful to obtain a higher production rate of the products, particularly methane, which was even higher than the rate of the best commercial TiO2 (Aeroxide P25, Evonik Industries AG, Essen, Germany) photocatalyst. PMID:24690396

  8. Oxidized dextran facilitated synthesis of a silica-based concanavalin a material for lectin affinity enrichment of glycoproteins/glycopeptides.

    PubMed

    Liu, Yujie; Fu, Dongmei; Yu, Long; Xiao, Yuansheng; Peng, Xiaojun; Liang, Xinmiao

    2016-07-15

    Lectin affinity chromatography (LAC) is an important enrichment technique in glycoproteomics analysis. In order to improve the effectiveness of enrichment, it is necessary to develop LAC materials with high specificity and efficiency. Herein, using oxidized dextran as the spacer, a silica-based concanavalin A material (SiO2-ODex Con A) was synthesized to enrich glycoproteins/glycopeptides. For comparison, the SiO2-Ald Con A material was synthesized using conventional (3-glycidoxypropyl) triethoxysilane (GPMS) as the initial spacer arm. The analytical merits of both Con A materials, such as non-specific adsorption, binding capacity and trapping efficiency, have been evaluated using ovalbumin. Under high performance liquid affinity chromatography (HPLAC) mode, the SiO2-ODex Con A material was highly effective in the enrichment of glycoproteins/glycopeptides attached to high-mannose-type and bi-antennary complex-type glycans. The promising potential of the SiO2-ODex Con A material was demonstrated by selective fractionation of glycoproteins from complex biological samples for glycosylation analysis.

  9. Photosynthetic oxygen evolution in mesoporous silica material: adsorption of photosystem II reaction center complex into 23 nm nanopores in SBA.

    PubMed

    Noji, Tomoyasu; Kamidaki, Chihiro; Kawakami, Keisuke; Shen, Jian-Ren; Kajino, Tsutomu; Fukushima, Yoshiaki; Sekitoh, Takeshi; Itoh, Shigeru

    2011-01-18

    An oxygen-evolving photosynthetic reaction center complex (PSII) was adsorbed into nanopores in SBA, a mesoporous silica compound. We purified the dimer of PSII complex from a thermophilic cyanobacterium, Thermosynechococcus vulcanus, which grows optimally at 57 °C. The thermally stable PSII dimeric complex has a diameter of 20 nm and a molecular mass of 756 kDa and binds more than 60 chlorophylls. The SBA particles, with average internal pore diameters of 15 nm (SBA(15)) and 23 nm (SBA(23)), adsorbed 4.7 and 15 mg of PSII/g SBA, respectively. Measurement with a confocal laser-scanning microscope indicated the adsorption of PSII to the surface and the inner space of the SBA(23) particles, indicating the adsorption of PSII into the 23 nm silica nanopores. PSII did not bind to the inner pores of SBA(15). PSII bound to SBA(23) showed the high and stable activity of a photosynthetic oxygen-evolving reaction, indicating the light-driven electron transport from water to the quinone molecules added in the outer medium. The PSII-SBA conjugate can be a new material for photosensors and artificial photosynthetic systems.

  10. Influence of methanol on the phase behavior of nonionic fluorinated surfactant: relation to the structure of mesoporous silica materials.

    PubMed

    Zimny, K; Blin, J L; Stébé, M J

    2009-02-15

    We have investigated the effect of methanol addition on the R(F)(8)(EO)(9) and R(F)(7)(EO)(8) surfactant-based systems. While upon the addition of methanol the L(1) micellar phase grows, the direct hexagonal (H(1)) and the lamellar (L(alpha)) liquid crystals progressively melt with the increase of alcohol content. Phase behavior and SAXS measurements proved that methanol molecules interact with the oxyethylene units of the surfactant. This involves a folding up of the hydrophobic chains in the liquid crystal phases. Moreover, for the R(F)(7)(EO)(8) surfactant, the cloud point curve is shifted to high temperatures upon addition of alcohol. Starting from these systems, we have prepared mesoporous materials. Results show that due to the hydrogen bonds between the alcohol and the EO groups, the hexagonal structure of the mesostructured silica obtained from R(F)(8)(EO)(9) is lost when the content of CH(3)OH is increased. In contrast, for the compounds prepared from the R(F)(7)(EO)(8)-based system, the pore ordering occurs in the presence of alcohol. This phenomenon has been related to the moving of the cloud point curve toward high temperatures with the addition of methanol. Our study reveals also that under our conditions the methanol released during the hydrolysis of the silica precursor does not affect the self-assembly mechanism in a positive or negative way. PMID:19058809

  11. Imaging System to Measure Kinetics of Material Cluster Ejection During Exit-Surface Damage Initiation and Growth in Fused Silica

    SciTech Connect

    Raman, R N; Negres, R A; Demos, S G

    2009-10-29

    Laser-induced damage on the surface of optical components typically is manifested by the formation of microscopic craters that can ultimately degrade the optics performance characteristics. It is believed that the damage process is the result of the material exposure to high temperatures and pressures within a volume on the order of several cubic microns located just below the surface. The response of the material following initial localized energy deposition by the laser pulse, including the timeline of events and the individual processes involved during this timeline, is still largely unknown. In this work we introduce a time-resolved microscope system designed to enable a detailed investigation of the sequence of dynamic events involved during surface damage. To best capture individual aspects of the damage timeline, this system is employed in multiple imaging configurations (such as multi-view image acquisition at a single time point and multi-image acquisition at different time points of the same event) and offers sensitivity to phenomena at very early delay times. The capabilities of this system are demonstrated with preliminary results from the study of exit-surface damage in fused silica. The time-resolved images provide information on the material response immediately following laser energy deposition, the processes later involved during crater formation or growth, the material ejecta kinetics, and overall material motion and transformation. Such results offer insight into the mechanisms governing damage initiation and growth in the optical components of ICF class laser systems.

  12. Does Dispersion Dominate over H-Bonds in Drug-Surface Interactions? The Case of Silica-Based Materials As Excipients and Drug-Delivery Agents.

    PubMed

    Delle Piane, Massimo; Corno, Marta; Ugliengo, Piero

    2013-05-14

    Amorphous silica is widely employed in pharmaceutical formulations both as a tableting, anticaking agent and as a drug delivery system, whereas MCM-41 mesoporous silica has been recently proposed as an efficient support for the controlled release of drugs. Notwithstanding the relevance of this topic, the atomistic details about the specific interactions between the surfaces of the above materials and drugs and the energetic of adsorption are almost unknown. In this work, we resort to a computational ab initio approach, based on periodic Density Functional Theory (DFT), to study the adsorption behavior of two popular drugs (aspirin and ibuprofen) on two models of an amorphous silica surface characterized by different hydrophilic/hydrophobic properties due to different SiOH surface groups' density. Particular effort was devoted to understand the role of dispersive (vdW) interactions in the adsorption mechanism and their interplay with H-bond interactions. On the hydrophilic silica surface, the H-bond pattern of the Si-OH groups rearranges to comply with the formation of new H-bond interactions triggered by the adsorbed drug. The interaction energy of ibuprofen with the hydrophilic model of the silica surface is computed to be very close to the sublimation energy of the ibuprofen molecular crystal, accounting for the experimental evidence of ibuprofen crystal amorphization induced by the contact with the mesoporous silica material. For both surface models, dispersion interactions play a crucial role in dictating the features of the drug/silica system, and they become dominant for the hydrophobic surface. It was proved that a competition may exist between directional H-bonds and nonspecific dispersion driven interactions, with important structural and energetic consequences for the adsorption. The results of this work emphasize the inadequacy of plain DFT methods to model adsorption processes involving inorganic surfaces and drugs of moderate size, due to the missing

  13. Parameters affecting the efficient delivery of mesoporous silica nanoparticle materials and gold nanorods into plant tissues by the biolistic method.

    PubMed

    Martin-Ortigosa, Susana; Valenstein, Justin S; Sun, Wei; Moeller, Lorena; Fang, Ning; Trewyn, Brian G; Lin, Victor S-Y; Wang, Kan

    2012-02-01

    Applying nanotechnology to plant science requires efficient systems for the delivery of nanoparticles (NPs) to plant cells and tissues. The presence of a cell wall in plant cells makes it challenging to extend the NP delivery methods available for animal research. In this work, research is presented which establishes an efficient NP delivery system for plant tissues using the biolistic method. It is shown that the biolistic delivery of mesoporous silica nanoparticle (MSN) materials can be improved by increasing the density of MSNs through gold plating. Additionally, a DNA-coating protocol is used based on calcium chloride and spermidine for MSN and gold nanorods to enhance the NP-mediated DNA delivery. Furthermore, the drastic improvement of NP delivery is demonstrated when the particles are combined with 0.6 μm gold particles during bombardment. The methodology described provides a system for the efficient delivery of NPs into plant cells using the biolistic method. PMID:22174078

  14. Performance and mechanism on a high durable silica alumina based cementitious material composed of coal refuse and coal combustion byproducts

    NASA Astrophysics Data System (ADS)

    Yao, Yuan

    Coal refuse and combustion byproducts as industrial solid waste stockpiles have become great threats to the environment. Recycling is one practical solution to utilize this huge amount of solid waste through activation as substitute for ordinary Portland cement. The central goal of this dissertation is to investigate and develop a new silica-alumina based cementitious material largely using coal refuse as a constituent that will be ideal for durable construction, mine backfill, mine sealing and waste disposal stabilization applications. This new material is an environment-friendly alternative to ordinary Portland cement. The main constituents of the new material are coal refuse and other coal wastes including coal sludge and coal combustion products (CCPs). Compared with conventional cement production, successful development of this new technology could potentially save energy and reduce greenhouse gas emissions, recycle vast amount of coal wastes, and significantly reduce production cost. A systematic research has been conducted to seek for an optimal solution for enhancing pozzolanic reactivity of the relatively inert solid waste-coal refuse in order to improve the utilization efficiency and economy benefit for construction and building materials. The results show that thermal activation temperature ranging from 20°C to 950°C significantly increases the workability and pozzolanic property of the coal refuse. The optimal activation condition is between 700°C to 800°C within a period of 30 to 60 minutes. Microanalysis illustrates that the improved pozzolanic reactivity contributes to the generated amorphous materials from parts of inert aluminosilicate minerals by destroying the crystallize structure during the thermal activation. In the coal refuse, kaolinite begins to transfer into metakaol in at 550°C, the chlorite minerals disappear at 750°C, and muscovite 2M1 gradually dehydroxylates to muscovite HT. Furthermore, this research examines the environmental

  15. Biosynthesis of metal-binding polypeptides and their precursors in response to cadmium in Datura innoxia

    SciTech Connect

    Jackson, P.J.; Delhaize, E.; Kuske, C.R.

    1991-01-01

    Metal-tolerant Datura innoxia cells synthesize large amounts of a class of metal-binding polypeptides, poly({gamma}-glutamylcysteinyl) glycines (({gamma}-EC){sub n}G, n=2-5), when exposed to Cd. These polypeptides have a high affinity for Cd (2) and certain other metal ions and are thought to play a role in metal tolerance in higher plants. ({gamma}-EC){sub n}G is biosynthetically derived from glutathione. Therefore, the response of Datura cells to Cd must include an increase in production of glutathione and its precursors, since cells rapidly accumulate very high concentrations of these metal-binding polypeptides. The biosynthesis of ({gamma}-EC){sub n}Gs, glutathione, and cysteine in response to Cd exposure is described. The physiological significance of the synthesis of these polypeptides and their precursors and its relevance to Cd tolerance and metal homeostasis are discussed. 34 refs., 6 figs., 1 tab.

  16. A study of the titrimetric potassium silicofluoride method for determination of silica in aluminosilicate materials.

    PubMed

    Sinha, B C; Saha, M R; Roy, S K

    1979-09-01

    A critical study of the titrimetric potassium silicofluoride method for determination of silica reveals that quantitative precipitation of the sificofluoride is possible in 3.5-7.5N acid containing 1% sodium fluoride and >/ 12% potassium chloride. An aqueous wash solution (pH approximately 5.3) containing 0.1% sodium fluoride and 12% potassium chloride has been found ideal for washing the precipitate without significant hydrolysis even at 35 degrees C. The interference of large amounts of aluminium (up to 160 mg of Al(2)O(3)) is eliminated by precipitating the silicofluoride in 6-7.5N acid solution, the aluminium then forming practically no fluoro-complex, because of extensive protonation of fluoride. Interference by large amounts of boron (up to 160 mg of B(2)O(3)) is eliminated by precipitating silicofluoride with the minimum permissible potassium chloride concentration (12%) and washing with the aqueous wash solution at room temperature. Nitrazene Yellow has been used as a more sensitive indicator.

  17. A study of the titrimetric potassium silicofluoride method for determination of silica in aluminosilicate materials.

    PubMed

    Sinha, B C; Saha, M R; Roy, S K

    1979-09-01

    A critical study of the titrimetric potassium silicofluoride method for determination of silica reveals that quantitative precipitation of the sificofluoride is possible in 3.5-7.5N acid containing 1% sodium fluoride and > trg 12% potassium chloride. An aqueous wash solution (pH approximately 5.3) containing 0.1% sodium fluoride and 12% potassium chloride has been found ideal for washing the precipitate without significant hydrolysis even at 35 degrees C. The interference of large amounts of aluminium (up to 160 mg of Al(2)O(3)) is eliminated by precipitating the silicofluoride in 6-7.5N acid solution, the aluminium then forming practically no fluoro-complex, because of extensive protonation of fluoride. Interference by large amounts of boron (up to 160 mg of B(2)O(3)) is eliminated by precipitating silicofluoride with the minimum permissible potassium chloride concentration (12%) and washing with the aqueous wash solution at room temperature. Nitrazene Yellow has been used as a more sensitive indicator.

  18. Metal-Binding Characteristics of the Gamma-Glutamyl Capsular Polymer of Bacillus licheniformis ATCC 9945.

    PubMed

    McLean, R J; Beauchemin, D; Clapham, L; Beveridge, T J

    1990-12-01

    The metal-binding affinity of the anionic poly-gamma-d-glutamyl capsule of Bacillus licheniformis was investigated by using Na, Mg, Al, Ca, Cr, Mn, Fe, Ni, and Cu. Purified capsule was suspended in various concentrations of the chloride salts of the various metals, and after dialysis the bound metals were analyzed either by graphite furnace atomic absorption spectroscopy or by inductively coupled plasma-mass spectrometry. Exposure of purified capsule to excess concentrations of Na revealed it to contain 8.2 mumol of anionic sites per mg on the basis of Na binding. This was confirmed by titration of the capsule with HCl and NaOH. Other metal ions were then added in ionic concentrations equivalent to 25, 50, 75, 100, 200, and 400% of the available anionic sites. The binding characteristics varied with the metal being investigated. Addition of Cu, Al, Cr, or Fe induced flocculation. These metal ions showed the greatest affinity for B. licheniformis capsule in competitive-binding experiments. Flocculation was not seen with the addition of other metal ions. With the exception of Ni and Fe all capsule-metal-binding sites readily saturated. Ni had low affinity for the polymer, and its binding was increased at high metal concentrations. Fe binding resulted in the development of rust-colored ferrihydrite which itself could bind additional metal. Metal-binding characteristics of B. licheniformis capsule appear to be influenced by the chemical and physical properties of both the capsule and the metal ions.

  19. Structural characterization of metal binding to a cold-adapted frataxin.

    PubMed

    Noguera, Martín E; Roman, Ernesto A; Rigal, Juan B; Cousido-Siah, Alexandra; Mitschler, André; Podjarny, Alberto; Santos, Javier

    2015-06-01

    Frataxin is an evolutionary conserved protein that participates in iron metabolism. Deficiency of this small protein in humans causes a severe neurodegenerative disease known as Friedreich's ataxia. A number of studies indicate that frataxin binds iron and regulates Fe-S cluster biosynthesis. Previous structural studies showed that metal binding occurs mainly in a region of high density of negative charge. However, a comprehensive characterization of the binding sites is required to gain further insights into the mechanistic details of frataxin function. In this work, we have solved the X-ray crystal structures of a cold-adapted frataxin from a psychrophilic bacterium in the presence of cobalt or europium ions. We have identified a number of metal-binding sites, mainly solvent exposed, several of which had not been observed in previous studies on mesophilic homologues. No major structural changes were detected upon metal binding, although the structures exhibit significant changes in crystallographic B-factors. The analysis of these B-factors, in combination with crystal packing and RMSD among structures, suggests the existence of localized changes in the internal motions. Based on these results, we propose that bacterial frataxins possess binding sites of moderate affinity for a quick capture and transfer of iron to other proteins and for the regulation of Fe-S cluster biosynthesis, modulating interactions with partner proteins.

  20. Study of the high-coercivity material based on ɛ-Fe2O3 nanoparticles in the silica gel matrix

    NASA Astrophysics Data System (ADS)

    Balaev, D. A.; Yakushkin, S. S.; Dubrovskii, A. A.; Bukhtiyarova, G. A.; Shaikhutdinov, K. A.; Martyanov, O. N.

    2016-04-01

    We report the results of investigations of ɛ-Fe2O3 magnetic nanoparticles obtained by incipient wetness impregnation of silica gel. It was established that the obtained samples with an iron content of 12‒16% mass % containing ɛ-Fe2O3 nanoparticles with an average size of 10 nm on the silica gel surface exhibit a room-temperature coercivity of about 10 kOe. Along with fabrication simplicity, this fact makes the prepared samples promising for application as a magnetically hard material.

  1. Periodic mesoporous hydridosilica--synthesis of an "impossible" material and its thermal transformation into brightly photoluminescent periodic mesoporous nanocrystal silicon-silica composite.

    PubMed

    Xie, Zhuoying; Henderson, Eric J; Dag, Ömer; Wang, Wendong; Lofgreen, Jennifer E; Kübel, Christian; Scherer, Torsten; Brodersen, Peter M; Gu, Zhong-Ze; Ozin, Geoffrey A

    2011-04-01

    There has always been a fascination with "impossible" compounds, ones that do not break any rules of chemical bonding or valence but whose structures are unstable and do not exist. This instability can usually be rationalized in terms of chemical or physical restrictions associated with valence electron shells, multiple bonding, oxidation states, catenation, and the inert pair effect. In the pursuit of these "impossible" materials, appropriate conditions have sometimes been found to overcome these instabilities and synthesize missing compounds, yet for others these tricks have yet to be uncovered and the materials remain elusive. In the scientifically and technologically important field of periodic mesoporous silicas (PMS), one such "impossible" material is periodic mesoporous hydridosilica (meso-HSiO(1.5)). It is the archetype of a completely interrupted silica open framework material: its pore walls are comprised of a three-connected three-dimensional network that should be so thermodynamically unstable that any mesopores present would immediately collapse upon removal of the mesopore template. In this study we show that meso-HSiO(1.5) can be synthesized by template-directed self-assembly of HSi(OEt)(3) under aqueous acid-catalyzed conditions and after template extraction remains stable to 300 °C. Above this temperature, bond redistribution reactions initiate a metamorphic transformation which eventually yields periodic mesoporous nanocrystalline silicon-silica, meso-ncSi/SiO(2), a nanocomposite material in which brightly photoluminescent silicon nanocrystallites are embedded within a silica matrix throughout the mesostructure. The integration of the properties of silicon nanocrystallinity with silica mesoporosity provides a wealth of new opportunities for emerging nanotechnologies.

  2. Mechanochemical synthesis of maghemite/silica nanocomposites: advanced materials for aqueous room-temperature catalysis.

    PubMed

    Ojeda, Manuel; Pineda, Antonio; Romero, Antonio A; Barrón, Vidal; Luque, Rafael

    2014-07-01

    A simple, environmentally friendly, and highly reproducible protocol has been developed for the mechanochemical preparation of advanced nanocatalytic materials in a one-pot process. The materials proved to have unprecedented activities in aqueous Suzuki couplings at room temperature, paving the way for a new generation of highly active and stable advanced nanocatalysts.

  3. Fungus-Mediated Preferential Bioleaching of Waste Material Such as Fly - Ash as a Means of Producing Extracellular, Protein Capped, Fluorescent and Water Soluble Silica Nanoparticles

    PubMed Central

    Khan, Shadab Ali; Uddin, Imran; Moeez, Sana; Ahmad, Absar

    2014-01-01

    In this paper, we for the first time show the ability of the mesophilic fungus Fusarium oxysporum in the bioleaching of waste material such as Fly-ash for the extracellular production of highly crystalline and highly stable, protein capped, fluorescent and water soluble silica nanoparticles at ambient conditions. When the fungus Fusarium oxysporum is exposed to Fly-ash, it is capable of selectively leaching out silica nanoparticles of quasi-spherical morphology within 24 h of reaction. These silica nanoparticles have been completely characterized by UV-vis spectroscopy, Photoluminescence (PL), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Energy dispersive analysis of X-rays (EDAX). PMID:25244567

  4. Use of (113)Cd NMR to probe the native metal binding sites in metalloproteins: an overview.

    PubMed

    Armitage, Ian M; Drakenberg, Torbjörn; Reilly, Brian

    2013-01-01

    Our laboratories have actively published in this area for several years and the objective of this chapter is to present as comprehensive an overview as possible. Following a brief review of the basic principles associated with (113)Cd NMR methods, we will present the results from a thorough literature search for (113)Cd chemical shifts from metalloproteins. The updated (113)Cd chemical shift figure in this chapter will further illustrate the excellent correlation of the (113)Cd chemical shift with the nature of the coordinating ligands (N, O, S) and coordination number/geometry, reaffirming how this method can be used not only to identify the nature of the protein ligands in uncharacterized cases but also the dynamics at the metal binding site. Specific examples will be drawn from studies on alkaline phosphatase, Ca(2+) binding proteins, and metallothioneins.In the case of Escherichia coli alkaline phosphatase, a dimeric zinc metalloenzyme where a total of six metal ions (three per monomer) are involved directly or indirectly in providing the enzyme with maximal catalytic activity and structural stability, (113)Cd NMR, in conjunction with (13)C and (31)P NMR methods, were instrumental in separating out the function of each class of metal binding sites. Perhaps most importantly, these studies revealed the chemical basis for negative cooperativity that had been reported for this enzyme under metal deficient conditions. Also noteworthy was the fact that these NMR studies preceded the availability of the X-ray crystal structure.In the case of the calcium binding proteins, we will focus on two proteins: calbindin D(9k) and calmodulin. For calbindin D(9k) and its mutants, (113)Cd NMR has been useful both to follow actual changes in the metal binding sites and the cooperativity in the metal binding. Ligand binding to calmodulin has been studied extensively with (113)Cd NMR showing that the metal binding sites are not directly involved in the ligand binding. The (113)Cd

  5. Electrochemical Sensors: Functionalized Silica

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Yantasee, Wassana

    2009-03-24

    This chapter summarizes recent devellopment of electrochemical sensors based on functionlized mesoporous silica materials. The nanomatrials based sensors have been developed for sensitive and selective enrironmental detection of toxic heavy metal and uranium ions.

  6. Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering.

    PubMed

    Shimizu, Wataru; Hokka, Junsuke; Sato, Takaaki; Usami, Hisanao; Murakami, Yasushi

    2011-08-01

    The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and

  7. Development of regenerative dye impregnated mesoporous silica materials for assessing exposure to ammonia.

    PubMed

    Chang, Yu-Chang; Bai, Hsunling; Chiang, Hsueh-Shih; Karthik, Mani; Li, Shou-Nan; Hsu, Jung-Nan; Shih, Hui-Ya

    2012-07-01

    The mesostructured materials MCM-41 and SBA-15 were studied as possible supports of bromocresol green (BG) dye impregnation for the ammonia gas detection because of their large surface area, high regenerative property, and high thermal stability. X-ray diffraction, transmission electron microscopy, scanning electron microscope, and N2 adsorption analysis were used to characterize the prepared materials. These materials could sense ammonia via visible color change from yellowish-orange to blue color. The color change process of the nanostructured materials was fully reversible during 10 cyclic tests. The results indicated that the ammonia absorption responses of the two nanostructured materials were both very sensitive, and high linear correlation and high precision were achieved. As the gaseous ammonia concentrations were 50 and 5 ppmv, the response times for the SBA-15/BG were only 1 and 5 min, respectively. Moreover the BG dye-impregnated SBA-15 was less affected by the variation in the relative humidity. It also had faster response for the detection of NH3, as well as lower manufacturing price as compared to that of the dye-impregnated MCM-41. Such feature enables SBA-15/BG to be a very promising material for the detection of ammonia gas.

  8. Thermolytic Molecular Precursor Route to Site-IsolatedVanadia-Silica Materials and Their Catalytic Performance in MethaneSelective Oxidation

    SciTech Connect

    Ruddy, Daniel A.; Ohler, Nicholas L.; Bell, Alexis T.; Tilley, T.Don

    2005-11-23

    The thermolytic molecular precursor (TMP) method was used to prepare site-isolated, high-surface area vanadia-silica (V/SBA15) materials of various V loadings via the grafting of two precursors, OV[OSi(O{sup t}Bu){sub 3}]{sub 3} (1) and Ov(O{sup t}Bu){sub 3} (2). Spectroscopic analysis indicates that excellent synthetic control was established for the exclusive formation of a pseudotetrahedral monovanadate (VO4) structure on all catalyst surfaces. Another V/SBA15 catalyst was prepared via conventional incipient wetness impregnation (WI) with aqueous NH4VO3. A spectroscopic investigation of this catalyst revealed the presence of monovanadate and polyvanadate species along with small domains of V2O5. The TMP materials behave as single-site catalysts in the selective oxidation of methane to formaldehyde up to a V coverage of 0.47 Vnm-2 and demonstrate superior activity compared with the WI catalyst. A space-time yield of 5.84 kgCH2Okg-1cat h-1 was observed, more than twice the highest value previously reported.

  9. Emergence of Zeolite Analogs and other Microporous Crystals in an Atomic Lattice Model of Silica and Related Materials.

    PubMed

    Jin, Lin; Auerbach, Scott M; Monson, Peter A

    2012-03-15

    The potential of tailored nanopores to transform technologies such as drug delivery, biofuel production, and optical-electronic devices depends on fundamental knowledge of the self-assembly of ordered nanoporous solids. Atomic-level geometries of critical nuclei that lead to such solids have remained hidden in the nanoscale blind spot between local (<0.5 nm) and collective (>5 nm) probes of structure. Heroic efforts at molecular simulation of nanopore formation have provided massive libraries of hypothetical structures; (1-5) however, to date no statistical simulation has generated a crystallization pathway from random initial condition to ordered nanoporous solid, until now. In this work, we show that a recently developed atomic lattice model of silica and related materials can form ordered nanoporous solids with a rich variety of structures including known chalcogenides, zeolite analogs, and layered materials. We find that whereas canonical Monte Carlo simulations of the model consistently produce the amorphous solids studied in our previous work, parallel tempering Monte Carlo gives rise to ordered nanoporous solids. The utility of parallel tempering highlights the existence of barriers between amorphous and crystalline phases of our model. Moreover, the self-assembly or nanoporous crystalline phases in the model open the door to detailed understanding of nanopore nucleation.

  10. Method to prevent recession loss of silica and silicon-containing materials in combustion gas environments

    DOEpatents

    Brun, Milivoj Konstantin; Luthra, Krishan Lal

    2003-01-01

    While silicon-containing ceramics or ceramic composites are prone to material loss in combustion gas environments, this invention introduces a method to prevent or greatly reduce the thickness loss by injecting directly an effective amount, generally in the part per million level, of silicon or silicon-containing compounds into the combustion gases.

  11. Formation of Mach angle profiles during wet etching of silica and silicon nitride materials

    NASA Astrophysics Data System (ADS)

    Ghulinyan, M.; Bernard, M.; Bartali, R.; Pucker, G.

    2015-12-01

    In integrated circuit technology peeling of masking photoresist films is a major drawback during the long-timed wet etching of materials. It causes an undesired film underetching, which is often accompanied by a formation of complex etch profiles. Here we report on a detailed study of wedge-shaped profile formation in a series of silicon oxide, silicon oxynitride and silicon nitride materials during wet etching in a buffered hydrofluoric acid (BHF) solution. The shape of etched profiles reflects the time-dependent adhesion properties of the photoresist to a particular material and can be perfectly circular, purely linear or a combination of both, separated by a knee feature. Starting from a formal analogy between the sonic boom propagation and the wet underetching process, we model the wedge formation mechanism analytically. This model predicts the final form of the profile as a function of time and fits the experimental data perfectly. We discuss how this knowledge can be extended to the design and the realization of optical components such as highly efficient etch-less vertical tapers for passive silicon photonics.

  12. Structure and Metal Binding Properties of ZnuA, a Periplasmic Zinc Transporter from Escherichia coli

    SciTech Connect

    Yatsunyk,L.; Easton, J.; Kim, L.; Sugarbaker, S.; Bennett, B.; Breece, R.; Vorontsov, I.; Tierney, D.; Crowder, M.; Rosenzweig, A.

    2008-01-01

    ZnuA is the periplasmic Zn(2+)-binding protein associated with the high-affinity ATP-binding cassette ZnuABC transporter from Escherichia coli. Although several structures of ZnuA and its homologs have been determined, details regarding metal ion stoichiometry, affinity, and specificity as well as the mechanism of metal uptake and transfer remain unclear. The crystal structures of E. coli ZnuA (Eco-ZnuA) in the apo, Zn(2+)-bound, and Co(2+)-bound forms have been determined. ZnZnuA binds at least two metal ions. The first, observed previously in other structures, is coordinated tetrahedrally by Glu59, His60, His143, and His207. Replacement of Zn(2+) with Co(2+) results in almost identical coordination geometry at this site. The second metal binding site involves His224 and several yet to be identified residues from the His-rich loop that is unique to Zn(2+) periplasmic metal binding receptors. Electron paramagnetic resonance and X-ray absorption spectroscopic data on CoZnuA provide additional insight into possible residues involved in this second site. The second site is also detected by metal analysis and circular dichroism (CD) titrations. Eco-ZnuA binds Zn(2+) (estimated K (d) < 20 nM), Co(2+), Ni(2+), Cu(2+), Cu(+), and Cd(2+), but not Mn(2+). Finally, conformational changes upon metal binding observed in the crystal structures together with fluorescence and CD data indicate that only Zn(2+) substantially stabilizes ZnuA and might facilitate recognition of ZnuB and subsequent metal transfer.

  13. Designing novel hybrid materials by one-pot co-condensation: from hydrophobic mesoporous silica nanoparticles to superamphiphobic cotton textiles.

    PubMed

    Pereira, C; Alves, C; Monteiro, A; Magén, C; Pereira, A M; Ibarra, A; Ibarra, M R; Tavares, P B; Araújo, J P; Blanco, G; Pintado, J M; Carvalho, A P; Pires, J; Pereira, M F R; Freire, C

    2011-07-01

    This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic. PMID:21615151

  14. Designing novel hybrid materials by one-pot co-condensation: from hydrophobic mesoporous silica nanoparticles to superamphiphobic cotton textiles.

    PubMed

    Pereira, C; Alves, C; Monteiro, A; Magén, C; Pereira, A M; Ibarra, A; Ibarra, M R; Tavares, P B; Araújo, J P; Blanco, G; Pintado, J M; Carvalho, A P; Pires, J; Pereira, M F R; Freire, C

    2011-07-01

    This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic.

  15. Cubic Mesoporous Silica Material as a Highly Efficient Solid Phase Extraction Sorbent for Bisphenol A, Tert-Nonylphenol from Water.

    PubMed

    Jin, Zhongxiu; Xu, Yuanyuan; Lin, Shilei; Sheng, Jie

    2016-06-01

    Endocrine disrupting chemicals (EDCs), including bisphenol A (BPA), tert-nonylphenol (t-NP) in aqueous solutions, were extracted by cubic mesoporous silica material (MCM-48) and determined by high performance liquid chromatography--fluorometric detection simultaneously. The effect of eluent solvent and its volume, the pH of sample solution and the sample volume on the extraction recovery of MCM-48 composite for EDCs was investigated by the batch techniques. Comparative studies showed that MCM-48 was superior to C18 for the extraction of the more polar analyte bisphenol A and and at least as effective as C18 for the extraction of tert-nonylphenol. The results showed that the excellent recovery towards BPA (87.4%-95.6%) and t-NP (83.6%-96.3%) was achieved by using this method. The good linearity was obtained for BPA and t-NP (R2 > 0.993) at a range from 5 to 1000 μg L(-1). Under the optimum conditions, the detection limits of this method were 96 and 150 ng L(-1) for BPA and t-NP in water sample, based on a signal-to-noise ratio (S/N) of 3, respectively. This method has been also successfully applied for the determination of other EDCs in natural environmental water samples. PMID:27427640

  16. Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water

    PubMed Central

    Yang, Kaijie; Chen, Baoliang; Zhu, Lizhong

    2015-01-01

    The substantial aggregation of pristine graphene nanosheets decreases its powerful adsorption capacity and diminishes its practical applications. To overcome this shortcoming, graphene-coated materials (GCMs) were prepared by loading graphene onto silica nanoparticles (SiO2). With the support of SiO2, the stacked interlamination of graphene was held open to expose the powerful adsorption sites in the interlayers. The adsorption of phenanthrene, a model aromatic pollutant, onto the loaded graphene nanosheets increased up to 100 fold compared with pristine graphene at the same level. The adsorption of GCMs increased with the loading amount of the graphene nanosheets and dramatically decreased with the introduction of oxygen-containing groups in the graphene nanosheets. The highly hydrophobic effect and the strong π-π stacking interactions of the exposed graphene nanosheets contributed to their superior adsorption of GCMs. An unusual GCM peak adsorption coefficient (Kd) was observed with the increase in sorbate concentration. The sorbate concentration at peak Kd shifted to lower values for the reduced graphene oxide and graphene relative to the graphene oxide. Therefore, the replacement of water nanodroplets attached to the graphene nanosheets through weak non-hydrogen bonding with phenanthrene molecules via strong π-π stacking interactions is hypothesized to be an additional adsorption mechanism for GCMs. PMID:26119007

  17. Preparation and adsorption behavior of berberine hydrochloride imprinted polymers by using silica gel as sacrificed support material

    NASA Astrophysics Data System (ADS)

    Li, Hui; Li, Yuzhuo; Li, Zhiping; Peng, Xiyang; Li, Yanan; Li, Gui; Tan, Xianzhou; Chen, Gongxi

    2012-03-01

    Preparation of berberine hydrochloride (B-Cl) imprinted polymers (MIPs) based on surface imprinting technique with silica gel as sacrificial support material was performed successfully by using B-Cl as template, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The prepared polymers were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption behavior of the MIPs for the template and its structural analogues was investigated. Sites distribution on the surface of MIPs was explored by using different isotherm adsorption models and thermodynamic parameters for the adsorption of B-Cl on the MIPs determined. Sample application and reusability for the MIPs was also evaluated. Results indicated the strong adsorption and high selectivity of the MIPs for B-Cl. Saturated adsorption capacity reached 27.2 μmol g-1 and the selectivity coefficient of the MIPs for B-Cl relative to jatrorrhizine hydrochloride (J-Cl) and palmatine palmatus hydrochloride (P-Cl) are 3.70 and 6.03, respectively. In addition, the MIPs were shown with good reusability and selectively retention ability in sample application.

  18. Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water.

    PubMed

    Yang, Kaijie; Chen, Baoliang; Zhu, Lizhong

    2015-01-01

    The substantial aggregation of pristine graphene nanosheets decreases its powerful adsorption capacity and diminishes its practical applications. To overcome this shortcoming, graphene-coated materials (GCMs) were prepared by loading graphene onto silica nanoparticles (SiO2). With the support of SiO2, the stacked interlamination of graphene was held open to expose the powerful adsorption sites in the interlayers. The adsorption of phenanthrene, a model aromatic pollutant, onto the loaded graphene nanosheets increased up to 100 fold compared with pristine graphene at the same level. The adsorption of GCMs increased with the loading amount of the graphene nanosheets and dramatically decreased with the introduction of oxygen-containing groups in the graphene nanosheets. The highly hydrophobic effect and the strong π-π stacking interactions of the exposed graphene nanosheets contributed to their superior adsorption of GCMs. An unusual GCM peak adsorption coefficient (Kd) was observed with the increase in sorbate concentration. The sorbate concentration at peak Kd shifted to lower values for the reduced graphene oxide and graphene relative to the graphene oxide. Therefore, the replacement of water nanodroplets attached to the graphene nanosheets through weak non-hydrogen bonding with phenanthrene molecules via strong π-π stacking interactions is hypothesized to be an additional adsorption mechanism for GCMs. PMID:26119007

  19. Studies on chelating adsorption properties of novel composite material polyethyleneimine/silica gel for heavy-metal ions

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; An, Fuqiang; Liu, Kangkai

    2006-12-01

    Firstly, the coordination processes of line-type polyethyleneimine with Cu 2+, Cd 2+ and Zn 2+ were studied by using visible light absorption spectroscopy and chelation conductivity titration method, and the structures of the chelates were determined. Afterwards, polyethyleneimine (PEI) was grafted onto the surface of silica gel particles via the coupling effect of γ-chloropropyl trimethoxysilane (CP), and the novel composite adsorption material PEI/SiO 2 with strong adsorption ability towards heavy-metal ions was prepared. The chelating adsorption properties of PEI/SiO 2 for Cu 2+, Cd 2+ and Zn 2+ were researched by both static (batch) and dynamic (flow) methods. The experiment results show that water-soluble polyamine PEI with line-type structure reacts with Cu 2+, Cd 2+ and Zn 2+ easily and quantitatively, and water-soluble chelates with four ligands are formed. The composite material PEI/SiO 2 possesses very strong chelating adsorption ability for heavy-metal ions, and the saturated adsorption amount can reach 25.94 mg g -1 and 50.01 mg g -1 for Cu 2+ under static and dynamic conditions, respectively. The isothermal adsorption data fit to Langmuir equation, and the adsorption is typical chemical adsorption with monomolecular layer. The adsorbing ability of PEI/SiO 2 towards the three kinds of the ions follows the order of Cu 2+ > Cd 2+ > Zn 2+. The pH value has great influence on the sorption, and at pH 6-7, the adsorption capacity is the greatest. The fact that adsorption capacity increases with temperature rising indicates the adsorbing process of PEI/SiO 2 for metal ions is endothermic. As diluted hydrochloric acid is used as eluent, the adsorbed heavy-metal ions are eluted easily from PEI/SiO 2, and the regeneration and reuse without decreasing sorption for PEI/SiO 2 are demonstrated.

  20. Immobilization of Lactobacillus rhamnosus in mesoporous silica-based material: An efficiency continuous cell-recycle fermentation system for lactic acid production.

    PubMed

    Zhao, Zijian; Xie, Xiaona; Wang, Zhi; Tao, Yanchun; Niu, Xuedun; Huang, Xuri; Liu, Li; Li, Zhengqiang

    2016-06-01

    Lactic acid bacteria immobilization methods have been widely used for lactic acid production. Until now, the most common immobilization matrix used is calcium alginate. However, Ca-alginate gel disintegrated during lactic acid fermentation. To overcome this deficiency, we developed an immobilization method in which Lactobacillus rhamnosus cells were successfully encapsulated into an ordered mesoporous silica-based material under mild conditions with a high immobilization efficiency of 78.77% by using elemental analysis. We also optimized the cultivation conditions of the immobilized L. rhamnosus and obtained a high glucose conversion yield of 92.4%. Furthermore, L. rhamnosus encapsulated in mesoporous silica-based material exhibited operational stability during repeated fermentation processes and no decrease in lactic acid production up to 8 repeated batches.

  1. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values.

  2. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values. PMID:26025186

  3. MamO Is a Repurposed Serine Protease that Promotes Magnetite Biomineralization through Direct Transition Metal Binding in Magnetotactic Bacteria.

    PubMed

    Hershey, David M; Ren, Xuefeng; Melnyk, Ryan A; Browne, Patrick J; Ozyamak, Ertan; Jones, Stephanie R; Chang, Michelle C Y; Hurley, James H; Komeili, Arash

    2016-03-01

    Many living organisms transform inorganic atoms into highly ordered crystalline materials. An elegant example of such biomineralization processes is the production of nano-scale magnetic crystals in magnetotactic bacteria. Previous studies implicated the involvement of two putative serine proteases, MamE and MamO, during the early stages of magnetite formation in Magnetospirillum magneticum AMB-1. Here, using genetic analysis and X-ray crystallography, we show that MamO has a degenerate active site, rendering it incapable of protease activity. Instead, MamO promotes magnetosome formation through two genetically distinct, noncatalytic activities: activation of MamE-dependent proteolysis of biomineralization factors and direct binding to transition metal ions. By solving the structure of the protease domain bound to a metal ion, we identify a surface-exposed di-histidine motif in MamO that contributes to metal binding and show that it is required to initiate biomineralization in vivo. Finally, we find that pseudoproteases are widespread in magnetotactic bacteria and that they have evolved independently in three separate taxa. Our results highlight the versatility of protein scaffolds in accommodating new biochemical activities and provide unprecedented insight into the earliest stages of biomineralization.

  4. MamO Is a Repurposed Serine Protease that Promotes Magnetite Biomineralization through Direct Transition Metal Binding in Magnetotactic Bacteria

    DOE PAGES

    Hershey, David M.; Ren, Xuefeng; Melnyk, Ryan A.; Browne, Patrick J.; Ozyamak, Ertan; Jones, Stephanie R.; Chang, Michelle C. Y.; Hurley, James H.; Komeili, Arash

    2016-03-16

    Many living organisms transform inorganic atoms into highly ordered crystalline materials. An elegant example of such biomineralization processes is the production of nano-scale magnetic crystals in magnetotactic bacteria. Previous studies have implicated the involvement of two putative serine proteases, MamE and MamO, during the early stages of magnetite formation in Magnetospirillum magneticum AMB-1. Here, using genetic analysis and X-ray crystallography, we show that MamO has a degenerate active site, rendering it incapable of protease activity. Instead, MamO promotes magnetosome formation through two genetically distinct, noncatalytic activities: activation of MamE-dependent proteolysis of biomineralization factors and direct binding to transition metal ions.more » By solving the structure of the protease domain bound to a metal ion, we identify a surface-exposed di-histidine motif in MamO that contributes to metal binding and show that it is required to initiate biomineralization in vivo. Finally, we find that pseudoproteases are widespread in magnetotactic bacteria and that they have evolved independently in three separate taxa. In conclusion, our results highlight the versatility of protein scaffolds in accommodating new biochemical activities and provide unprecedented insight into the earliest stages of biomineralization.« less

  5. MamO Is a Repurposed Serine Protease that Promotes Magnetite Biomineralization through Direct Transition Metal Binding in Magnetotactic Bacteria

    PubMed Central

    Hershey, David M.; Ren, Xuefeng; Melnyk, Ryan A.; Browne, Patrick J.; Ozyamak, Ertan; Jones, Stephanie R.; Chang, Michelle C. Y.; Hurley, James H.; Komeili, Arash

    2016-01-01

    Many living organisms transform inorganic atoms into highly ordered crystalline materials. An elegant example of such biomineralization processes is the production of nano-scale magnetic crystals in magnetotactic bacteria. Previous studies implicated the involvement of two putative serine proteases, MamE and MamO, during the early stages of magnetite formation in Magnetospirillum magneticum AMB-1. Here, using genetic analysis and X-ray crystallography, we show that MamO has a degenerate active site, rendering it incapable of protease activity. Instead, MamO promotes magnetosome formation through two genetically distinct, noncatalytic activities: activation of MamE-dependent proteolysis of biomineralization factors and direct binding to transition metal ions. By solving the structure of the protease domain bound to a metal ion, we identify a surface-exposed di-histidine motif in MamO that contributes to metal binding and show that it is required to initiate biomineralization in vivo. Finally, we find that pseudoproteases are widespread in magnetotactic bacteria and that they have evolved independently in three separate taxa. Our results highlight the versatility of protein scaffolds in accommodating new biochemical activities and provide unprecedented insight into the earliest stages of biomineralization. PMID:26981620

  6. Influence of chemical and environmental stresses on metal-binding proteins: Species-dependent effects

    SciTech Connect

    Baer, K.N.

    1988-01-01

    The development of tolerance to cadmium toxicity was investigated in mammals. In adult mice pretreated with 20 mg Cd/kg, no mortality was observed following administration of a 100 mg/kg cadmium challenge dose. In animals receiving prior exposure to cold stress a mortality of 40% was observed, while in animals receiving no pretreatment an 80% mortality was observed following cadmium challenge. Analysis of the metal-binding proteins using G-75 gel-filtration chromatography revealed that MT-like protein was responsible, in part, for the observed tolerance to cadmium toxicity. For example, following 20 mg Cd/kg and cold pretreatment, the MT-like reserve capacity was 56 and 42 nmoles cadmium, respectively, compared to a control value of 12 nmoles cadmium. The influence of pretreatments on the subcellular distribution of cadmium was also examined. The influence of chemical and environmental stresses on metal-binding proteins in teleosts was investigated. Following cadmium exposure, cadmium increased in the MT fraction in both the gill and liver. However, following exposure to environmental stresses such as cold and hypoxia, significant decreases in zinc and copper were observed in the gill MT fraction, as compared to control. In the liver, no significant alterations were observed in the MT fraction, as compared to control.

  7. A new metal binding domain involved in cadmium, cobalt and zinc transport

    PubMed Central

    Smith, Aaron T.; Barupala, Dulmini; Stemmler, Timothy L.; Rosenzweig, Amy C.

    2015-01-01

    The P1B-ATPases, which couple cation transport across membranes to ATP hydrolysis, are central to metal homeostasis in all organisms. An important feature of P1B-ATPases is the presence of soluble metal binding domains that regulate transport activity. Only one type of MBD has been characterized extensively, but bioinformatics analyses indicate that a diversity of MBDs may exist in nature. Here we report the biochemical, structural, and functional characterization of a new MBD from the Cupriavidus metallidurans P1B-4-ATPase CzcP (CzcP MBD). The CzcP MBD binds two Cd2+, Co2+, or Zn2+ ions in distinct and unique sites, and adopts an unexpected fold consisting of two fused ferredoxin-like domains. Both in vitro and in vivo activity assays using full length CzcP, truncated CzcP, and several variants indicate a regulatory role for the MBD and distinct functions for the two metal binding sites. Taken together, these findings elucidate a previously unknown MBD and suggest new regulatory mechanisms for metal transport by P1B-ATPases. PMID:26192600

  8. A New Metal Binding Domain Involved in Cadmium, Cobalt and Zinc Transport

    SciTech Connect

    Smith, Aaron T.; Barupala, Dulmini; Stemmler, Timothy L.; Rosenzweig, Amy C.

    2015-07-20

    In the P1B-ATPases, which couple cation transport across membranes to ATP hydrolysis, are central to metal homeostasis in all organisms. An important feature of P1B-ATPases is the presence of soluble metal binding domains (MBDs) that regulate transport activity. Only one type of MBD has been characterized extensively, but bioinformatics analyses indicate that a diversity of MBDs may exist in nature. Here we report the biochemical, structural and functional characterization of a new MBD from the Cupriavidus metallidurans P1B-4-ATPase CzcP (CzcP MBD). The CzcP MBD binds two Cd2+, Co2+ or Zn2+ ions in distinct and unique sites and adopts an unexpected fold consisting of two fused ferredoxin-like domains. Both in vitro and in vivo activity assays using full-length CzcP, truncated CzcP and several variants indicate a regulatory role for the MBD and distinct functions for the two metal binding sites. Moreover, these findings elucidate a previously unknown MBD and suggest new regulatory mechanisms for metal transport by P1B-ATPases.

  9. Exploring the influence of the protein environment on metal-binding pharmacophores.

    PubMed

    Martin, David P; Blachly, Patrick G; McCammon, J Andrew; Cohen, Seth M

    2014-08-28

    The binding of a series of metal-binding pharmacophores (MBPs) related to the ligand 1-hydroxypyridine-2-(1H)-thione (1,2-HOPTO) in the active site of human carbonic anhydrase II (hCAII) has been investigated. The presence and/or position of a single methyl substituent drastically alters inhibitor potency and can result in coordination modes not observed in small-molecule model complexes. It is shown that this unexpected binding mode is the result of a steric clash between the methyl group and a highly ordered water network in the active site that is further stabilized by the formation of a hydrogen bond and favorable hydrophobic contacts. The affinity of MBPs is dependent on a large number of factors including donor atom identity, orientation, electrostatics, and van der Waals interactions. These results suggest that metal coordination by metalloenzyme inhibitors is a malleable interaction and that it is thus more appropriate to consider the metal-binding motif of these inhibitors as a pharmacophore rather than a "chelator". The rational design of inhibitors targeting metalloenzymes will benefit greatly from a deeper understanding of the interplay between the variety of forces governing the binding of MBPs to active site metal ions. PMID:25116076

  10. Cobalt(III), a probe of metal binding sites of Escherichia coli alkaline phosphatase.

    PubMed Central

    Anderson, R A; Vallee, B L

    1975-01-01

    To facilitate the study of individual metal binding sites of polymeric metalloproteins, conversion of exchange-labile Co(II) in E. coli alkaline phosphatase (EC 3.1.3.1) to exchange-inert Co(III) was examined. Oxidation of Co(II) alkaline phosphatase with hydrogen peroxide results in a single absorption maximum at 530 nm and loss both of the characteristic electron paramagnetic signal and of enzymatic activity. Zinc neither reactivates this enzyme nor displaces the oxidized cobalt atoms. Metal and amino-acid analyses demonstrate that oxidation alters neither cobalt binding nor amino-acid composition of the enzyme. Al data are consistent with the conclusion that hydrogen peroxide oxidizes Co(II) in alkaline phosphatase to Co(III). Polymeric metalloenzymes can contain different categories of metal atoms serving in catalysis, structure stabilization, and/or control and exerting their effects independently or interdependently. The in situ conversion of exchange-labile Co(II) to exchange-stable (Co(III) offers a method to selectively and differentially "freeze" cobalt atoms at their respective binding sites. The accompanying spectral changes and concomitant retardation in ligand exchange reactions may be used to differentiate between specific metal binding sites that serve different roles in polymeric metalloenzymes. PMID:164026

  11. Metal-binding and redox properties of substituted linear and cyclic ATCUN motifs.

    PubMed

    Neupane, Kosh P; Aldous, Amanda R; Kritzer, Joshua A

    2014-10-01

    The amino-terminal copper and nickel binding (ATCUN) motif is a short peptide sequence found in human serum albumin and other proteins. Synthetic ATCUN-metal complexes have been used to oxidatively cleave proteins and DNA, cross-link proteins, and damage cancer cells. The ATCUN motif consists of a tripeptide that coordinates Cu(II) and Ni(II) ions in a square planar geometry, anchored by chelation sites at the N-terminal amine, histidine imidazole and two backbone amides. Many studies have shown that the histidine is required for tight binding and square planar geometry. Previously, we showed that macrocyclization of the ATCUN motif can lead to high-affinity binding with altered metal ion selectivity and enhanced Cu(II)/Cu(III) redox cycling (Inorg. Chem. 2013, 52, 2729-2735). In this work, we synthesize and characterize several linear and cyclic ATCUN variants to explore how substitutions at the histidine alter the metal-binding and catalytic properties. UV-visible spectroscopy, EPR spectroscopy and mass spectrometry indicate that cyclization can promote the formation of ATCUN-like complexes even in the absence of imidazole. We also report several novel ATCUN-like complexes and quantify their redox properties. These findings further demonstrate the effects of conformational constraints on short, metal-binding peptides, and also provide novel redox-active metallopeptides suitable for testing as catalysts for stereoselective or regioselective oxidation reactions.

  12. Metal-binding characteristics of the gamma-glutamyl capsular polymer of Bacillus licheniformis ATCC 9945

    SciTech Connect

    McLean, R.J.C.; Beauchemin, D.; Clapham, L.; Beveridge, T.J. Univ. of Guelph, Ontario )

    1990-12-01

    The metal-binding affinity of the anionic poly-{gamma}-D-glutamyl capsule of Bacillus licheniformis was investigated by using Na{sup +}, Mg{sup 2+}, Al{sup 3+}, Ca{sup 2+}, Cr{sup 3+}, Mn{sup 2+}, Fe{sup 3+}, Ni{sup 2+}, and Cu{sup 2+}. Exposure of purified capsule to excess concentrations of Na{sup +} revealed it to contain 8.2 {mu}mol of anionic sites per mg on the basis of Na binding. Other metal ions were then added in ionic concentrations equivalent to 25, 50, 75, 100, 200, and 400% of the available anionic sites. The binding characteristics varied with the metal being investigated. Addition of Cu{sup 2+}, Al{sup 3+}, Cr{sup 3+}, or Fe{sup 3+} induced flocculation. These metal ions showed the greatest affinity for B. licheniformis capsule in competitive-binding experiments. Flocculation was not seen with the addition of other metal ions. With the exception of Ni{sup 2+} and Fe{sup 3+} all capsule-metal-binding sites readily saturated. Ni{sup 2+} had low affinity for the polymer, and its binding was increased at high metal concentrations. Fe{sup 3+} binding resulted in the development of rust-colored ferrihydrite which itself could bind additional metal.

  13. Characterization of metal-binding bioflocculants produced by the cyanobacterial component of mixed microbial mats.

    PubMed Central

    Bender, J; Rodriguez-Eaton, S; Ekanemesang, U M; Phillips, P

    1994-01-01

    Mixed-species microbial mats that were dominated by the cyanobacterium Oscillatoria sp. and contained heterotrophic and purple autotrophic bacteria were constructed for specific bioremediation applications. When the mats were challenged with metals, production and secretion of metal-binding extracellular polysaccharide bioflocculants were observed. The concentration of these negatively charged polysaccharides was correlated with the removal of manganese from the water column beneath a surface microbial mat. Bioflocculants from an Oscillatoria sp. that was isolated from the mat were collected and concentrated for characterization. A chromatographic analysis revealed a heterogeneous population of polysaccharides with respect to charge density and molecular size. The subpopulation of polysaccharides which exhibited the highest level of flocculating activity was polyanionic and had a molecular weight of more than 200,000. A glycosyl analysis of the bioflocculants revealed the presence of galacturonic acid (2.2%) and glucuronic acid (1.86%). The presence of these components, which were negatively charged at the pH levels generated by the mats during photosynthesis (pH > 7.5), may account for the metal-binding properties of the mats. PMID:8074512

  14. Heavy metal binding capacity (HMBC) of municipal solid waste landfill leachates.

    PubMed

    Ward, Marnie L; Bitton, Gabriel; Townsend, Timothy

    2005-07-01

    This research describes the use of a toxicity assay for the identification of metal toxicity, bioavailability and heavy metal binding capacity (HMBC) of municipal solid waste (MSW) landfill leachates. MetPLATE, an assay specific for heavy metal toxicity, was used to determine the HMBC of MSW leachates collected from 14 sites in Florida, with a wide range of chemical and physical characteristics. The leachates displayed a low toxicity which was attributed to the site-specific parameters, including, high concentrations of both organic and inorganic ligands. The HMBC test was undertaken to measure the effect of these site-specific parameters on metal toxicity. The potential for MSW leachate to bind and, thus, detoxify heavy metals was investigated with copper, zinc, and mercury. The HMBC values obtained ranged from 3 to 115, 5 to 93 and 4 to 101 for HMBC-Cu+2, HMBC-Zn+2, and HMBC-Hg+2, respectively. Additionally, the high strength leachates displayed the highest binding capacities, although the landfills sampled represented a wide range of characteristics. For comparison, the HMBC values reported with local lake water, Lake Alice and Lake Beverly, and a wastewater treatment plant effluent were all below 3. A partial fractionation of MSW leachate samples from sites 1, 5 and 8, was conducted to further investigate the influence of selected site-specific physico-chemical parameters on metal binding. The fractionation revealed that the HMBC of the leachate samples was heavily influenced by the concentration of solids, organics and hardness.

  15. Metal-Binding and Redox Properties of Substituted Linear and Cyclic ATCUN Motifs

    PubMed Central

    Neupane, Kosh P.; Aldous, Amanda R.; Kritzer, Joshua A.

    2014-01-01

    The amino-terminal copper and nickel binding (ATCUN) motif is a short peptide sequence found in human serum albumin and other proteins. Synthetic ATCUN-metal complexes have been used to oxidatively cleave proteins and DNA, cross-link proteins, and damage cancer cells. The ATCUN motif consists of a tripeptide that coordinates Cu(II) and Ni(II) ions in a square planar geometry, anchored by chelation sites at the N-terminal amine, histidine imidazole and two backbone amides. Many studies have shown that the histidine is required for tight binding and square planar geometry. Previously, we showed that macrocyclization of the ATCUN motif can lead to high-affinity binding with altered metal ion selectivity and enhanced Cu(II)/Cu(III) redox cycling (Inorg. Chem. 2013, 52, 2729-2735). In this work, we synthesize and characterize several linear and cyclic ATCUN variants to explore how substitutions at the histidine alter the metal-binding and catalytic properties. UV-visible spectroscopy, EPR spectroscopy and mass spectrometry indicate that cyclization can promote the formation of ATCUN-like complexes even in the absence of imidazole. We also report several novel ATCUN-like complexes and quantify their redox properties. These findings further demonstrate the effects of conformational constraints on short, metal-binding peptides, and also provide novel redox-active metallopeptides suitable for testing as catalysts for stereoselective or regioselective oxidation reactions. PMID:24980953

  16. Pore Size Effect on Methane Adsorption in Mesoporous Silica Materials Studied by Small-Angle Neutron Scattering.

    PubMed

    Chiang, Wei-Shan; Fratini, Emiliano; Baglioni, Piero; Chen, Jin-Hong; Liu, Yun

    2016-09-01

    Methane adsorption in model mesoporous silica materials with the size range characteristic of shale is studied by small-angle neutron scattering (SANS). Size effect on the temperature-dependent gas adsorption at methane pressure about 100 kPa is investigated by SANS using MCM-41 and SBA-15 as adsorbents. Above the gas-liquid condensation temperature, the thickness of the adsorption layer is found to be roughly constant as a function of the temperature. Moreover, the gas adsorption properties, such as the adsorbed layer thickness and the specific amount of adsorbed gas, have little dependence on the pore size being studied, i.e., pore radius of 16.5 and 34.1 Å, but are mainly affected by the roughness of the pore surfaces. Hence, the surface properties of the pore wall are more dominant than the pore size in determining the methane gas adsorption of pores at the nanometer size range. Not surprisingly, the gas-liquid condensation temperature is observed to be sensitive to pore size and shifts to higher temperature when the pore size is smaller. Below the gas-liquid condensation temperature, even though the majority of gas adsorption experiments/simulations have assumed the density of confined liquid to be the same as the bulk density, the measured methane mass density in our samples is found to be appreciably smaller than the bulk methane density regardless of the pore sizes studied here. The mass density of liquid/solid methane in pores with different sizes shows different temperature dependence below the condensation temperature. With decreasing temperature, the methane density in larger pores (SBA-15) abruptly increases at approximately 65 K and then plateaus. In contrast, the density in smaller pores (MCM-41) monotonically increases with decreasing temperature before reaching a plateau at approximately 30 K.

  17. Pore Size Effect on Methane Adsorption in Mesoporous Silica Materials Studied by Small-Angle Neutron Scattering.

    PubMed

    Chiang, Wei-Shan; Fratini, Emiliano; Baglioni, Piero; Chen, Jin-Hong; Liu, Yun

    2016-09-01

    Methane adsorption in model mesoporous silica materials with the size range characteristic of shale is studied by small-angle neutron scattering (SANS). Size effect on the temperature-dependent gas adsorption at methane pressure about 100 kPa is investigated by SANS using MCM-41 and SBA-15 as adsorbents. Above the gas-liquid condensation temperature, the thickness of the adsorption layer is found to be roughly constant as a function of the temperature. Moreover, the gas adsorption properties, such as the adsorbed layer thickness and the specific amount of adsorbed gas, have little dependence on the pore size being studied, i.e., pore radius of 16.5 and 34.1 Å, but are mainly affected by the roughness of the pore surfaces. Hence, the surface properties of the pore wall are more dominant than the pore size in determining the methane gas adsorption of pores at the nanometer size range. Not surprisingly, the gas-liquid condensation temperature is observed to be sensitive to pore size and shifts to higher temperature when the pore size is smaller. Below the gas-liquid condensation temperature, even though the majority of gas adsorption experiments/simulations have assumed the density of confined liquid to be the same as the bulk density, the measured methane mass density in our samples is found to be appreciably smaller than the bulk methane density regardless of the pore sizes studied here. The mass density of liquid/solid methane in pores with different sizes shows different temperature dependence below the condensation temperature. With decreasing temperature, the methane density in larger pores (SBA-15) abruptly increases at approximately 65 K and then plateaus. In contrast, the density in smaller pores (MCM-41) monotonically increases with decreasing temperature before reaching a plateau at approximately 30 K. PMID:27512895

  18. Synthesis Mechanism and Thermal Optimization of an Economical Mesoporous Material Using Silica: Implications for the Effective Removal or Delivery of Ibuprofen

    PubMed Central

    Kittappa, Shanmuga; Cui, Mingcan; Ramalingam, Malarvili; Ibrahim, Shaliza; Khim, Jeehyeong; Yoon, Yeomin; Snyder, Shane A.; Jang, Min

    2015-01-01

    Mesoporous silica materials (MSMs) were synthesized economically using silica (SiO2) as a precursor via a modified alkaline fusion method. The MSM prepared at 500°C (MSM–500) had the highest surface area, pore size, and volume, and the results of isotherms and the kinetics of ibuprofen (IBP) removal indicated that MSM–500 had the highest sorption capacity and fastest removal speed vs. SBA–15 and zeolite. Compared with commercial granular activated carbon (GAC), MSM–500 had a ~100 times higher sorption rate at neutral pH. IBP uptake by MSM–500 was thermodynamically favorable at room temperature, which was interpreted as indicating relatively weak bonding because the entropy (∆adsS, –0.07 J mol–1 K–1) was much smaller. Five times recycling tests revealed that MSM–500 had 83–87% recovery efficiencies and slower uptake speeds due to slight deformation of the outer pore structure. In the IBP delivery test, MSM–500 drug loading was 41%, higher than the reported value of SBA–15 (31%). The in vitro release of IBP was faster, almost 100%, reaching equilibrium within a few hours, indicating its effective loading and unloading characteristics. A cost analysis study revealed that the MSM was ~10–70 times cheaper than any other mesoporous silica material for the removal or delivery of IBP. PMID:26161510

  19. Preparation and physical characterization of calcium sulfate cement/silica-based mesoporous material composites for controlled release of BMP-2.

    PubMed

    Tan, Honglue; Yang, Shengbing; Dai, Pengyi; Li, Wuyin; Yue, Bing

    2015-01-01

    As a commonly used implant material, calcium sulfate cement (CSC), has some shortcomings, including low compressive strength, weak osteoinduction capability, and rapid degradation. In this study, silica-based mesoporous materials such as SBA-15 were synthesized and combined with CSC to prepare CSC/SBA-15 composites. The properties of SBA-15 were characterized by X-ray diffraction, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. SBA-15 was blended into CSC at 0, 5, 10, and 20 wt%, referred to as CSC, CSC-5S (5% mass ratio), CSC-10S (10% mass ratio), and CSC-20S (20% mass ratio), respectively. Fourier-transform infrared spectroscopy and compression tests were used to determine the structure and mechanical properties of the composites, respectively. The formation of hydroxyapatite on composite surfaces was analyzed using scanning electron microscopy and X-ray diffraction after soaking in simulated body fluid. BMP-2 was loaded into the composites by vacuum freeze-drying, and its release characteristics were detected by Bradford protein assay. The in vitro degradation of the CSC/SBA-15 composite was investigated by measuring weight loss. The results showed that the orderly, nanostructured, mesoporous SBA-15 possessed regular pore size and structure. The compressive strength of CSC/SBA-15 increased with the increase in SBA-15 mass ratio, and CSC-20S demonstrated the maximum strength. Compared to CSC, hydroxyapatite that formed on the surfaces of CSC/SBA-15 was uniform and compact. The degradation rate of CSC/SBA-15 decreased with increasing mass ratio of SBA-15. The adsorption of BMP-2 increased and released at a relatively slow rate; the release rate of BMP-2 in CSC-20S was the slowest, and presented characteristics of low doses of release. In vitro experiments demonstrated that the physical properties of pure CSC incorporated with SBA-15 could be improved significantly, which made the CSC/SBA-15 composite more suitable for bone repair

  20. Preparation and physical characterization of calcium sulfate cement/silica-based mesoporous material composites for controlled release of BMP-2

    PubMed Central

    Tan, Honglue; Yang, Shengbing; Dai, Pengyi; Li, Wuyin; Yue, Bing

    2015-01-01

    As a commonly used implant material, calcium sulfate cement (CSC), has some shortcomings, including low compressive strength, weak osteoinduction capability, and rapid degradation. In this study, silica-based mesoporous materials such as SBA-15 were synthesized and combined with CSC to prepare CSC/SBA-15 composites. The properties of SBA-15 were characterized by X-ray diffraction, transmission electron microscopy, and nitrogen adsorption–desorption isotherms. SBA-15 was blended into CSC at 0, 5, 10, and 20 wt%, referred to as CSC, CSC-5S (5% mass ratio), CSC-10S (10% mass ratio), and CSC-20S (20% mass ratio), respectively. Fourier-transform infrared spectroscopy and compression tests were used to determine the structure and mechanical properties of the composites, respectively. The formation of hydroxyapatite on composite surfaces was analyzed using scanning electron microscopy and X-ray diffraction after soaking in simulated body fluid. BMP-2 was loaded into the composites by vacuum freeze-drying, and its release characteristics were detected by Bradford protein assay. The in vitro degradation of the CSC/SBA-15 composite was investigated by measuring weight loss. The results showed that the orderly, nanostructured, mesoporous SBA-15 possessed regular pore size and structure. The compressive strength of CSC/SBA-15 increased with the increase in SBA-15 mass ratio, and CSC-20S demonstrated the maximum strength. Compared to CSC, hydroxyapatite that formed on the surfaces of CSC/SBA-15 was uniform and compact. The degradation rate of CSC/SBA-15 decreased with increasing mass ratio of SBA-15. The adsorption of BMP-2 increased and released at a relatively slow rate; the release rate of BMP-2 in CSC-20S was the slowest, and presented characteristics of low doses of release. In vitro experiments demonstrated that the physical properties of pure CSC incorporated with SBA-15 could be improved significantly, which made the CSC/SBA-15 composite more suitable for bone repair

  1. The properties of silica-gelatin composites

    NASA Astrophysics Data System (ADS)

    Stavinskaya, O. N.; Laguta, I. V.

    2010-06-01

    Silica-gelatin composites with various silica-to-gelatin ratios were obtained. The influence of high-dispersity silica on the swelling of composites in water and desorption of pyridoxine and thiamine vitamins incorporated into the material was studied. The addition of silica to gelatin was shown to increase the time of the dissolution of the materials in aqueous medium and decelerate the desorption of vitamins.

  2. Zinc-induced interaction of the metal-binding domain of amyloid-β peptide with DNA.

    PubMed

    Khmeleva, Svetlana A; Mezentsev, Yuri V; Kozin, Sergey A; Tsvetkov, Philipp O; Ivanov, Alexis S; Bodoev, Nikolay V; Makarov, Alexander A; Radko, Sergey P

    2013-01-01

    The interaction of the 16-mer synthetic peptide (Aβ16), which represents the metal-binding domain of the amyloid-β with DNA, was studied employing the surface plasmon resonance technique. It has been shown that Aβ16 binds to the duplex DNA in the presence of zinc ions and thus the metal-binding domain can serve as a zinc-dependent DNA-binding site of the amyloid-β. The interaction of Aβ16 with DNA most probably depends on oligomerization of the peptide and is dominated by interaction with phosphates of the DNA backbone.

  3. Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica

    NASA Astrophysics Data System (ADS)

    Gómez-Cazalilla, M.; Mérida-Robles, J. M.; Gurbani, A.; Rodríguez-Castellón, E.; Jiménez-López, A.

    2007-03-01

    A series of Al-containing SBA-15 type materials with different Si/Al ratio, were prepared by post-synthesis modification of a pure highly ordered mesoporous silica SBA-15 obtained by using sodium silicate as silica source, and amphiphilic block copolymer as structure-directing agent. A high level of aluminum incorporation was achieved, reaching an Si/Al ratio of up to 5.5, without any significant loss in the textural properties of SBA-15. These materials were fully characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), 27Al NMR spectroscopy, and N 2 adsorption at 77 K. The acid properties of these materials have been evaluated by NH 3-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FTIR spectroscopy. The effective acidity of these materials was evaluated using two catalytic reactions: 2-propanol dehydrogenation and 1-butene isomerization. The adsorption of basic probe molecules and the catalytic behavior revealed an evolution of the acid properties with the Al content. These studies have shown that the Al-SBA-15 materials contain Brønsted and Lewis acid sites with medium acidity which makes them appropriate to be used as acid catalysts in heterogeneous catalysis, catalytic supports, and adsorbents.

  4. Absorption Spectroscopy Study of Acid-Base and Metal-Binding Properties of Flavanones

    NASA Astrophysics Data System (ADS)

    Shubina, V. S.; Shatalina, Yu. V.

    2013-11-01

    We have used absorption spectroscopy to study the acid-base and metal-binding properties of two structurally similar flavanones: taxifolin and naringenin. We have determined the acid dissociation constants for taxifolin (pKa1 = 7.10 ± 0.05, pKa2 = 8.60 ± 0.09, pKa3 = 8.59 ± 0.19, pKa4 = 11.82 ± 0.36) and naringenin (pKa1 = 7.05 ± 0.05, pKa2 = 8.85 ± 0.09, pKa3 = 12.01 ± 0.38). The appearance of new absorption bands in the visible wavelength region let us determine the stoichiometric composition of the iron (II) complexes of the flavanones. We show that at pH 5, in solution there is a mixture of complexes between taxifolin and iron (II) ions in stoichiometric ratio 2:1 and 1:2, while at pH 7.4 and pH 9, we detect a 1:1 taxifolin:Fe(II) complex. We established that at these pH values, naringenin forms a 2:1 complex with iron (II) ions. We propose structures for the complexes formed. Comprehensive study of the acid-base properties and the metal-binding capability of the two structurally similar flavanones let us determine the structure-properties relation and the conditions under which antioxidant activity of the polyphenols appears, via chelation of variable-valence metal ions.

  5. Growth-inhibitory and metal-binding proteins in Chlorella vulgaris exposed to cadmium or zinc.

    PubMed

    Huang, Zhiyong; Li, Lianping; Huang, Gaoling; Yan, Qingpi; Shi, Bing; Xu, Xiaoqin

    2009-01-18

    Phytochelatins, with the general structure of (gamma-Glu-Cys)n-Gly (n=2-11), are usually recognized as being strongly induced by metals in microalgae and play an important role in the detoxification of heavy metals in environment. However, there have been few studies on metallothionein (MT) synthesis in Chlorella vulgaris (C. vulgaris) exposed to heavy metals. The present study describes the growth inhibition of C. vulgaris exposed to different concentrations of cadmium and zinc, and the induction of metal-binding MT-like proteins in the cells. The amounts of metal-binding proteins, induced in the alga exposed to different concentrations of Cd and Zn, were analyzed with a size-exclusion HPLC coupled to ICP-MS. After being purified with a gel filtration column (Sephadex G-75, 3.5cmx80cm) and a desalting column (G-25, 1.5cmx30cm), the isoforms and sub-isoforms of Zn-binding protein were characterized by a reverse phase-HPLC coupled to electrospray ionization and a triple quadrupole mass spectrometer (HPLC-ESI-MS/MS). In addition, the ultraviolet spectra of purified Zn-binding proteins were analyzed in media with different pH values. The results showed that the significant inhibitory effects (at p<0.05) on the cell growth were observed when excessive metals such as 80micromoll(-1) of Cd, and 60 and 80micromoll(-1) of Zn were added. The Cd/Zn-binding proteins induced in C. vulgaris exposed to Cd and Zn were referred to as Cd/Zn-MT-like proteins in which the mean molecular mass of the apo-MT-like was 6152Da. The induced Cd/Zn-MT-like proteins might be involved in the detoxification of heavy metals, such as cadmium and zinc, by the alga. PMID:19019465

  6. Double layer approach to create durable superhydrophobicity on cotton fabric using nano silica and auxiliary non fluorinated materials

    NASA Astrophysics Data System (ADS)

    Manatunga, Danushika Charyangi; de Silva, Rohini M.; de Silva, K. M. Nalin

    2016-01-01

    Creation of differential superhydrophobicity by applying different non-fluorinated hydrophobization agents on a cotton fabric roughened with silica nanoparticles was studied. Cotton fabric surface has been functionalized with silica nanoparticles and further hydrophobized with different hydrophobic agents such as hexadecyltrimethoxy silane (HDTMS), stearic acid (SA), triethoxyoctyl silane (OTES) and hybrid mixtures of HDTMS/SA and HDTMS/OTES. The cotton fabrics before and after the treatment were characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM) and thermogravimetric analysis (TGA). The wetting behavior of cotton samples was investigated by water contact angle (WCA) measurement, water uptake, water repellency and soil repellency testing. The treated fabrics exhibited excellent water repellency and high water contact angles (WCA). When the mixture of two hydrophobization agents such as HDTMS/OTES and HDTMS/SA is used, the water contact angle has increased (145°-160°) compared to systems containing HDTMS, OTES, SA alone (130°-140°). It was also noted that this fabricated double layer (silica + hydrophobization agent) was robust even after applying harsh washing conditions and there is an excellent anti-soiling effect observed over different stains. Therefore superhydrophobic cotton surfaces with high WCA and soil repellency could be obtained with silica and mixture of hydrophobization agents which are cost effective and environmentally friendly when compared with the fluorosilane treatment.

  7. One-step synthesis of amine-functionalized hollow mesoporous silica nanoparticles as efficient antibacterial and anticancer materials

    PubMed Central

    Hao, Nanjing; Jayawardana, Kalana W.; Chen, Xuan; De Zoysa, Thareendra

    2015-01-01

    In this study, amine-functionalized hollow mesoporous silica nanoparticles with an average diameter of ~100 nm and shell thickness of ~20 nm were prepared by an one-step process. This new nanoparticulate system exhibited excellent killing efficiency against mycobacterial (M. smegmatis strain mc2 651) and cancer cells (A549). PMID:25562524

  8. High-resolution magic angle spinning description of the interaction states and their kinetics among basic solutes and functionalized silica materials.

    PubMed

    Lopez, Claire; Carrara, Caroline; Tchapla, Alain; Caldarelli, Stefano

    2013-12-20

    Modeling of the interaction is crucial to understanding and predicting chromatography. However, the complexity and variety of the grafted motifs render the creation of an accurate model overwhelmingly challenging, so that most often the classification of column separation properties is described by monitoring the retention times of carefully selected control molecules. We analyzed here the characteristics of the interplay of compounds of basic nature by (1)H HRMAS NMR, which provide relevant descriptors for products with pharmaceutical properties, with chromatographic phases for Reversed Phase Liquid Chromatography. Eight grafted silica phases were selected, differing to enhance specific structural properties (monomeric and polymeric grafts, endcapping or not, carbon content, alkyl with polar embedded group or alkyl bonded chain, chemical nature of end capping, native silica). These materials were put in interaction with five basic molecules, previously chosen as probes for the evaluation of efficient base deactivated liquid stationary phases using five theoretical molecular descriptors to cover a large scale of molecular volume, polar surface area, LogP, hydrogen-bond donor capacity and finally hydrogen-bond acceptor capacity. (1)H HRMAS NMR was capable of describing qualitatively a wealth of interaction states, characterized both thermodynamically and kinetically. In one case (penbutolol) up to five interaction states could be differentiated. Variable temperature experiments revealed the complexity of the retention process on grafted silica as in some cases the kinetics of the interaction is shown to slow down on increasing the temperature.

  9. Silica, hybrid silica, hydride silica and non-silica stationary phases for liquid chromatography.

    PubMed

    Borges, Endler M

    2015-04-01

    Free silanols on the surface of silica are the "villains", which are responsible for detrimental interactions of those compounds and the stationary phase (i.e., bad peak shape, low efficiency) as well as low thermal and chemical stability. For these reasons, we began this review describing new silica and hybrid silica stationary phases, which have reduced and/or shielded silanols. At present, in liquid chromatography for the majority of analyses, reversed-phase liquid chromatography is the separation mode of choice. However, the needs for increased selectivity and increased retention of hydrophilic bases have substantially increased the interest in hydrophilic interaction chromatography (HILIC). Therefore, stationary phases and this mode of separation are discussed. Then, non-silica stationary phases (i.e., zirconium oxide, titanium oxide, alumina and porous graphitized carbon), which afford increased thermal and chemical stability and also selectivity different from those obtained with silica and hybrid silica, are discussed. In addition, the use of these materials in HILIC is also reviewed.

  10. Sol-gel encapsulation of binary Zn(II) compounds in silica nanoparticles. Structure-activity correlations in hybrid materials targeting Zn(II) antibacterial use.

    PubMed

    Halevas, E; Nday, C M; Kaprara, E; Psycharis, V; Raptopoulou, C P; Jackson, G E; Litsardakis, G; Salifoglou, A

    2015-10-01

    In the emerging issue of enhanced multi-resistant properties in infectious pathogens, new nanomaterials with optimally efficient antibacterial activity and lower toxicity than other species attract considerable research interest. In an effort to develop such efficient antibacterials, we a) synthesized acid-catalyzed silica-gel matrices, b) evaluated the suitability of these matrices as potential carrier materials for controlled release of ZnSO4 and a new Zn(II) binary complex with a suitably designed well-defined Schiff base, and c) investigated structural and textural properties of the nanomaterials. Physicochemical characterization of the (empty-loaded) silica-nanoparticles led to an optimized material configuration linked to the delivery of the encapsulated antibacterial zinc load. Entrapment and drug release studies showed the competence of hybrid nanoparticles with respect to the a) zinc loading capacity, b) congruence with zinc physicochemical attributes, and c) release profile of their zinc load. The material antimicrobial properties were demonstrated against Gram-positive (Staphylococcus aureus, Bacillus subtilis, Bacillus cereus) and negative (Escherichia coli, Pseudomonas aeruginosa, Xanthomonas campestris) bacteria using modified agar diffusion methods. ZnSO4 showed less extensive antimicrobial behavior compared to Zn(II)-Schiff, implying that the Zn(II)-bound ligand enhances zinc antimicrobial properties. All zinc-loaded nanoparticles were less antimicrobially active than zinc compounds alone, as encapsulation controls their release, thereby attenuating their antimicrobial activity. To this end, as the amount of loaded zinc increases, the antimicrobial behavior of the nano-agent improves. Collectively, for the first time, sol-gel zinc-loaded silica-nanoparticles were shown to exhibit well-defined antimicrobial activity, justifying due attention to further development of antibacterial nanotechnology.

  11. MODELING OF METAL BINDING ON HUMIC SUBSTANCES USING THE NIST DATABASE: AN A PRIORI FUNCTIONAL GROUP APPROACH

    EPA Science Inventory

    Various modeling approaches have been developed for metal binding on humic substances. However, most of these models are still curve-fitting exercises-- the resulting set of parameters such as affinity constants (or the distribution of them) is found to depend on pH, ionic stren...

  12. A Rapid and Sensitive Strip-Based Quick Test for Nerve Agents Tabun, Sarin, and Soman Using BODIPY-Modified Silica Materials.

    PubMed

    Climent, Estela; Biyikal, Mustafa; Gawlitza, Kornelia; Dropa, Tomáš; Urban, Martin; Costero, Ana M; Martínez-Máñez, Ramón; Rurack, Knut

    2016-08-01

    Test strips that in combination with a portable fluorescence reader or digital camera can rapidly and selectively detect chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB), and Soman (GD) and their simulants in the gas phase have been developed. The strips contain spots of a hybrid indicator material consisting of a fluorescent BODIPY indicator covalently anchored into the channels of mesoporous SBA silica microparticles. The fluorescence quenching response allows the sensitive detection of CWAs in the μg m(-3) range in a few seconds. PMID:27124609

  13. A Rapid and Sensitive Strip-Based Quick Test for Nerve Agents Tabun, Sarin, and Soman Using BODIPY-Modified Silica Materials.

    PubMed

    Climent, Estela; Biyikal, Mustafa; Gawlitza, Kornelia; Dropa, Tomáš; Urban, Martin; Costero, Ana M; Martínez-Máñez, Ramón; Rurack, Knut

    2016-08-01

    Test strips that in combination with a portable fluorescence reader or digital camera can rapidly and selectively detect chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB), and Soman (GD) and their simulants in the gas phase have been developed. The strips contain spots of a hybrid indicator material consisting of a fluorescent BODIPY indicator covalently anchored into the channels of mesoporous SBA silica microparticles. The fluorescence quenching response allows the sensitive detection of CWAs in the μg m(-3) range in a few seconds.

  14. Novel silica surface charge density mediated control of the optical properties of embedded optically active materials and its application for fiber optic pH sensing at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Wang, Congjun; Ohodnicki, Paul R.; Su, Xin; Keller, Murphy; Brown, Thomas D.; Baltrus, John P.

    2015-01-01

    Silica and silica incorporated nanocomposite materials have been extensively studied for a wide range of applications. Here we demonstrate an intriguing optical effect of silica that, depending on the solution pH, amplifies or attenuates the optical absorption of a variety of embedded optically active materials with very distinct properties, such as plasmonic Au nanoparticles, non-plasmonic Pt nanoparticles, and the organic dye rhodamine B (not a pH indicator), coated on an optical fiber. Interestingly, the observed optical response to varying pH appears to follow the surface charge density of the silica matrix for all the three different optically active materials. To the best of our knowledge, this optical effect has not been previously reported and it appears universal in that it is likely that any optically active material can be incorporated into the silica matrix to respond to solution pH or surface charge density variations. A direct application of this effect is for optical pH sensing which has very attractive features that can enable minimally invasive, remote, real time and continuous distributed pH monitoring. Particularly, as demonstrated here, using highly stable metal nanoparticles embedded in an inorganic silica matrix can significantly improve the capability of pH sensing in extremely harsh environments which is of increasing importance for applications in unconventional oil and gas resource recovery, carbon sequestration, water quality monitoring, etc. Our approach opens a pathway towards possible future development of robust optical pH sensors for the most demanding environmental conditions. The newly discovered optical effect of silica also offers the potential for control of the optical properties of optically active materials for a range of other potential applications such as electrochromic devices.Silica and silica incorporated nanocomposite materials have been extensively studied for a wide range of applications. Here we demonstrate an

  15. Designed synthesis of carbon-functional magnetic graphene mesoporous silica materials using polydopamine as carbon precursor for the selective enrichment of N-linked glycan.

    PubMed

    Sun, Nianrong; Yao, Jizong; Deng, Chunhui

    2016-02-01

    Glycosylation, which has been confirmed to be associated with many diseases, is an important protein post-translation modification. Taking into account the low abundant of glycan, the purification of complex biological samples is considered to be very significant before mass spectrometry detection. In this work, carbon-functionalized magnetic graphene /mesoporous silica materials (C-Mag G@mSiO2 materials) with high content of carbon were designed and synthesized by using polydopamine as carbon precursor. Taking advantage of the special interaction between carbon and glycan, C-Mag G@mSiO2 materials were successfully applied to enrich N-linked glycans in different complex samples, such as standard glycoprotein digestion, the mixture of standard glycoprotein digestion, glycoprotein and non-glycoprotein, and human serum.

  16. The Fungus Tremella mesenterica Encodes the Longest Metallothionein Currently Known: Gene, Protein and Metal Binding Characterization.

    PubMed

    Iturbe-Espinoza, Paul; Gil-Moreno, Selene; Lin, Weiyu; Calatayud, Sara; Palacios, Òscar; Capdevila, Mercè; Atrian, Sílvia

    2016-01-01

    Fungal Cu-thioneins, and among them, the paradigmatic Neurospora crassa metallothionein (MT) (26 residues), were once considered as the shortest MTs--the ubiquitous, versatile metal-binding proteins--among all organisms, and thus representatives of their primeval forms. Nowadays, fungal MTs of diverse lengths and sequence features are known, following the huge heterogeneity of the Kingdom of Fungi. At the opposite end of N. crassa MT, the recently reported Cryptococcus neoformans CnMT1 and CnMT2 (122 and 186 aa) constitute the longest reported fungal MTs, having been identified as virulence factors of this pathogen. CnMTs are high-capacity Cu-thioneins that appear to be built by tandem amplification of a basic unit, a 7-Cys segment homologous to N. crassa MT. Here, we report the in silico, in vivo and in vitro study of a still longer fungal MT, belonging to Tremella mesenterica (TmMT), a saprophytic ascomycete. The TmMT gene has 10 exons, and it yields a 779-bp mature transcript that encodes a 257 residue-long protein. This MT is also built by repeated fragments, but of variable number of Cys: six units of the 7-Cys building blocks--CXCX3CSCPPGXCXCAXCP-, two fragments of six Cys, plus three Cys at the N-terminus. TmMT metal binding abilities have been analyzed through the spectrophotometric and spectrometric characterization of its recombinant Zn-, Cd- and Cu-complexes. Results allow it to be unambiguous classified as a Cu-thionein, also of extraordinary coordinating capacity. According to this feature, when the TmMT cDNA is expressed in MT-devoid yeast cells, it is capable of restoring a high Cu tolerance level. Since it is not obvious that T. mesenterica shares the same physiological needs for a high capacity Cu-binding protein with C. neoformans, the existence of this peculiar MT might be better explained on the basis of a possible role in Cu-handling for the Cu-enzymes responsible in lignin degradation pathways. PMID:26882011

  17. The Fungus Tremella mesenterica Encodes the Longest Metallothionein Currently Known: Gene, Protein and Metal Binding Characterization

    PubMed Central

    Lin, Weiyu; Calatayud, Sara; Palacios, Òscar; Capdevila, Mercè; Atrian, Sílvia

    2016-01-01

    Fungal Cu-thioneins, and among them, the paradigmatic Neurospora crassa metallothionein (MT) (26 residues), were once considered as the shortest MTs -the ubiquitous, versatile metal-binding proteins- among all organisms, and thus representatives of their primeval forms. Nowadays, fungal MTs of diverse lengths and sequence features are known, following the huge heterogeneity of the Kingdom of Fungi. At the opposite end of N. crassa MT, the recently reported Cryptococcus neoformans CnMT1 and CnMT2 (122 and 186 aa) constitute the longest reported fungal MTs, having been identified as virulence factors of this pathogen. CnMTs are high-capacity Cu-thioneins that appear to be built by tandem amplification of a basic unit, a 7-Cys segment homologous to N. crassa MT. Here, we report the in silico, in vivo and in vitro study of a still longer fungal MT, belonging to Tremella mesenterica (TmMT), a saprophytic ascomycete. The TmMT gene has 10 exons, and it yields a 779-bp mature transcript that encodes a 257 residue-long protein. This MT is also built by repeated fragments, but of variable number of Cys: six units of the 7-Cys building blocks-CXCX3CSCPPGXCXCAXCP-, two fragments of six Cys, plus three Cys at the N-terminus. TmMT metal binding abilities have been analyzed through the spectrophotometric and spectrometric characterization of its recombinant Zn-, Cd- and Cu-complexes. Results allow it to be unambiguous classified as a Cu-thionein, also of extraordinary coordinating capacity. According to this feature, when the TmMT cDNA is expressed in MT-devoid yeast cells, it is capable of restoring a high Cu tolerance level. Since it is not obvious that T. mesenterica shares the same physiological needs for a high capacity Cu-binding protein with C. neoformans, the existence of this peculiar MT might be better explained on the basis of a possible role in Cu-handling for the Cu-enzymes responsible in lignin degradation pathways. PMID:26882011

  18. ETMB-RBF: Discrimination of Metal-Binding Sites in Electron Transporters Based on RBF Networks with PSSM Profiles and Significant Amino Acid Pairs

    PubMed Central

    Ou, Yu-Yen; Chen, Shu-An; Wu, Sheng-Cheng

    2013-01-01

    Background Cellular respiration is the process by which cells obtain energy from glucose and is a very important biological process in living cell. As cells do cellular respiration, they need a pathway to store and transport electrons, the electron transport chain. The function of the electron transport chain is to produce a trans-membrane proton electrochemical gradient as a result of oxidation–reduction reactions. In these oxidation–reduction reactions in electron transport chains, metal ions play very important role as electron donor and acceptor. For example, Fe ions are in complex I and complex II, and Cu ions are in complex IV. Therefore, to identify metal-binding sites in electron transporters is an important issue in helping biologists better understand the workings of the electron transport chain. Methods We propose a method based on Position Specific Scoring Matrix (PSSM) profiles and significant amino acid pairs to identify metal-binding residues in electron transport proteins. Results We have selected a non-redundant set of 55 metal-binding electron transport proteins as our dataset. The proposed method can predict metal-binding sites in electron transport proteins with an average 10-fold cross-validation accuracy of 93.2% and 93.1% for metal-binding cysteine and histidine, respectively. Compared with the general metal-binding predictor from A. Passerini et al., the proposed method can improve over 9% of sensitivity, and 14% specificity on the independent dataset in identifying metal-binding cysteines. The proposed method can also improve almost 76% sensitivity with same specificity in metal-binding histidine, and MCC is also improved from 0.28 to 0.88. Conclusions We have developed a novel approach based on PSSM profiles and significant amino acid pairs for identifying metal-binding sites from electron transport proteins. The proposed approach achieved a significant improvement with independent test set of metal-binding electron transport proteins

  19. Novel silica surface charge density mediated control of the optical properties of embedded optically active materials and its application for fiber optic pH sensing at elevated temperatures.

    PubMed

    Wang, Congjun; Ohodnicki, Paul R; Su, Xin; Keller, Murphy; Brown, Thomas D; Baltrus, John P

    2015-02-14

    Silica and silica incorporated nanocomposite materials have been extensively studied for a wide range of applications. Here we demonstrate an intriguing optical effect of silica that, depending on the solution pH, amplifies or attenuates the optical absorption of a variety of embedded optically active materials with very distinct properties, such as plasmonic Au nanoparticles, non-plasmonic Pt nanoparticles, and the organic dye rhodamine B (not a pH indicator), coated on an optical fiber. Interestingly, the observed optical response to varying pH appears to follow the surface charge density of the silica matrix for all the three different optically active materials. To the best of our knowledge, this optical effect has not been previously reported and it appears universal in that it is likely that any optically active material can be incorporated into the silica matrix to respond to solution pH or surface charge density variations. A direct application of this effect is for optical pH sensing which has very attractive features that can enable minimally invasive, remote, real time and continuous distributed pH monitoring. Particularly, as demonstrated here, using highly stable metal nanoparticles embedded in an inorganic silica matrix can significantly improve the capability of pH sensing in extremely harsh environments which is of increasing importance for applications in unconventional oil and gas resource recovery, carbon sequestration, water quality monitoring, etc. Our approach opens a pathway towards possible future development of robust optical pH sensors for the most demanding environmental conditions. The newly discovered optical effect of silica also offers the potential for control of the optical properties of optically active materials for a range of other potential applications such as electrochromic devices. PMID:25572664

  20. Novel silica surface charge density mediated control of the optical properties of embedded optically active materials and its application for fiber optic pH sensing at elevated temperatures.

    PubMed

    Wang, Congjun; Ohodnicki, Paul R; Su, Xin; Keller, Murphy; Brown, Thomas D; Baltrus, John P

    2015-02-14

    Silica and silica incorporated nanocomposite materials have been extensively studied for a wide range of applications. Here we demonstrate an intriguing optical effect of silica that, depending on the solution pH, amplifies or attenuates the optical absorption of a variety of embedded optically active materials with very distinct properties, such as plasmonic Au nanoparticles, non-plasmonic Pt nanoparticles, and the organic dye rhodamine B (not a pH indicator), coated on an optical fiber. Interestingly, the observed optical response to varying pH appears to follow the surface charge density of the silica matrix for all the three different optically active materials. To the best of our knowledge, this optical effect has not been previously reported and it appears universal in that it is likely that any optically active material can be incorporated into the silica matrix to respond to solution pH or surface charge density variations. A direct application of this effect is for optical pH sensing which has very attractive features that can enable minimally invasive, remote, real time and continuous distributed pH monitoring. Particularly, as demonstrated here, using highly stable metal nanoparticles embedded in an inorganic silica matrix can significantly improve the capability of pH sensing in extremely harsh environments which is of increasing importance for applications in unconventional oil and gas resource recovery, carbon sequestration, water quality monitoring, etc. Our approach opens a pathway towards possible future development of robust optical pH sensors for the most demanding environmental conditions. The newly discovered optical effect of silica also offers the potential for control of the optical properties of optically active materials for a range of other potential applications such as electrochromic devices.

  1. Synthesis of a metal binding protein designed on the alpha/beta scaffold of charybdotoxin.

    PubMed

    Pierret, B; Virelizier, H; Vita, C

    1995-12-01

    The alpha/beta scaffold of the scorpion toxin charybdotoxin has been used for the engineering of a metal binding site. Nine substitutions, including three histidines as metal ligands, have been introduced into the original toxin sequence. The newly designed sequence, 37 amino acids long, has been assembled by solid-phase synthesis and HBTU (2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate) coupling of Fmoc-protected amino acids. Formation of the three disulfide bonds occurred efficiently and rapidly in the presence of glutathione, and this post-synthesis modification has facilitated the purification task enormously. The process of synthesis and purification was performed in less than a week with an overall 10.2% yield. Circular dichroism analysis showed that the newly designed protein is folded in a alpha/beta structure, similarly to the parent toxin. Electronic absorption spectroscopy, circular dichroism and gel filtration experiments have been used to show that Cu2+ and Zn2+ ions bind with high affinity to the newly engineered protein. These results demonstrate that the alpha/beta fold, common to all scorpion toxins, is a very versatile basic structure, tolerant for substitutions and able to present new sequences in a predetermined conformation. The chemical approach is shown to be effective, rapid and practical for the production of novel designed small proteins.

  2. Metal-binding peptides: Their role in responses to metal stress

    SciTech Connect

    Rauser, W.E. )

    1989-04-01

    Excess metals are one stress that plants may encounter. The metals Cd, Cu, Ni, and Zn are considered because of concern for their entry into the foodchain of animals and man. Studies of metal tolerant plants and cell cultures suggest three types of responses: exclusion of metal from protoplasts by binding to cell walls, differential membrane transport reducing metal exposure of enzymes, and intracellular chelation of metal in innocuous forms. One group of compounds involved in the latter response are metal-binding peptides designated phytochelatins. They are a family of small peptides composed of five kinds of amino acids, including 2 to 11 cysteines which provide thiols for selective binding of metal. Metals induce the synthesis of phytochelatins through unknown enzymes involving glutathione. In plant cell cultures the peptides bind about 90% of the intracellular Cd. In roots of young plants up to half of the metal is bound by phytochelatins. Intact plants probably use a combination of responses to deal with excess metals, phytochelatins may dominate in certain cases.

  3. Evolutionary history of redox metal-binding domains across the tree of life.

    PubMed

    Harel, Arye; Bromberg, Yana; Falkowski, Paul G; Bhattacharya, Debashish

    2014-05-13

    Oxidoreductases mediate electron transfer (i.e., redox) reactions across the tree of life and ultimately facilitate the biologically driven fluxes of hydrogen, carbon, nitrogen, oxygen, and sulfur on Earth. The core enzymes responsible for these reactions are ancient, often small in size, and highly diverse in amino acid sequence, and many require specific transition metals in their active sites. Here we reconstruct the evolution of metal-binding domains in extant oxidoreductases using a flexible network approach and permissive profile alignments based on available microbial genome data. Our results suggest there were at least 10 independent origins of redox domain families. However, we also identified multiple ancient connections between Fe2S2- (adrenodoxin-like) and heme- (cytochrome c) binding domains. Our results suggest that these two iron-containing redox families had a single common ancestor that underwent duplication and divergence. The iron-containing protein family constitutes ∼50% of all metal-containing oxidoreductases and potentially catalyzed redox reactions in the Archean oceans. Heme-binding domains seem to be derived via modular evolutionary processes that ultimately form the backbone of redox reactions in both anaerobic and aerobic respiration and photosynthesis. The empirically discovered network allows us to peer into the ancient history of microbial metabolism on our planet.

  4. Earthworm Lumbricus rubellus MT-2: Metal Binding and Protein Folding of a True Cadmium-MT.

    PubMed

    Kowald, Gregory R; Stürzenbaum, Stephen R; Blindauer, Claudia A

    2016-01-05

    Earthworms express, as most animals, metallothioneins (MTs)-small, cysteine-rich proteins that bind d(10) metal ions (Zn(II), Cd(II), or Cu(I)) in clusters. Three MT homologues are known for Lumbricus rubellus, the common red earthworm, one of which, wMT-2, is strongly induced by exposure of worms to cadmium. This study concerns composition, metal binding affinity and metal-dependent protein folding of wMT-2 expressed recombinantly and purified in the presence of Cd(II) and Zn(II). Crucially, whilst a single Cd₇wMT-2 species was isolated from wMT-2-expressing E. coli cultures supplemented with Cd(II), expressions in the presence of Zn(II) yielded mixtures. The average affinities of wMT-2 determined for either Cd(II) or Zn(II) are both within normal ranges for MTs; hence, differential behaviour cannot be explained on the basis of overall affinity. Therefore, the protein folding properties of Cd- and Zn-wMT-2 were compared by ¹H NMR spectroscopy. This comparison revealed that the protein fold is better defined in the presence of cadmium than in the presence of zinc. These differences in folding and dynamics may be at the root of the differential behaviour of the cadmium- and zinc-bound protein in vitro, and may ultimately also help in distinguishing zinc and cadmium in the earthworm in vivo.

  5. Evolutionary history of redox metal-binding domains across the tree of life.

    PubMed

    Harel, Arye; Bromberg, Yana; Falkowski, Paul G; Bhattacharya, Debashish

    2014-05-13

    Oxidoreductases mediate electron transfer (i.e., redox) reactions across the tree of life and ultimately facilitate the biologically driven fluxes of hydrogen, carbon, nitrogen, oxygen, and sulfur on Earth. The core enzymes responsible for these reactions are ancient, often small in size, and highly diverse in amino acid sequence, and many require specific transition metals in their active sites. Here we reconstruct the evolution of metal-binding domains in extant oxidoreductases using a flexible network approach and permissive profile alignments based on available microbial genome data. Our results suggest there were at least 10 independent origins of redox domain families. However, we also identified multiple ancient connections between Fe2S2- (adrenodoxin-like) and heme- (cytochrome c) binding domains. Our results suggest that these two iron-containing redox families had a single common ancestor that underwent duplication and divergence. The iron-containing protein family constitutes ∼50% of all metal-containing oxidoreductases and potentially catalyzed redox reactions in the Archean oceans. Heme-binding domains seem to be derived via modular evolutionary processes that ultimately form the backbone of redox reactions in both anaerobic and aerobic respiration and photosynthesis. The empirically discovered network allows us to peer into the ancient history of microbial metabolism on our planet. PMID:24778258

  6. Metal Binding in Photosystem II Super- and Subcomplexes from Barley Thylakoids.

    PubMed

    Schmidt, Sidsel Birkelund; Persson, Daniel Pergament; Powikrowska, Marta; Frydenvang, Jens; Schjoerring, Jan K; Jensen, Poul Erik; Husted, Søren

    2015-08-01

    Metals exert important functions in the chloroplast of plants, where they act as cofactors and catalysts in the photosynthetic electron transport chain. In particular, manganese (Mn) has a key function because of its indispensable role in the water-splitting reaction of photosystem II (PSII). More and better knowledge is required on how the various complexes of PSII are affected in response to, for example, nutritional disorders and other environmental stress conditions. We here present, to our knowledge, a new method that allows the analysis of metal binding in intact photosynthetic complexes of barley (Hordeum vulgare) thylakoids. The method is based on size exclusion chromatography coupled to inductively coupled plasma triple-quadrupole mass spectrometry. Proper fractionation of PSII super- and subcomplexes was achieved by critical selection of elution buffers, detergents for protein solubilization, and stabilizers to maintain complex integrity. The applicability of the method was shown by quantification of Mn binding in PSII from thylakoids of two barley genotypes with contrasting Mn efficiency exposed to increasing levels of Mn deficiency. The amount of PSII supercomplexes was drastically reduced in response to Mn deficiency. The Mn efficient genotype bound significantly more Mn per unit of PSII under control and mild Mn deficiency conditions than the inefficient genotype, despite having lower or similar total leaf Mn concentrations. It is concluded that the new method facilitates studies of the internal use of Mn and other biometals in various PSII complexes as well as their relative dynamics according to changes in environmental conditions. PMID:26084923

  7. Earthworm Lumbricus rubellus MT-2: Metal Binding and Protein Folding of a True Cadmium-MT

    PubMed Central

    Kowald, Gregory R.; Stürzenbaum, Stephen R.; Blindauer, Claudia A.

    2016-01-01

    Earthworms express, as most animals, metallothioneins (MTs)—small, cysteine-rich proteins that bind d10 metal ions (Zn(II), Cd(II), or Cu(I)) in clusters. Three MT homologues are known for Lumbricus rubellus, the common red earthworm, one of which, wMT-2, is strongly induced by exposure of worms to cadmium. This study concerns composition, metal binding affinity and metal-dependent protein folding of wMT-2 expressed recombinantly and purified in the presence of Cd(II) and Zn(II). Crucially, whilst a single Cd7wMT-2 species was isolated from wMT-2-expressing E. coli cultures supplemented with Cd(II), expressions in the presence of Zn(II) yielded mixtures. The average affinities of wMT-2 determined for either Cd(II) or Zn(II) are both within normal ranges for MTs; hence, differential behaviour cannot be explained on the basis of overall affinity. Therefore, the protein folding properties of Cd- and Zn-wMT-2 were compared by 1H NMR spectroscopy. This comparison revealed that the protein fold is better defined in the presence of cadmium than in the presence of zinc. These differences in folding and dynamics may be at the root of the differential behaviour of the cadmium- and zinc-bound protein in vitro, and may ultimately also help in distinguishing zinc and cadmium in the earthworm in vivo. PMID:26742040

  8. Heterogeneity in metal binding by individual fluorescent components in a eutrophic algae-rich lake.

    PubMed

    Xu, Huacheng; Yan, Zaisheng; Cai, Haiyuan; Yu, Guanghui; Yang, Liuyan; Jiang, Helong

    2013-12-01

    Dissolved organic matter (DOM) affects the toxicity, mobility and bioavailability of metals in aquatic environment. In this study, the interactions between two metals of environmental concern [Cu(II) and Fe(III)] with DOM in a euthrophic algae-rich lake (Lake Taihu, China), including dissolved natural organic matter (NOM) and algal extracellular polymeric substance (EPS), were studied using fluorescence excitation-emission matrix (EEM) quenching titration combined with parallel factor (PARAFAC) analysis. Obvious protein-like peaks were detected in algal EPS matrix, while both protein- and humic-like peaks can be found in NOM. PARAFAC analysis identified four fluorescent components, including one humic-, one tryptophan- and two tyrosine-like components, from 114 EEM samples. It was shown that fluorescent tyrosine- (log K(M) > 5.21) and humic-like substances (log K(M) > 4.84) in NOM fraction exhibited higher metal binding capacities than those in EPS matrix, while algal EPS was characterized with a high metal-tryptophan-like substances affinity (log K(M) > 5.08). Moreover, for the eutrophic algae-rich lakes, fluorescent tryptophan- and humic-like substances were responsible for Cu transportation, whereas the mobility of Fe would be related with the tyrosine-like substances. The results facilitate a further insight into the biogeochemical behaviors of metals in eutrophic algae-rich ecosystems as well as other related aquatic environments.

  9. Metal Binding in Photosystem II Super- and Subcomplexes from Barley Thylakoids1

    PubMed Central

    Schmidt, Sidsel Birkelund; Persson, Daniel Pergament; Powikrowska, Marta; Frydenvang, Jens; Schjoerring, Jan K.; Jensen, Poul Erik; Husted, Søren

    2015-01-01

    Metals exert important functions in the chloroplast of plants, where they act as cofactors and catalysts in the photosynthetic electron transport chain. In particular, manganese (Mn) has a key function because of its indispensable role in the water-splitting reaction of photosystem II (PSII). More and better knowledge is required on how the various complexes of PSII are affected in response to, for example, nutritional disorders and other environmental stress conditions. We here present, to our knowledge, a new method that allows the analysis of metal binding in intact photosynthetic complexes of barley (Hordeum vulgare) thylakoids. The method is based on size exclusion chromatography coupled to inductively coupled plasma triple-quadrupole mass spectrometry. Proper fractionation of PSII super- and subcomplexes was achieved by critical selection of elution buffers, detergents for protein solubilization, and stabilizers to maintain complex integrity. The applicability of the method was shown by quantification of Mn binding in PSII from thylakoids of two barley genotypes with contrasting Mn efficiency exposed to increasing levels of Mn deficiency. The amount of PSII supercomplexes was drastically reduced in response to Mn deficiency. The Mn efficient genotype bound significantly more Mn per unit of PSII under control and mild Mn deficiency conditions than the inefficient genotype, despite having lower or similar total leaf Mn concentrations. It is concluded that the new method facilitates studies of the internal use of Mn and other biometals in various PSII complexes as well as their relative dynamics according to changes in environmental conditions. PMID:26084923

  10. "Gray Areas": Silica gels, amorphous silica and cryptocrystalline silica on fault surfaces

    NASA Astrophysics Data System (ADS)

    Rowe, C. D.; Kirkpatrick, J. D.; White, J. C.; Faber, C.; Caine, J. S.

    2012-12-01

    Silica gels, in the form of their solid-phase equivalents, are widely found in brittle fault zones and are commonly associated with mineral deposits. High- to moderate-velocity rotary friction experiments have produced silica gels on sliding surfaces coeval with dramatic slip weakening. In light of the latter, silica gel formation has been proposed as a potential mechanism of slip weakening during earthquakes in the shallow crust. However, low velocity sliding experiments have also produced significant amounts of amorphous material distributed throughout slipping layers, and dramatic weakening is not observed. Comparison of the products of laboratory experiments to geological examples is complicated by the diagenesis and lithification of silica gels. They may form hydrous and amorphous solids, hydrous crystalline solids, or dehydrate to quartz. In addition, the abundance and style of occurrence of these products in faults suggest that there are multiple origins for silica gels in faults. We review the mechanisms by which silica gels may form in fault zones and describe the solidification, crystallization and dehydration evolution of the silica. Analytical transmission electron microscope (TEM) observations of slip-surface silica deposits from the Corona Fault, San Francisco, the Dixie Valley Fault, Nevada, and the Olive Fault, Namibia typify the nano- to micro-structural evolution of the fault surface silica layers. We suggest criteria for identifying these materials in natural fault rocks. Some of these gels may form by comminution and hydrolization of silica-rich wall rocks, as has been observed in high-velocity experiments (Corona Fault). Others may form by depressurization and boiling of aqueous fluids, probably during fault valving (Olive Fault). Silica saturated hydrothermal fluids released during faulting may contribute in some cases (Dixie Valley Fault). Regardless of the mechanism of gel formation, the dramatic rheological weakening observed in friction

  11. Novel Sol–Gel Precursors for Thin Mesoporous Eu3+-Doped Silica Coatings as Efficient Luminescent Materials.

    PubMed Central

    2012-01-01

    Europium(III) ions containing mesoporous silica coatings have been prepared via a solvent evaporation-induced self-assembly (EISA) approach of different single-source precursors (SSPs) in the presence of Pluronic P123 as a structure-directing agent, using the spin-coating process. A deliberate tailoring of the chemical composition of the porous coatings with various Si:Eu ratios was achieved by processing mixtures of tetraethylorthosilicate (TEOS) and Eu3+-coordinated SSPs. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) analyses demonstrate that the thin metal oxide-doped silica coatings consist of a porous network with a short-range order of the pore structure, even at high europium(III) loadings. Furthermore, luminescence properties were investigated at different temperatures and different degrees of Eu3+ contents. The photoluminescence spectra clearly show characteristic emission peaks corresponding to the 5D0 → 7FJ (J = 0–5) transitions resulting in a red luminescence visible by the eyes, although the films have a very low thickness (150–200 nm). PMID:23503160

  12. Large-area electrochromic coatings: Composites of polyaniline and polyacrylate-silica hybrid sol-gel materials

    SciTech Connect

    Jang, G.W.; Chen, C.; Gumbs, R.W.; Wei, Y.; Yeh, J.M.

    1996-08-01

    A low-cost technique for fabricating large-area electrochromic coatings is described. Polyaniline was incorporated into polyacrylate-silica hybrid sol-gel networks using suspended particles or solutions. A solution of polyaniline and poly[methyl methacrylate-co-3-(trimethoxysilyl)propyl methacrylate] can be spray- or brush-coated on transparent indium-tin oxide substrates to form robust electrochromic coatings. Silane functional groups on the polyacrylate chain act as coupling and cross-linking agents to improve surface adhesion and mechanical properties of the resulting composite coatings. These coatings showed reversible transparent to green color change when polarized at potentials between {minus}0.4 and +0.4 V vs. Ag/AgCl in a 0.2 M LiClO{sub 4}/acetonitrile electrolyte solution. The cycle lifetimes of polyaniline films were improved by incorporating the polymer in the polyacrylate-silica matrix. Electrochromic switching was demonstrated for the composite coatings in large-area all-solid-state devices.

  13. Direct Measurement of the Nanomechanical Stability of a Redox Protein Active Site and Its Dependence upon Metal Binding.

    PubMed

    Giannotti, Marina I; Cabeza de Vaca, Israel; Artés, Juan M; Sanz, Fausto; Guallar, Victor; Gorostiza, Pau

    2015-09-10

    The structural basis of the low reorganization energy of cupredoxins has long been debated. These proteins reconcile a conformationally heterogeneous and exposed metal-chelating site with the highly rigid copper center required for efficient electron transfer. Here we combine single-molecule mechanical unfolding experiments with statistical analysis and computer simulations to show that the metal-binding region of apo-azurin is mechanically flexible and that high mechanical stability is imparted by copper binding. The unfolding pathway of the metal site depends on the pulling residue and suggests that partial unfolding of the metal-binding site could be facilitated by the physical interaction with certain regions of the redox protein. PMID:26305718

  14. Direct Measurement of the Nanomechanical Stability of a Redox Protein Active Site and Its Dependence upon Metal Binding.

    PubMed

    Giannotti, Marina I; Cabeza de Vaca, Israel; Artés, Juan M; Sanz, Fausto; Guallar, Victor; Gorostiza, Pau

    2015-09-10

    The structural basis of the low reorganization energy of cupredoxins has long been debated. These proteins reconcile a conformationally heterogeneous and exposed metal-chelating site with the highly rigid copper center required for efficient electron transfer. Here we combine single-molecule mechanical unfolding experiments with statistical analysis and computer simulations to show that the metal-binding region of apo-azurin is mechanically flexible and that high mechanical stability is imparted by copper binding. The unfolding pathway of the metal site depends on the pulling residue and suggests that partial unfolding of the metal-binding site could be facilitated by the physical interaction with certain regions of the redox protein.

  15. Two metal-binding peptides from the insect Orchesella cincta (Collembola) as a result of metallothionein cleavage.

    PubMed

    Hensbergen, P J; Donker, M H; Hunziker, P E; van der Schors, R C; van Straalen, N M

    2001-10-01

    Metallothionein (MT) is an ubiquitous heavy metal-binding protein which has been identified in animals, plants, protists, fungi and bacteria. In insects, primary structures of MTs are known only for Drosophila and the collembolan, Orchesella cincta. The MT cDNA from O. cincta encodes a 77 amino acid protein with 19 cysteines. Isolations of the protein itself have demonstrated the presence of two smaller metal-binding peptides, whose amino acid sequences correspond to parts of the cDNA, and which apparently result from cleavage of the native protein. The present study was undertaken to complete the picture of cleavage sites within the MT protein by applying protein isolation techniques in combination with mass spectrometry and N-terminal sequence analysis. Further, recombinant expression allowed us to study the intrinsic stability of the MT and to perform in vitro cleavage studies. The results show that the MT from O. cincta is specifically cleaved at two sites, both after the amino acid sequence Thr-Gln (TQ). One of these sites is located in the N-terminal region and the other in the linker region between two putative metal-binding clusters. When expressed in Escherichia coli, the recombinant O. cincta MT can be isolated in an uncleaved form; however, this protein can be cleaved in vitro by the proteolytic activity of O. cincta. In combination with other studies, the results suggest that the length of the linker region is important for the stability of MT as a two domain metal-binding protein.

  16. The metal binding site of the hepatitis C virus NS3 protease. A spectroscopic investigation.

    PubMed

    Urbani, A; Bazzo, R; Nardi, M C; Cicero, D O; De Francesco, R; Steinkühler, C; Barbato, G

    1998-07-24

    The NS3 region of the hepatitis C virus encodes for a serine protease activity, which is necessary for the processing of the nonstructural region of the viral polyprotein. The minimal domain with proteolytic activity resides in the N terminus, where a structural tetradentate zinc binding site is located. The ligands being been identified by x-ray crystallography as being three cysteines (Cys97, Cys99, and Cys145) and one histidine residue (His149), which is postulated to coordinate the metal through a water molecule. In this article, we present an analysis of the role of metal coordination with respect to enzyme activity and folding. Using NMR spectroscopy, the resonances of His149 were assigned based on their isotropic shift in a Co(II)-substituted protein. Data obtained with 15N-labeled NS3 protease were compatible with the involvement of the delta-N of His149 in metal coordination. pH titration experiments showed that the cooperative association of at least two protons is required in the protonation process of His149. Changes in the NMR signals of this residue between pH 7 and 5 are interpreted as evidence for a structural change at the metal binding site, which switches from a "closed" to an "open" conformation. Site-directed mutagenesis of His149 has shown the importance of this residue in the metal incorporation pathway and for achieving an active fold. The metal coordination of the protease was also investigated by circular dichroism and electronic absorption spectroscopies using a Co(II)-substituted enzyme. We show evidence for rearrangements of the metal coordination geometry induced by complex formation with an NS4A peptide cofactor. No such changes were observed upon binding to a substrate peptide. Also, CN- and N3- induced Co(II) ligand field perturbations, which went along with an 1.5-fold enhancement of protease activity.

  17. Hepatic cadmium, metal-binding proteins and bioaccumulation in bluegills exposed to aqueous cadmium

    USGS Publications Warehouse

    Cope, W.G.; Atchison, G.J.; Wiener, J.G.

    1994-01-01

    We examined sublethal responses of juvenile bluegills Lepomis macrochirus to aqueous cadmium in two 28-d tests (test I, 0.0-8.4 μg Cd per liter; test II, 0.0-32.3 μg Cd per liter) in an intermittent-flow diluter. The experimental design was completely randomized, with two replicates in each of eight treatments (seven Cd exposures and one water control with 25 fish per replicate). Cadmium did not affect the growth of test fish. The mean whole-body concentrations of Cd in exposed fish were 1.8- to 44-fold those in controls in the two tests. Mean concentrations of hepatic nonthionein cytosolic Cd (not bound by metal-binding proteins, MBP) in all Cd treatments greatly exceeded those in controls, and mean concentrations of hepatic MBP in all treatments except one (0.8 μg Cd per liter in test I) exceeded those in controls. Nonthionein cytosolic Cd, hepatic MBP, and whole-body Cd in bluegills were linearly related to exposure concentrations within the range 0 to 20 μg Cd per liter. Much of the total Cd-binding capacity of hepatic MBP per fish was occupied by Cd after the 28-d exposures, although additional Cd-binding capacity remained unoccupied by Cd in fish in all treatments. The mean total Cd-binding capacity of hepatic MBP per fish, which ranged from 1.7 to 14 nmol Cd in test I and from 0.8 to 24 nmol Cd in test II, increased in a concentration-response manner at exposure concentrations below 13 μg/L. Nonthionein cytosolic Cd was the most sensitive indicator of Cd exposure, based on an LOEC of 0.8 μg Cd per liter.

  18. Evolutionary Implications of Metal Binding Features in Different Species’ Prion Protein: An Inorganic Point of View

    PubMed Central

    La Mendola, Diego; Rizzarelli, Enrico

    2014-01-01

    Prion disorders are a group of fatal neurodegenerative conditions of mammals. The key molecular event in the pathogenesis of such diseases is the conformational conversion of prion protein, PrPC, into a misfolded form rich in β-sheet structure, PrPSc, but the detailed mechanistic aspects of prion protein conversion remain enigmatic. There is uncertainty on the precise physiological function of PrPC in healthy individuals. Several evidences support the notion of its role in copper homeostasis. PrPC binds Cu2+ mainly through a domain composed by four to five repeats of eight amino acids. In addition to mammals, PrP homologues have also been identified in birds, reptiles, amphibians and fish. The globular domain of protein is retained in the different species, suggesting that the protein carries out an essential common function. However, the comparison of amino acid sequences indicates that prion protein has evolved differently in each vertebrate class. The primary sequences are strongly conserved in each group, but these exhibit a low similarity with those of mammals. The N-terminal domain of different prions shows tandem amino acid repeats with an increasing amount of histidine residues going from amphibians to mammals. The difference in the sequence affects the number of copper binding sites, the affinity and the coordination environment of metal ions, suggesting that the involvement of prion in metal homeostasis may be a specific characteristic of mammalian prion protein. In this review, we describe the similarities and the differences in the metal binding of different species’ prion protein, as revealed by studies carried out on the entire protein and related peptide fragments. PMID:24970230

  19. Metal binding sites of the estradiol receptor from calf uterus and their possible role in the regulation of receptor function

    SciTech Connect

    Medici, N.; Minucci, S.; Nigro, V.; Abbondanza, C.; Armetta, I.; Molinari, A.M.; Puca, G.A. )

    1989-01-10

    The existence of putative metal binding sites on the estradiol receptor (ER) molecule from calf uterus was evaluated by immobilizing various divalent metals to iminodiacetate-Sepharose. ER from both crude and highly purified preparations binds to metal-containing adsorbents complexed with Zn(II), Ni(II), Co(II), and Cu(II), but not to those complexed with Fe(II) and Cd(II). Analysis of affinity-labeled ER by ({sup 3}H)tamoxifen aziridine after elution from a column of Zn(II)-charged iminodiacetate-Sepharose showed that ER fragments obtained by extensive trypsinization were also bound. Zn(II) and the same other metals able to bind ER, when immobilized on resins, inhibit the binding of estradiol to the receptor at micromolar concentration. This inhibition is noncompetitive and can be reversed by EDTA. The inhibition of the hormone binding was still present after trypsin treatment of the cytosol, and it was abolished by preincubation with the hormone. Micromolar concentrations of these metals were able to block those chemical-physical changes occurring during the process of ER transformation in vitro. The presence of metal binding sites that modulate the ER activity in the hormone binding domain of ER is speculated. Since progesterone receptor showed the same pattern of binding and elution from metal-containing adsorbents, the presence of metal binding regulatory sites could be a property of all steroid receptors.

  20. Template-directed covalent conjugation of DNA to native antibodies, transferrin and other metal-binding proteins

    NASA Astrophysics Data System (ADS)

    Rosen, Christian B.; Kodal, Anne L. B.; Nielsen, Jesper S.; Schaffert, David H.; Scavenius, Carsten; Okholm, Anders H.; Voigt, Niels V.; Enghild, Jan J.; Kjems, Jørgen; Tørring, Thomas; Gothelf, Kurt V.

    2014-09-01

    DNA-protein conjugates are important in bioanalytical chemistry, molecular diagnostics and bionanotechnology, as the DNA provides a unique handle to identify, functionalize or otherwise manipulate proteins. To maintain protein activity, conjugation of a single DNA handle to a specific location on the protein is often needed. However, preparing such high-quality site-specific conjugates often requires genetically engineered proteins, which is a laborious and technically challenging approach. Here we demonstrate a simpler method to create site-selective DNA-protein conjugates. Using a guiding DNA strand modified with a metal-binding functionality, we directed a second DNA strand to the vicinity of a metal-binding site of His6-tagged or wild-type metal-binding proteins, such as serotransferrin, where it subsequently reacted with lysine residues at that site. This method, DNA-templated protein conjugation, facilitates the production of site-selective protein conjugates, and also conjugation to IgG1 antibodies via a histidine cluster in the constant domain.

  1. Cadmium accumulation and toxicity in the unicellular alga Pseudokirchneriella subcapitata: Influence of metal-binding exudates and exposure time.

    PubMed

    Paquet, Nathalie; Lavoie, Michel; Maloney, Frédéric; Duval, Jérôme F L; Campbell, Peter G C; Fortin, Claude

    2015-07-01

    Predicting metal availability and toxicity for chronic (several hours or days) metal exposure scenarios, even for unicellular algae, is a major challenge to existing toxicity models. This is because several factors affecting metal uptake and toxicity, such as the release of metal-binding exudates, changes in the kinetics of metal uptake and toxicity over time, and algal physiological acclimation to internalized metals, are still poorly understood. The present study assessed the influence of these factors on Cd uptake and toxicity in laboratory batch cultures of the freshwater alga Pseudokirchneriella subcapitata. To do so, changes in the free Cd(2+) concentrations caused by the release of metal-binding algal exudates were monitored, (109)Cd accumulation in algal cells was measured, and Cd-induced inhibition of algal growth as a function of exposure time (from 12 h to 96 h) was followed. Results indicate that metal-binding exudates may decrease the proportion of the free Cd(2+) ion in solution up to 2-fold, a decrease that affects Cd uptake and toxicity. Pseudokirchneriella subcapitata has the capacity to decrease net Cd uptake rate on short time scales (<24 h), but this reduction in the Cd uptake rate disappeared after 24 h, and Cd toxicity occurred at relatively high Cd concentrations in solution. These data illustrate some of the pitfalls of standard algal toxicity assays, which were designed for acute exposures, and suggest how robust chronic bioassays might be developed.

  2. Enhanced Bioaccumulation of Heavy Metal Ions by Bacterial Cells Due to Surface Display of Short Metal Binding Peptides

    PubMed Central

    Kotrba, Pavel; Dolečková, Lucie; de Lorenzo, Víctor; Ruml, Tomas

    1999-01-01

    Metal binding peptides of sequences Gly-His-His-Pro-His-Gly (named HP) and Gly-Cys-Gly-Cys-Pro-Cys-Gly-Cys-Gly (named CP) were genetically engineered into LamB protein and expressed in Escherichia coli. The Cd2+-to-HP and Cd2+-to-CP stoichiometries of peptides were 1:1 and 3:1, respectively. Hybrid LamB proteins were found to be properly folded in the outer membrane of E. coli. Isolated cell envelopes of E. coli bearing newly added metal binding peptides showed an up to 1.8-fold increase in Cd2+ binding capacity. The bioaccumulation of Cd2+, Cu2+, and Zn2+ by E. coli was evaluated. Surface display of CP multiplied the ability of E. coli to bind Cd2+ from growth medium fourfold. Display of HP peptide did not contribute to an increase in the accumulation of Cu2+ and Zn2+. However, Cu2+ ceased contribution of HP for Cd2+ accumulation, probably due to the strong binding of Cu2+ to HP. Thus, considering the cooperation of cell structures with inserted peptides, the relative affinities of metal binding peptide and, for example, the cell wall to metal ion should be taken into account in the rational design of peptide sequences possessing specificity for a particular metal. PMID:10049868

  3. Silaffins in Silica Biomineralization and Biomimetic Silica Precipitation

    PubMed Central

    Lechner, Carolin C.; Becker, Christian F. W.

    2015-01-01

    Biomineralization processes leading to complex solid structures of inorganic material in biological systems are constantly gaining attention in biotechnology and biomedical research. An outstanding example for biomineral morphogenesis is the formation of highly elaborate, nano-patterned silica shells by diatoms. Among the organic macromolecules that have been closely linked to the tightly controlled precipitation of silica in diatoms, silaffins play an extraordinary role. These peptides typically occur as complex posttranslationally modified variants and are directly involved in the silica deposition process in diatoms. However, even in vitro silaffin-based peptides alone, with and without posttranslational modifications, can efficiently mediate biomimetic silica precipitation leading to silica material with different properties as well as with encapsulated cargo molecules of a large size range. In this review, the biomineralization process of silica in diatoms is summarized with a specific focus on silaffins and their in vitro silica precipitation properties. Applications in the area of bio- and nanotechnology as well as in diagnostics and therapy are discussed. PMID:26295401

  4. Mesoporous Silica: A Suitable Adsorbent for Amines

    PubMed Central

    2009-01-01

    Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices. PMID:20628459

  5. Research and Development of a New Silica-Alumina Based Cementitious Material Largely Using Coal Refuse for Mine Backfill, Mine Sealing and Waste Disposal Stabilization

    SciTech Connect

    Henghu Sun; Yuan Yao

    2012-06-29

    Coal refuse and coal combustion byproducts as industrial solid waste stockpiles have become great threats to the environment. To activate coal refuse is one practical solution to recycle this huge amount of solid waste as substitute for Ordinary Portland Cement (OPC). The central goal of this project is to investigate and develop a new silica-alumina based cementitious material largely using coal refuse as a constituent that will be ideal for durable construction, mine backfill, mine sealing and waste disposal stabilization applications. This new material is an environment-friendly alternative to Ordinary Portland Cement. The main constituents of the new material are coal refuse and other coal wastes including coal sludge and coal combustion products (CCPs). Compared with conventional cement production, successful development of this new technology could potentially save energy and reduce greenhouse gas emissions, recycle vast amount of coal wastes, and significantly reduce production cost. A systematic research has been conducted to seek for an optimal solution for enhancing pozzolanic reactivity of the relatively inert solid waste-coal refuse in order to improve the utilization efficiency and economic benefit as a construction and building material.

  6. Comparison of the O Kα x-ray emission bands in micro- and mesoporous silica materials and in α-quartz

    NASA Astrophysics Data System (ADS)

    Khyzhun, O. Yu.; Strunskus, T.; Wöll, Ch.; Gies, H.; Staemmler, V.

    2008-08-01

    X-ray emission spectroscopy (XES) at the O Kα threshold has been used to investigate the electronic structure of a microporous pure calcined zeolite with the crystal structure of the MFI-type framework (silicalite), a deboronated MFI zeolite (DB-MFI), a pure mesoporous cubic MCM-48 material, a MCM-48 loaded with copper and zinc oxide nanoparticles (Cu/ZnO-MCM-48), and a crystalline layered silicic acid H-RUB-18. For comparison, the XES O Kα spectrum of pure α-quartz has also been recorded. In the nonresonant energy regime the XES O Kα spectra for all these compounds look very similar indicating that the electronic structure of the micro- and mesoporous silica materials is very similar to that of quartz. In the resonant regime, however, the spectra exhibit significant differences. In all the materials under study, the resonant XES O Kα spectra recorded at photon energies close to the positions of the O K edges show Raman-type inelastic peaks with an energy loss of 11 eV, originating from electronic excitations within these insulating materials. The prominent features in the XES O Kα spectra of α-quartz and H-RUB-18 are analyzed by means of quantum chemical ab initio cluster calculations.

  7. The Role of Silica in Precious Metal Supported Titania Hybrid Mesoporous Materials for Remediation and Energy Production

    NASA Astrophysics Data System (ADS)

    Kibombo, Harrison S.

    Semiconductor photocatalysis is an advanced oxidation process (AOP) that continues to show promise for the concomitant mineralization of non--biodegradable noxious and persistent organic pollutants (POPs) to environmentally benign products, and the splitting of water. This work examined the use of sol--gel chemistry as a viable approach for the incorporation of transparent silica (SiO2) matrix and/or platinum onto titania (TiO2) so as to optimize physico-chemical properties such as charge separation, crystallinity, surface area, and particle size. It was determined that crystallinity of anatase in the mixed oxide photocatalyst can be improved by the addition of simple non-polar aromatic co-solvents in the sol-gel route, and subsequently enhance the photocatalytic degradation of phenol under UV--light irradiation. The Pt of smaller particle sizes in Pt--TiO2--SiO 2 resulted in higher phenol degradation efficiencies under solar simulated conditions, irrespective of the synthesis method employed. The presence of Pt in the lowest oxidation state, Pt0, is crucial for enhanced phenol degradation whereas PtO2 (Pt4+) serves as a mild recombination center for photogenerated charge carriers rather than demonstrating total inactivity. The production of ·OH radicals was shown to be imperative for sustaining the degradation process. In the water splitting reaction for hydrogen production, the role of the crystallinity of anatase is reaffirmed when TiO2--SiO2 is used, as the surface defects present in the silica phase seem to serve as recombination centers. However, in Pt--TiO2 photocatalysts, the presence of Pt 0 or PtO2 in close contact with TiO2 (heterojunction) allows for more efficient electron propagation and facilitates minimization of electron--hole recombination, hence improved solar simulated photocatalytic hydrogen evolution. Extensive characterization of the photocatalysts were carried out by powder X--ray Diffraction (XRD), Nitrogen Physisorption Studies, Diffuse

  8. Porous carbon-coated silica macroparticles as anode materials for lithium ion batteries: Effect of boric acid

    NASA Astrophysics Data System (ADS)

    Kim, Young-Kuk; Moon, Jong-Woo; Lee, Jung-Goo; Baek, Youn-Kyung; Hong, Seong-Hyun

    2014-12-01

    We report carbon-coated porous silica macroparticles (SiO2@C) prepared using polymeric templates and subsequent carbonization with sucrose for improved electrochemical energy storage in lithium-ion batteries (LIBs). In addition, boron is introduced to improve the stability of electrochemical cells by pyrolyzing mixtures of sucrose and boric acid (SiO2@C + B) under inert atmosphere. The initially large surface area of porous SiO2 (SBET ∼ 658 m2 g-1) is reduced to 102 m2 g-1 after carbonization and introduction of boric acid. Surface of both SiO2@C and SiO2@C + B are covered with amorphous carbon. In particular, SiO2@C + B particles containing borosilicate (Si-O-B) phase and B-O bondings and Si-C-O bondings are also detected from the X-ray photoelectron spectra. The SiO2@C + B macroparticles shows high reversible charge capacity up to 503 mAh g-1 after 103 cycles of Li intercalation/de-intercalation although initial capacity was 200 mAh g-1. The improved charge capacity of SiO2@C + B is attributed to formation of advantageous microstructures induced from boric acid.

  9. Modified mesoporous silica materials for on-line separation and preconcentration of hexavalent chromium using a microcolumn coupled with flame atomic absorption spectrometry.

    PubMed

    Wang, Zheng; Fang, Dong-Mei; Li, Qing; Zhang, Ling-Xia; Qian, Rong; Zhu, Yan; Qu, Hai-Yun; Du, Yi-Ping

    2012-05-01

    A modified SBA-15 mesoporous silica material NH(2)-SBA-15 was synthesized successfully by grafting γ-aminopropyl-triethoxysilane. The material was characterized using transmission electron microscopy (TEM) and Fourier transform infrared/Raman (FT-IR/Raman) spectroscopy, and used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Effective sorption of Cr (VI) was achieved at pH 2.0 with no interference from Cr (III) and other ions and 0.5 mol L(-1) NH(3)·H(2)O solution was found optimal for the complete elution of Cr (VI). An enrichment factor of 44 and was achieved under optimized experimental conditions at a sample loading of 2.0 mL min(-1) sample loading (300 s) and an elution flow rate of 2.0 mL min(-1) (24s). The precision of the 11 replicate Cr (VI) measurements was 2.1% at the 100 μg L(-1) level with a detection limit of 0.2 μg L(-1) (3s, n=10) using the FAAS. The developed method was successfully applied to trace chromium determination in waste water. The accuracy was validated using a certified reference material of riverine water (GBW08607). PMID:22502615

  10. Cellular membrane trafficking of mesoporous silica nanoparticles

    SciTech Connect

    Fang, I-Ju

    2012-01-01

    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  11. Silica/Polymer and Silica/Polymer/Fiber Composite Aerogels

    NASA Technical Reports Server (NTRS)

    Ou, Danny; Stepanian, Christopher J.; Hu, Xiangjun

    2010-01-01

    Aerogels that consist, variously, of neat silica/polymer alloys and silica/polymer alloy matrices reinforced with fibers have been developed as materials for flexible thermal-insulation blankets. In comparison with prior aerogel blankets, these aerogel blankets are more durable and less dusty. These blankets are also better able to resist and recover from compression . an important advantage in that maintenance of thickness is essential to maintenance of high thermal-insulation performance. These blankets are especially suitable as core materials for vacuum- insulated panels and vacuum-insulated boxes of advanced, nearly seamless design. (Inasmuch as heat leakage at seams is much greater than heat leakage elsewhere through such structures, advanced designs for high insulation performance should provide for minimization of the sizes and numbers of seams.) A silica/polymer aerogel of the present type could be characterized, somewhat more precisely, as consisting of multiply bonded, linear polymer reinforcements within a silica aerogel matrix. Thus far, several different polymethacrylates (PMAs) have been incorporated into aerogel networks to increase resistance to crushing and to improve other mechanical properties while minimally affecting thermal conductivity and density. The polymethacrylate phases are strongly linked into the silica aerogel networks in these materials. Unlike in other organic/inorganic blended aerogels, the inorganic and organic phases are chemically bonded to each other, by both covalent and hydrogen bonds. In the process for making a silica/polymer alloy aerogel, the covalent bonds are introduced by prepolymerization of the methacrylate monomer with trimethoxysilylpropylmethacrylate, which serves as a phase cross-linker in that it contains both organic and inorganic monomer functional groups and hence acts as a connector between the organic and inorganic phases. Hydrogen bonds are formed between the silanol groups of the inorganic phase and the

  12. Spectroscopic and metal-binding properties of DF3: an artificial protein able to accommodate different metal ions

    PubMed Central

    Torres Martin de Rosales, Rafael; Faiella, Marina; Farquhar, Erik; Que, Lawrence; Andreozzi, Concetta; Pavone, Vincenzo; Maglio, Ornella; Nastri, Flavia

    2010-01-01

    The design, synthesis, and metal-binding properties of DF3, a new de novo designed di-iron protein model are described (“DF” represents due ferri, Italian for “two iron,” “di-iron”). DF3 is the latest member of the DF family of synthetic proteins. They consist of helix–loop–helix hairpins, designed to dimerize and form an antiparallel four-helix bundle that encompasses a metal-binding site similar to those of non-heme carboxylate-bridged di-iron proteins. Unlike previous DF proteins, DF3 is highly soluble in water (up to 3 mM) and forms stable complexes with several metal ions (Zn, Co, and Mn), with the desired secondary structure and the expected stoichiometry of two ions per protein. UV–vis studies of Co(II) and Fe(III) complexes confirm a metal-binding environment similar to previous di-Co(II)- and di-Fe(III)-DF proteins, including the presence of a µ-oxo-di-Fe(III) unit. Interestingly, UV–vis, EPR, and resonance Raman studies suggest the interaction of a tyro-sine adjacent to the di-Fe(III) center. The design of DF3 was aimed at increasing the accessibility of small molecules to the active site of the four-helix bundle. Indeed, binding of azide to the di-Fe(III) site demonstrates a more accessible metal site compared with previous DFs. In fact, fitting of the binding curve to the Hill equation allows us to quantify a 150% accessibility enhancement, with respect to DF2. All these results represent a significant step towards the development of a functional synthetic DF metalloprotein. PMID:20225070

  13. Oxidation Protection in Metal-Binding Peptide Motif and Its Application to Antibody for Site-Selective Conjugation

    PubMed Central

    Chung, Hye-Shin; Lee, Sunbae; Park, Soon Jae

    2016-01-01

    Here, we demonstrate that a metal ion binding motif could serve as an efficient and robust tool for site-specific conjugation strategy. Cysteine-containing metal binding motifs were constructed as single repeat or tandem repeat peptides and their metal binding characteristics were investigated. The tandem repeats of the Cysteine-Glycine-Histidine (CGH) metal ion binding motif exhibited concerted binding to Co(II) ions, suggesting that conformational transition of peptide was triggered by the sequential metal ion binding. Evaluation of the free thiol content after reduction by reducing reagent showed that metal-ion binding elicited strong retardation of cysteine oxidation in the order of Zn(II)>Ni(II)>Co(II). The CGH metal ion binding motif was then introduced to the C-terminus of antibody heavy chain and the metal ion-dependent characteristics of oxidation kinetics were investigated. As in the case of peptides, CGH-motif-introduced antibody exhibited strong dependence on metal ion binding to protect against oxidation. Zn(II)-saturated antibody with tandem repeat of CGH motif retains the cysteine reactivity as long as 22 hour even with saturating O2 condition. Metal-ion dependent fluorophore labeling clearly indicated that metal binding motifs could be employed as an efficient tool for site-specific conjugation. Whereas Trastuzumab without a metal ion binding site exhibited site-nonspecific dye conjugation, Zn(II) ion binding to antibody with a tandem repeat of CGH motif showed that fluorophores were site-specifically conjugated to the heavy chain of antibody. We believe that this strong metal ion dependence on oxidation protection and the resulting site-selective conjugation could be exploited further to develop a highly site-specific conjugation strategy for proteins that contain multiple intrinsic cysteine residues, including monoclonal antibodies. PMID:27420328

  14. Hints for metal-preference protein sequence determinants: different metal binding features of the five tetrahymena thermophila metallothioneins.

    PubMed

    Espart, Anna; Marín, Maribel; Gil-Moreno, Selene; Palacios, Òscar; Amaro, Francisco; Martín-González, Ana; Gutiérrez, Juan C; Capdevila, Mercè; Atrian, Sílvia

    2015-01-01

    The metal binding preference of metallothioneins (MTs) groups them in two extreme subsets, the Zn/Cd- and the Cu-thioneins. Ciliates harbor the largest MT gene/protein family reported so far, including 5 paralogs that exhibit relatively low sequence similarity, excepting MTT2 and MTT4. In Tetrahymena thermophila, three MTs (MTT1, MTT3 and MTT5) were considered Cd-thioneins and two (MTT2 and MTT4) Cu-thioneins, according to gene expression inducibility and phylogenetic analysis. In this study, the metal-binding abilities of the five MTT proteins were characterized, to obtain information about the folding and stability of their cognate- and non-cognate metal complexes, and to characterize the T. thermophila MT system at protein level. Hence, the five MTTs were recombinantly synthesized as Zn(2+)-, Cd(2+)- or Cu(+)-complexes, which were analyzed by electrospray mass spectrometry (ESI-MS), circular dichroism (CD), and UV-vis spectrophotometry. Among the Cd-thioneins, MTT1 and MTT5 were optimal for Cd(2+) coordination, yielding unique Cd17- and Cd8- complexes, respectively. When binding Zn(2+), they rendered a mixture of Zn-species. Only MTT5 was capable to coordinate Cu(+), although yielding heteronuclear Zn-, Cu-species or highly unstable Cu-homometallic species. MTT3 exhibited poor binding abilities both for Cd(2+) and for Cu(+), and although not optimally, it yielded the best result when coordinating Zn(2+). The two Cu-thioneins, MTT2 and MTT4 isoforms formed homometallic Cu-complexes (major Cu20-MTT) upon synthesis in Cu-supplemented hosts. Contrarily, they were unable to fold into stable Cd-complexes, while Zn-MTT species were only recovered for MTT4 (major Zn10-MTT4). Thus, the metal binding preferences of the five T. thermophila MTs correlate well with their previous classification as Cd- and Cu-thioneins, and globally, they can be classified from Zn/Cd- to Cu-thioneins according to the gradation: MTT1>MTT5>MTT3>MTT4>MTT2. The main mechanisms underlying the

  15. NMR and X-ray analysis of structural additivity in metal binding site-swapped hybrids of rubredoxin

    PubMed Central

    LeMaster, David M; Anderson, Janet S; Wang, Limin; Guo, Yi; Li, Hongmin; Hernández, Griselda

    2007-01-01

    Background Chimeric hybrids derived from the rubredoxins of Pyrococcus furiosus (Pf) and Clostridium pasteurianum (Cp) provide a robust system for the characterization of protein conformational stability and dynamics in a differential mode. Interchange of the seven nonconserved residues of the metal binding site between the Pf and Cp rubredoxins yields a complementary pair of hybrids, for which the sum of the thermodynamic stabilities is equal to the sum for the parental proteins. Furthermore, the increase in amide hydrogen exchange rates for the hyperthermophile-derived metal binding site hybrid is faithfully mirrored by a corresponding decrease for the complementary hybrid that is derived from the less thermostable rubredoxin, indicating a degree of additivity in the conformational fluctuations that underlie these exchange reactions. Results Initial NMR studies indicated that the structures of the two complementary hybrids closely resemble "cut-and-paste" models derived from the parental Pf and Cp rubredoxins. This protein system offers a robust opportunity to characterize differences in solution structure, permitting the quantitative NMR chemical shift and NOE peak intensity data to be analyzed without recourse to the conventional conversion of experimental NOE peak intensities into distance restraints. The intensities for 1573 of the 1652 well-resolved NOE crosspeaks from the hybrid rubredoxins were statistically indistinguishable from the intensities of the corresponding parental crosspeaks, to within the baseplane noise level of these high sensitivity data sets. The differences in intensity for the remaining 79 NOE crosspeaks were directly ascribable to localized dynamical processes. Subsequent X-ray analysis of the metal binding site-swapped hybrids, to resolution limits of 0.79 Å and 1.04 Å, demonstrated that the backbone and sidechain heavy atoms in the NMR-derived structures lie within the range of structural variability exhibited among the individual

  16. Structural Comparisons of Apo- and Metalated Three-Stranded Coiled Coils Clarify Metal Binding Determinants in Thiolate Containing Designed Peptides

    SciTech Connect

    Chakraborty, Saumen; Touw, Debra S.; Peacock, Anna F.A.; Stuckey, Jeanne; Pecoraro, Vincent L.

    2010-11-05

    Over the past two decades, designed metallopeptides have held the promise for understanding a variety of fundamental questions in metallobiochemistry; however, these dreams have not yet been realized because of a lack of structural data to elaborate the protein scaffolds before metal complexation and the resultant metalated structures which ultimately exist. This is because there are few reports of structural characterization of such systems either in their metalated or nonmetalated forms and no examples where an apo structure and the corresponding metalated peptide assembly have both been defined by X-ray crystallography. Herein we present X-ray structures of two de novo designed parallel three-stranded coiled coils (designed using the heptad repeat (a {yields} g)) CSL9C (CS = Coil Ser) and CSL19C in their nonmetalated forms, determined to 1.36 and 2.15 {angstrom} resolutions, respectively. Leucines from either position 9 (a site) or 19 (d site) are replaced by cysteine to generate the constructs CSL9C and CSL19C, respectively, yielding thiol-rich pockets at the hydrophobic interior of these peptides, suitable to bind heavy metals such as As(III), Hg(II), Cd(II), and Pb(II). We use these structures to understand the inherent structural differences between a and d sites to clarify the basis of the observed differential spectroscopic behavior of metal binding in these types of peptides. Cys side chains of (CSL9C){sub 3} show alternate conformations and are partially preorganized for metal binding, whereas cysteines in (CSL19C){sub 3} are present as a single conformer. Zn(II) ions, which do not coordinate or influence Cys residues at the designed metal sites but are essential for forming X-ray quality crystals, are bound to His and Glu residues at the crystal packing interfaces of both structures. These 'apo' structures are used to clarify the changes in metal site organization between metalated As(CSL9C){sub 3} and to speculate on the differential basis of Hg

  17. Structural Comparisons of Apo- and Metallated Three Stranded Coiled Coils Clarify Metal Binding Determinants in Thiolate Containing Designed Peptides

    PubMed Central

    Chakraborty, Saumen; Touw, Debra S.; Peacock, Anna F. A.; Stuckey, Jeanne; Pecoraro, Vincent L.

    2010-01-01

    Over the past two decades, designed metallopeptides have held the promise for understanding a variety of fundamental questions in metallobiochemistry; however, these dreams have not yet been realized because of a lack of structural data to elaborate the protein scaffolds before metal complexation and the resultant metallated structures which ultimately exist. This is because there are few reports of structural characterization of such systems either in their metallated or non-metallated forms and no examples where an apo structure and the corresponding metallated peptide assembly have both been defined by x-ray crystallography. Herein we present x-ray structures of two de novo designed parallel three-stranded coiled coils (designed using the heptad repeat (a→g)) CSL9C (CS = Coil Ser) and CSL19C in their non-metallated forms, determined to 1.36 Å and 2.15 Å resolutions, respectively. Leucines from either position 9 (a site) or 19 (d site) are replaced by cysteine to generate the constructs CSL9C and CSL19C, respectively, yielding thiol-rich pockets at the hydrophobic interior of these peptides, suitable to bind heavy metals such as As(III), Hg(II), Cd(II) and Pb(II). We use these structures to understand the inherent structural differences between a and d sites to clarify the basis of the observed differential spectroscopic behavior of metal binding in these types of peptides. Cys side chains of (CSL9C)3 show alternate conformations and are partially preorganized for metal binding, whereas cysteines in (CSL19C)3 are present as a single conformer. Zn(II) ions, which do not coordinate or influence Cys residues at the designed metal sites but are essential for forming x-ray quality crystals, are bound to His and Glu residues at the crystal packing interfaces of both structures. These “apo” structures are used to clarify the changes in metal site organization between metallated As(CSL9C)3 and to speculate on the differential basis of Hg(II) binding in a versus d

  18. Assessing the potential of ToF-SIMS as a complementary approach to investigate cement-based materials — Applications related to alkali–silica reaction

    SciTech Connect

    Bernard, Laetitia; Leemann, Andreas

    2015-02-15

    In this study, the potential of time-of-flight secondary ion mass spectrometry (ToF-SIMS) for the application in cement-based materials is assessed in combination and comparison with scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). Mortar, concrete and samples from model systems providing products formed by the alkali–silica reaction (ASR) were studied. ToF-SIMS provides qualitative data on alkalis in cases where EDX reaches its limits in regard to detectable concentration, lateral resolution and atomic number of the elements. Due to its high in-depth resolution of a few atomic monolayers, thin layers of reaction products can be detected on the surfaces and chemically analyzed with ToF-SIMS. Additionally, it delivers information on the molecular conformation within the ASR product, its hydrogen content and its isotope ratios, information not provided by EDX. Provided the samples are carefully prepared, ToF-SIMS opens up new possibilities in the analysis of cement-based materials.

  19. Synthesis, characterization, and light-controlled antibiotic application of a composite material derived from polyurethane and silica xerogel with embedded photoactive manganese nitrosyl.

    PubMed

    Heilman, Brandon J; Halpenny, Genevieve M; Mascharak, Pradip K

    2011-11-01

    The synthesis of a light-sensitive polyurethane-based composite material (PUX-NO) is described. In its polyurethane medium, PUX-NO contains entrapped silica xerogel particles in which a photoactive manganese nitrosyl has been incorporated. Green flexible films of PUX-NO readily release nitric oxide (NO) only when exposed to low power (mW) visible light. Incorporation of the nitrosyl in the xerogel not only retains the nitrosyl (NO donor) within the composite material but also provides the right extent of hydration. Pre-swelled films of PUX-NO have water content close to 30 Wt % and such films can be stored for months under slightly moist condition without loss in NO-delivering capacity. The NO-releasing parameters of the film have been determined. The NO-releasing capacity of PUX-NO films can be conveniently altered by changing the amount of the nitrosyl as well as the thickness of the films. Patches of PUX-NO film have been successfully employed to reduce drastically bacterial loads of both gram-positive and gram-negative bacteria including methicillin-resistant Staphylococcus aureus and Acinetobacter baumannii under the total control of light. Effective control of infections by these bacterial pathogens via delivery of proper doses of NO only to the sites of infection appears feasible with PUX-NO films.

  20. Fast characterization of functionalized silica materials by silicon-29 surface-enhanced NMR spectroscopy using dynamic nuclear polarization.

    PubMed

    Lelli, Moreno; Gajan, David; Lesage, Anne; Caporini, Marc A; Vitzthum, Veronika; Miéville, Pascal; Héroguel, Florent; Rascón, Fernando; Roussey, Arthur; Thieuleux, Chloé; Boualleg, Malika; Veyre, Laurent; Bodenhausen, Geoffrey; Copéret, Christophe; Emsley, Lyndon

    2011-02-23

    We demonstrate fast characterization of the distribution of surface bonding modes and interactions in a series of functionalized materials via surface-enhanced nuclear magnetic resonance spectroscopy using dynamic nuclear polarization (DNP). Surface-enhanced silicon-29 DNP NMR spectra were obtained by using incipient wetness impregnation of the sample with a solution containing a polarizing radical (TOTAPOL). We identify and compare the bonding topology of functional groups in materials obtained via a sol-gel process and in materials prepared by post-grafting reactions. Furthermore, the remarkable gain in time provided by surface-enhanced silicon-29 DNP NMR spectroscopy (typically on the order of a factor 400) allows the facile acquisition of two-dimensional correlation spectra. PMID:21280606

  1. Metal-binding proteins and peptides in the aquatic fungi Fontanospora fusiramosa and Flagellospora curta exposed to severe metal stress.

    PubMed

    Guimarães-Soares, Luís; Felícia, Helena; João Bebianno, Maria; Cássio, Fernanda

    2006-12-15

    The production of thiol-containing proteins/peptides and its role in metal-binding was examined in the aquatic hyphomycetes Fontanospora fusiramosa and Flagellospora curta exposed to Cu, Cd, or Zn at concentrations inhibiting the biomass production in 80%. Heat-treated cell-free extracts were separated by size-exclusion chromatography and the thiol and metal content in the fractions was determined. F. curta, the species tolerant to metals, showed higher absolute levels of thiol compounds, which bound higher amounts of Cu and Cd than F. fusiramosa. Peptides with very low molecular weight (<9 kDa), most likely glutathione and phytochelatins, were the major Cu- and Zn-binding components in both species of aquatic hyphomycetes. In most cases, proteins with high molecular weight (>26 kDa) were induced by metal ions and they were the major Cd-binding component in both species. Proteins with characteristics of metallothioneins were also induced by exposure to metals in both species, but they showed a minor role in metal-binding, suggesting they might have other functions in fungal cells. PMID:17083969

  2. Metal-binding proteins and peptides in the aquatic fungi Fontanospora fusiramosa and Flagellospora curta exposed to severe metal stress.

    PubMed

    Guimarães-Soares, Luís; Felícia, Helena; João Bebianno, Maria; Cássio, Fernanda

    2006-12-15

    The production of thiol-containing proteins/peptides and its role in metal-binding was examined in the aquatic hyphomycetes Fontanospora fusiramosa and Flagellospora curta exposed to Cu, Cd, or Zn at concentrations inhibiting the biomass production in 80%. Heat-treated cell-free extracts were separated by size-exclusion chromatography and the thiol and metal content in the fractions was determined. F. curta, the species tolerant to metals, showed higher absolute levels of thiol compounds, which bound higher amounts of Cu and Cd than F. fusiramosa. Peptides with very low molecular weight (<9 kDa), most likely glutathione and phytochelatins, were the major Cu- and Zn-binding components in both species of aquatic hyphomycetes. In most cases, proteins with high molecular weight (>26 kDa) were induced by metal ions and they were the major Cd-binding component in both species. Proteins with characteristics of metallothioneins were also induced by exposure to metals in both species, but they showed a minor role in metal-binding, suggesting they might have other functions in fungal cells.

  3. Does Variation of the Inter-Domain Linker Sequence Modulate the Metal Binding Behaviour of Helix pomatia Cd-Metallothionein?

    PubMed Central

    Gil-Moreno, Selene; Jiménez-Martí, Elena; Palacios, Òscar; Zerbe, Oliver; Dallinger, Reinhard; Capdevila, Mercè; Atrian, Sílvia

    2015-01-01

    Snail metallothioneins (MTs) constitute an ideal model to study structure/function relationships in these metal-binding polypeptides. Helix pomatia harbours three MT isoforms: the highly specific CdMT and CuMT, and an unspecific Cd/CuMT, which represent paralogous proteins with extremely different metal binding preferences while sharing high sequence similarity. Preceding work allowed assessing that, although, the Cys residues are responsible for metal ion coordination, metal specificity or preference is achieved by diversification of the amino acids interspersed between them. The metal-specific MT polypeptides fold into unique, energetically-optimized complexes of defined metal content, when binding their cognate metal ions, while they produce a mixture of complexes, none of them representing a clear energy minimum, with non-cognate metal ions. Another critical, and so far mostly unexplored, region is the stretch linking the individual MT domains, each of which represents an independent metal cluster. In this work, we have designed and analyzed two HpCdMT constructs with substituted linker segments, and determined their coordination behavior when exposed to both cognate and non-cognate metal ions. Results unequivocally show that neither length nor composition of the inter-domain linker alter the features of the Zn(II)- and Cd(II)-complexes, but surprisingly that they influence their ability to bind Cu(I), the non-cognate metal ion. PMID:26703589

  4. Structure of Human J-type Co-chaperone HscB Reveals a Tetracysteine Metal-binding Domain

    SciTech Connect

    Bitto, Eduard; Bingman, Craig A.; Bittova, Lenka; Kondrashov, Dmitry A.; Bannen, Ryan M.; Fox, Brian G.; Markley, John L.; Phillips, Jr., George N.

    2008-11-24

    Iron-sulfur proteins play indispensable roles in a broad range of biochemical processes. The biogenesis of iron-sulfur proteins is a complex process that has become a subject of extensive research. The final step of iron-sulfur protein assembly involves transfer of an iron-sulfur cluster from a cluster-donor to a cluster-acceptor protein. This process is facilitated by a specialized chaperone system, which consists of a molecular chaperone from the Hsc70 family and a co-chaperone of the J-domain family. The 3.0 A crystal structure of a human mitochondrial J-type co-chaperone HscB revealed an L-shaped protein that resembles Escherichia coli HscB. The important difference between the two homologs is the presence of an auxiliary metal-binding domain at the N terminus of human HscB that coordinates a metal via the tetracysteine consensus motif CWXCX(9-13)FCXXCXXXQ. The domain is found in HscB homologs from animals and plants as well as in magnetotactic bacteria. The metal-binding site of the domain is structurally similar to that of rubredoxin and several zinc finger proteins containing rubredoxin-like knuckles. The normal mode analysis of HscB revealed that this L-shaped protein preferentially undergoes a scissors-like motion that correlates well with the conformational changes of human HscB observed in the crystals.

  5. Granulated activated carbon modified with hydrophobic silica aerogel-potential composite materials for the removal of uranium from aqueous solutions.

    PubMed

    Coleman, Sabre J; Coronado, Paul R; Maxwell, Robert S; Reynolds, John G

    2003-05-15

    Aqueous solutions of 100 parts per billion (ppb) uranium at pH 7 were treated with granulated activated carbon (GAC) that had been modified with various formulations of hydrophobic aerogels. The composite materials were found to be superior in removing uranium from a stock solution compared to GAC alone evaluated by a modified ASTM D 3860-98 method for batch testing. The testing results were evaluated using a Freundlich adsorption model. The best performing material has parameters of n = 287 and Kf = 1169 compared to n = 1.00, and Kf = 20 for GAC alone. The composite materials were formed by mixing (CH3O)4Si with the hydrophobic sol-gel precursor, (CH3O)3SiCH2CH2CF3 and with specified modifiers, such as H3PO4, Ca(NO3)2, and (C2H5O)3SiCH2CH2P(O)(OC2H5)2, elation catalysts, and GAC in a supercritical reactor system. After gelation, supercritical extraction, and sieving, the composites were tested. Characterization by FTIR and 31P NMR indicate the formation of phosphate in the case of the H3PO4 and Ca(NO3)2 composites and phosphonic acid related compounds in the phosphonate composite. These composite materials have potential application in the clean up of groundwater at DOE and other facilities.

  6. Enhanced thermal properties of novel shape-stabilized PEG composite phase change materials with radial mesoporous silica sphere for thermal energy storage

    PubMed Central

    Min, Xin; Fang, Minghao; Huang, Zhaohui; Liu, Yan’gai; Huang, Yaoting; Wen, Ruilong; Qian, Tingting; Wu, Xiaowen

    2015-01-01

    Radial mesoporous silica (RMS) sphere was tailor-made for further applications in producing shape-stabilized composite phase change materials (ss-CPCMs) through a facile self-assembly process using CTAB as the main template and TEOS as SiO2 precursor. Novel ss-CPCMs composed of polyethylene glycol (PEG) and RMS were prepared through vacuum impregnating method. Various techniques were employed to characterize the structural and thermal properties of the ss-CPCMs. The DSC results indicated that the PEG/RMS ss-CPCM was a promising candidate for building thermal energy storage applications due to its large latent heat, suitable phase change temperature, good thermal reliability, as well as the excellent chemical compatibility and thermal stability. Importantly, the possible formation mechanisms of both RMS sphere and PEG/RMS composite have also been proposed. The results also indicated that the properties of the PEG/RMS ss-CPCMs are influenced by the adsorption limitation of the PEG molecule from RMS sphere with mesoporous structure and the effect of RMS, as the impurities, on the perfect crystallization of PEG. PMID:26261089

  7. Enhanced thermal properties of novel shape-stabilized PEG composite phase change materials with radial mesoporous silica sphere for thermal energy storage.

    PubMed

    Min, Xin; Fang, Minghao; Huang, Zhaohui; Liu, Yan'gai; Huang, Yaoting; Wen, Ruilong; Qian, Tingting; Wu, Xiaowen

    2015-01-01

    Radial mesoporous silica (RMS) sphere was tailor-made for further applications in producing shape-stabilized composite phase change materials (ss-CPCMs) through a facile self-assembly process using CTAB as the main template and TEOS as SiO2 precursor. Novel ss-CPCMs composed of polyethylene glycol (PEG) and RMS were prepared through vacuum impregnating method. Various techniques were employed to characterize the structural and thermal properties of the ss-CPCMs. The DSC results indicated that the PEG/RMS ss-CPCM was a promising candidate for building thermal energy storage applications due to its large latent heat, suitable phase change temperature, good thermal reliability, as well as the excellent chemical compatibility and thermal stability. Importantly, the possible formation mechanisms of both RMS sphere and PEG/RMS composite have also been proposed. The results also indicated that the properties of the PEG/RMS ss-CPCMs are influenced by the adsorption limitation of the PEG molecule from RMS sphere with mesoporous structure and the effect of RMS, as the impurities, on the perfect crystallization of PEG. PMID:26261089

  8. Enhanced thermal properties of novel shape-stabilized PEG composite phase change materials with radial mesoporous silica sphere for thermal energy storage

    NASA Astrophysics Data System (ADS)

    Min, Xin; Fang, Minghao; Huang, Zhaohui; Liu, Yan'Gai; Huang, Yaoting; Wen, Ruilong; Qian, Tingting; Wu, Xiaowen

    2015-08-01

    Radial mesoporous silica (RMS) sphere was tailor-made for further applications in producing shape-stabilized composite phase change materials (ss-CPCMs) through a facile self-assembly process using CTAB as the main template and TEOS as SiO2 precursor. Novel ss-CPCMs composed of polyethylene glycol (PEG) and RMS were prepared through vacuum impregnating method. Various techniques were employed to characterize the structural and thermal properties of the ss-CPCMs. The DSC results indicated that the PEG/RMS ss-CPCM was a promising candidate for building thermal energy storage applications due to its large latent heat, suitable phase change temperature, good thermal reliability, as well as the excellent chemical compatibility and thermal stability. Importantly, the possible formation mechanisms of both RMS sphere and PEG/RMS composite have also been proposed. The results also indicated that the properties of the PEG/RMS ss-CPCMs are influenced by the adsorption limitation of the PEG molecule from RMS sphere with mesoporous structure and the effect of RMS, as the impurities, on the perfect crystallization of PEG.

  9. Phase transition of silica in the TMB-P123-H2O-TEOS quadru-component system: a feasible route to different mesostructured materials.

    PubMed

    Xin, Chunling; Zhao, Ning; Zhan, Haijuan; Xiao, Fukui; Wei, Wei; Sun, Yuhan

    2014-11-01

    Various siliceous structures were obtained using a nonionic block copolymer (Pluronic P123) surfactant and trimethylbenzene (TMB) as a hydrophobic additive by hydrolysis and condensation of tetraethoxysilane (TEOS) in a sol-gel process. The resultant materials were characterized by small-angle X-ray diffraction (SAXRD), nitrogen adsorption analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results revealed the structure transformation from hexagonal structure (HEX) to multilamellar vesicles (MLVs) and then to mesocellular foams (MCFs) in the TMB-P123-H2O-TEOS quadru-component system. The morphology of the mesoporous silica was mainly controlled by the mass ratio of TMB/P123 resulted from the increasing volume of the hydrophobic chain of micelle of P123 that caused by more amount of TMB dissolved in the PPO segment of polymer. The fact that the occurrence of rod-like particles with curved ends and the coexistence of the MLVs and the HEX structure indicates that the MLVs are developed from the ends of HEX structures, rather than formed by a direct cooperative self-assembly mechanism. Further increasing of packing parameter of surfactant resulted from TMB addition transforms lamellar micelles to reversed micelles, leading to the formation of MCFs. PMID:25128865

  10. Silica-titania sol-gel hybrid materials: synthesis, characterization and potential application in solid phase extraction.

    PubMed

    de Moraes, Sandra V M; Passos, Joana B; Schossler, Patricia; Caramão, Elina B; Moro, Celso C; Costa, Tania M H; Benvenutti, Edilson V

    2003-04-10

    The biphenilaminepropylsilica and biphenilaminepropylsilicatitania were synthesized by sol-gel method, in two steps: (a) biphenylamine reacts with chloropropyltrimethoxysilane and (b) the product of reaction was polycondensed with tetraethylorthosilicate (TEOS) or TEOS and titanium isopropoxide. The sol-gel materials were characterized using infrared spectroscopy and N(2) adsorption-desorption isotherms and they were employed as sorbents for carcinogenic N-containing compound retention, in aqueous solution, using the SPE technique. The N-containing compounds adsorption was influenced by the titania presence and the sorption process seems to happen in the pores with higher organic density.

  11. The Hydrothermal System at Home Plate in Gusev Crater, Mars: Formation of High Silica Material by Acid-Sulfate Alteration of Basalt

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Ming, D. W.; Gellert, R.; Yen, A.; Clark, B. C.; Gnaff, T. G.; Arvidson, R. E.; Squyres, S. W.

    2008-01-01

    The Alpha Particle X-ray Spectrometer (APXS) instrument on the Mars Exploration Rover (MER) Spirit measured three targets on or adjacent to Home Plate in Gusev Crater that have unusually high SiO2 concentrations (68% to 91%), unusually low FeO concentrations (1% to 7%, with total Fe as FeO), and unusually high TiO2/FeO ratios (0.2 to 1.2 by weight) [1]. Two targets (Kenosha Comets and Lefty Ganote) are located on high albedo soil (Gertrude Weise) that was exposed by the rover wheels, and one target is a float rock called Fuzzy Smith. Kenosha Comets has the highest SiO2 concentration, lowest FeO concentration, and highest TiO2/FeO ratio. Mineralogical evidence from the MER Miniature Thermal Emission Spectrometer (Mini-TES) suggests that the SiO2 is present as amorphous (noncrystalline) SiO2 at Gertrude Weise and nearby targets [2,3]. Mini-TES data were not acquired for Fuzzy Smith. Home Plate is considered to have an explosive volcanic origin, resulting when basaltic magma came into contact with ground water or ice [4]. Within 50 m to 1 km of Home Plate are sulfate rich soil deposits (Paso Robles class soils with 22-35% SO3) which are considered to be probable fumarolic and/or hydrothermal deposits associated with the volcanism [5]. We develop the model here, suggested by [5], that the high-silica materials are another manifestation of acid-sulfate processes associated with fumarolic and hydrothermal activity at Home Plate. This is done by analogy with basaltic materials altered by acid sulfate processes on the Island of Hawaii.

  12. Coumarin-based fluorescence hybrid silica material used for selective detection and absorption of Hg2+ in aqueous media

    NASA Astrophysics Data System (ADS)

    Meng, Qingtao; Jia, Hongmin; Wang, Cuiping; Zhao, Hongbin; Lu, Gonghao; Hu, Zhizhi; Zhang, Zhiqiang; Duan, Chunying

    2014-11-01

    An inorganic-organic hybrid fluorescence material (C-SBA-15) was prepared by covalent immobilization of a coumarin derivative within the channels of SBA-15. The characterization results of XRD, TEM micrographs, FT-IR and UV-vis demonstrate that coumarin is successfully grafted onto the inner surface of SBA-15 and its organized structure is preserved. C-SBA-15 can detect Hg2+ with high selectivity to Pb2+, Zn2+, Cu2+, Mn2+, Cd2+, Co2+, Ag+, Fe3+, Ni2+, K+, Na+, Ca2+, Mg2+ and Li+ in water. Furthermore, the fluorogenical response is reversible by treating with EDTA and do not vary over a broad pH range (5.0-10.5). C-SBA-15 features more outstanding absorbing capacity for Hg2+ among other HTM ions in water.

  13. Nanoscale control of silica particle formation via silk-silica fusion proteins for bone regeneration.

    PubMed

    Mieszawska, Aneta J; Nadkarni, Lauren D; Perry, Carole C; Kaplan, David L

    2010-10-26

    The biomimetic design of silk/silica fusion proteins was carried out, combining the self assembling domains of spider dragline silk (Nephila clavipes) and silaffin derived R5 peptide of Cylindrotheca fusiformis that is responsible for silica mineralization. Genetic engineering was used to generate the protein-based biomaterials incorporating the physical properties of both components. With genetic control over the nanodomain sizes and chemistry, as well as modification of synthetic conditions for silica formation, controlled mineralized silk films with different silica morphologies and distributions were successfully generated; generating 3D porous networks, clustered silica nanoparticles (SNPs), or single SNPs. Silk serves as the organic scaffolding to control the material stability and multiprocessing makes silk/silica biomaterials suitable for different tissue regenerative applications. The influence of these new silk-silica composite systems on osteogenesis was evaluated with human mesenchymal stem cells (hMSCs) subjected to osteogenic differentiation. hMSCs adhered, proliferated, and differentiated towards osteogenic lineages on the silk/silica films. The presence of the silica in the silk films influenced osteogenic gene expression, with the upregulation of alkaline phosphatase (ALP), bone sialoprotein (BSP), and collagen type 1 (Col 1) markers. Evidence for early bone formation as calcium deposits was observed on silk films with silica. These results indicate the potential utility of these new silk/silica systems towards bone regeneration. PMID:20976116

  14. Design of a novel metal binding peptide by molecular dynamics simulation to sequester Cu and Zn ions

    PubMed Central

    Mahnam, K.; Saffar, B.; Mobini-Dehkordi, M.; Fassihi, A.; Mohammadi, A.

    2014-01-01

    Heavy metal toxicity has serious adverse effects on the environment. The metal sequestering characteristics of a novel metal binding peptide (Glu-Cys)11 Gly+linker+hexahistidine (EC11:His6) was investigated to determine if it can absorb Cu2+ or Zn2+ cations. Molecular dynamics simulations were carried out using a model of 6 Cu2+ or Zn2+ and other ions enclosed in a fully hydrated simulation box with the designed peptide. Totally, 240 nano second (ns) simulations were done in three phases. Results showed that the selected linker is able to separate two domains of this peptide and that the carboxyl oxygens of Glu residues of EC11 in the designed peptide can absorb these ions. Sequestration of Cu2+ or Zn2+ ions by the designed peptide does not change overall tertiary and secondary structures of peptide. PMID:25598801

  15. Silica Lubrication in Faults (Invited)

    NASA Astrophysics Data System (ADS)

    Rowe, C. D.; Rempe, M.; Lamothe, K.; Kirkpatrick, J. D.; White, J. C.; Mitchell, T. M.; Andrews, M.; Di Toro, G.

    2013-12-01

    Silica-rich rocks are common in the crust, so silica lubrication may be important for causing fault weakening during earthquakes if the phenomenon occurs in nature. In laboratory friction experiments on chert, dramatic shear weakening has been attributed to amorphization and attraction of water from atmospheric humidity to form a 'silica gel'. Few observations of the slip surfaces have been reported, and the details of weakening mechanism(s) remain enigmatic. Therefore, no criteria exist on which to make comparisons of experimental materials to natural faults. We performed a series of friction experiments, characterized the materials formed on the sliding surface, and compared these to a geological fault in the same rock type. Experiments were performed in the presence of room humidity at 2.5 MPa normal stress with 3 and 30 m total displacement for a variety of slip rates (10-4 - 10-1 m/s). The friction coefficient (μ) reduced from >0.6 to ~0.2 at 10-1 m/s, but only fell to ~0.4 at 10-2 - 10-4 m/s. The slip surfaces and wear material were observed using laser confocal Raman microscopy, electron microprobe, X-ray diffraction, and transmission electron microscopy. Experiments at 10-1 m/s formed wear material consisting of ≤1 μm powder that is aggregated into irregular 5-20 μm clumps. Some material disaggregated during analysis with electron beams and lasers, suggesting hydrous and unstable components. Compressed powder forms smooth pavements on the surface in which grains are not visible (if present, they are <100 nm). Powder contains amorphous material and as yet unidentified crystalline and non-crystalline forms of silica (not quartz), while the worn chert surface underneath shows Raman spectra consistent with a mixture of quartz and amorphous material. If silica amorphization facilitates shear weakening in natural faults, similar wear materials should be formed, and we may be able to identify them through microstructural studies. However, the sub

  16. The sea urchin metallothionein system: Comparative evaluation of the SpMTA and SpMTB metal-binding preferences☆

    PubMed Central

    Tomas, Mireia; Domènech, Jordi; Capdevila, Mercè; Bofill, Roger; Atrian, Sílvia

    2013-01-01

    Metallothioneins (MTs) constitute a superfamily of ubiquitous metal-binding proteins of low molecular weight and high Cys content. They are involved in metal homeostasis and detoxification, amongst other proposed biological functions. Two MT isoforms (SpMTA and SpMTB) have been reported in the echinoderm Strongylocentrotus purpuratus (sea urchin), both containing 20 Cys residues and presenting extremely similar sequences, although showing distinct tissular and ontogenic expression patterns. Although exhaustive information is available for the Cd(II)-SpMTA complex, this including the full resolution of its 3D structure, no data has been reported concerning either SpMTA Zn(II) and Cu(I) binding properties, or the characterization of SpMTB at protein level. In this work, both the SpMTA and SpMTB isoforms, as well as their separate α and β domains, have been recombinantly synthesized in the presence of Zn(II), Cd(II) or Cu(II), and the corresponding metal complexes have been analyzed using electrospray mass spectrometry, and CD, ICP-AES and UV–vis spectroscopies. The results clearly show a better performance of isoform A when binding Zn(II) and Cd(II), and of isoform B when coordinating Cu(I). Thus, our results confirm the differential metal binding preference of SpMTA and SpMTB, which, together with the reported induction pattern of the respective genes, highlights how also in Echinodermata the MT polymorphism may be linked to the evolution of different physiological roles. PMID:23847757

  17. Dissociation and metal-binding characteristics of yellow lichen substances suggest a relationship with site preferences of lichens

    PubMed Central

    Hauck, Markus; Jürgens, Sascha-René; Willenbruch, Karen; Huneck, Siegfried; Leuschner, Christoph

    2009-01-01

    Background and Aims Many species of lichen-forming fungi contain yellow or orange extracellular pigments belonging to the dibenzofurans (usnic acid), anthraquinones (e.g. parietin) or pulvinic acid group. These pigments are all equally efficient light screens, leading us to question the potential ecological and evolutionary significance of diversity in yellow and orange lichen substances. Here the hypothesis is tested that the different pigments differ in metal-binding characteristics, which suggest that they may contribute to adaptation to sites differing in pH and metal availability. Methods UV spectroscopy was used to study the dissociation and the pH dependence of the metal-binding behaviour of seven isolated lichen substances in methanol. Metals applied were selected macro- and micro-nutrients (Cu2+, Fe2+, Fe3+, Mg2+, Mn2+ and Zn2+). Key Results All the pigments studied are strong to moderate acids with pKa1 values between 2·8 and 4·5. Metal complexation is common in the lichen substances studied. Complexation takes place under acidic conditions with usnic acid, but under alkaline conditions with parietin and most compounds of the pulvinic acid group. The pulvinic acid derivative rhizocarpic acid forms metal complexes both in the acidic and the alkaline range. Conclusions Metal complexation by lichen substances could be a prerequisite for lichen substance-mediated control of metal uptake. Assuming such an effect at pH values where the affinity of the metal for the lichen substance is intermediate would explain the strong preference of lichens with usnic or rhizocarpic acids to acidic substrata. Moreover, it would explain the preference of lichens with parietin and some lichens with compounds of the pulvinic acid group either for nutrient-rich substrata at low pH or for calcareous substrata. PMID:18977765

  18. Optothermal nonlinearity of silica aerogel

    NASA Astrophysics Data System (ADS)

    Braidotti, Maria Chiara; Gentilini, Silvia; Fleming, Adam; Samuels, Michiel C.; Di Falco, Andrea; Conti, Claudio

    2016-07-01

    We report on the characterization of silica aerogel thermal optical nonlinearity, obtained by z-scan technique. The results show that typical silica aerogels have nonlinear optical coefficient similar to that of glass (≃10-12 m2/W), with negligible optical nonlinear absorption. The nonlinear coefficient can be increased to values in the range of 10-10 m2/W by embedding an absorbing dye in the aerogel. This value is one order of magnitude higher than that observed in the pure dye and in typical highly nonlinear materials like liquid crystals.

  19. Disentangling protein-silica interactions.

    PubMed

    Giussani, Lara; Tabacchi, Gloria; Gianotti, Enrica; Coluccia, Salvatore; Fois, Ettore

    2012-03-28

    We present the results of modelling studies aimed at the understanding of the interaction of a 7 nm sized water droplet containing a negatively charged globular protein with flat silica surfaces. We show how the droplet interaction with the surface depends on the electrostatic surface charge, and that adhesion of the droplet occurs when the surface is negatively charged as well. The key role of water and of the charge-balancing counter ions in mediating the surface-protein adhesion is highlighted. The relevance of the present results with respect to the production of bioinorganic hybrids via encapsulation of proteins inside mesoporous silica materials is discussed.

  20. Biomimetic silica encapsultation of living cells

    NASA Astrophysics Data System (ADS)

    Jaroch, David Benjamin

    Living cells perform complex chemical processes on size and time scales that artificial systems cannot match. Cells respond dynamically to their environment, acting as biological sensors, factories, and drug delivery devices. To facilitate the use of living systems in engineered constructs, we have developed several new approaches to create stable protective microenvironments by forming bioinspired cell-membrane-specific silica-based encapsulants. These include vapor phase deposition of silica gels, use of endogenous membrane proteins and polysaccharides as a site for silica nucleation and polycondensation in a saturated environment, and protein templated ordered silica shell formation. We demonstrate silica layer formation at the surface of pluripotent stem-like cells, bacterial biofilms, and primary murine and human pancreatic islets. Materials are characterized by AFM, SEM and EDS. Viability assays confirm cell survival, and metabolite flux measurements demonstrate normal function and no major diffusion limitations. Real time PCR mRNA analysis indicates encapsulated islets express normal levels of genetic markers for β-cells and insulin production. The silica glass encapsulant produces a secondary bone like calcium phosphate mineral layer upon exposure to media. Such bioactive materials can improve device integration with surrounding tissue upon implantation. Given the favorable insulin response, bioactivity, and long-term viability observed in silica-coated islets, we are currently testing the encapsulant's ability to prevent immune system recognition of foreign transplants for the treatment of diabetes. Such hybrid silica-cellular constructs have a wide range of industrial, environmental, and medical applications.

  1. Precipitated silica as flow regulator.

    PubMed

    Müller, Anne-Kathrin; Ruppel, Joanna; Drexel, Claus-Peter; Zimmermann, Ingfried

    2008-08-01

    Flow regulators are added to solid pharmaceutical formulations to improve the flow properties of the powder mixtures. The primary particles of the flow regulators exist in the form of huge agglomerates which are broken down into smaller aggregates during the blending process. These smaller aggregates adsorb at the surface of the solid's grains and thus diminish attractive Van-der-Waals-forces by increasing the roughness of the host's surface. In most cases amorphous silica is used as flow additive but material properties like particle size or bond strength influence the desagglomeration tendency of the agglomerates and thus the flow regulating potency of each silica. For some silica types we will show that the differences in their flow regulating potency are due to the rate and extent by which they are able to cover the surface of the host particles. Binary powder mixtures consisting of a pharmaceutical excipient and an added flow regulator were blended in a Turbula mixer for a defined period of time. As pharmaceutical excipient corn starch was used. The flow regulators were represented by a selection of amorphous silicon dioxide types like a commercial fumed silica and various types of SIPERNAT precipitated silica provided by Evonik-Degussa GmbH, Hanau, Germany. Flowability parameters of the mixtures were characterized by means of a tensile strength tester. The reduction of tensile strength with the blending time can be correlated with an increase in fragmentation of the flow regulator. PMID:18595668

  2. Metal binding to the N-terminal cytoplasmic domain of the PIB ATPase HMA4 is required for metal transport in Arabidopsis.

    PubMed

    Laurent, Clémentine; Lekeux, Gilles; Ukuwela, Ashwinie A; Xiao, Zhiguang; Charlier, Jean-Benoit; Bosman, Bernard; Carnol, Monique; Motte, Patrick; Damblon, Christian; Galleni, Moreno; Hanikenne, Marc

    2016-03-01

    PIB ATPases are metal cation pumps that transport metals across membranes. These proteins possess N- and C-terminal cytoplasmic extensions that contain Cys- and His-rich high affinity metal binding domains, which may be involved in metal sensing, metal ion selectivity and/or in regulation of the pump activity. The PIB ATPase HMA4 (Heavy Metal ATPase 4) plays a central role in metal homeostasis in Arabidopsis thaliana and has a key function in zinc and cadmium hypertolerance and hyperaccumulation in the extremophile plant species Arabidopsis halleri. Here, we examined the function and structure of the N-terminal cytoplasmic metal-binding domain of HMA4. We mutagenized a conserved CCTSE metal-binding motif in the domain and assessed the impact of the mutations on protein function and localization in planta, on metal-binding properties in vitro and on protein structure by Nuclear Magnetic Resonance spectroscopy. The two Cys residues of the motif are essential for the function, but not for localization, of HMA4 in planta, whereas the Glu residue is important but not essential. These residues also determine zinc coordination and affinity. Zinc binding to the N-terminal domain is thus crucial for HMA4 protein function, whereas it is not required to maintain the protein structure. Altogether, combining in vivo and in vitro approaches in our study provides insights towards the molecular understanding of metal transport and specificity of metal P-type ATPases. PMID:26797794

  3. Structural Biology of The sequestration & Transport of Heavy Metal Toxins: NMR Structure Determination of Proteins Containing the CYS-X-Y-Metal Binding Motif

    SciTech Connect

    Stanley J. Opella

    2004-03-10

    The support from the Department of Energy enabled us to initiate research on several proteins from the bacterial mercury detoxification system; in particular, we were able to determine the structures of MerP and related metal binding sequences. We have also worked on the membrane transport proteins MerF and MerT.

  4. Arabidopsis AtNaKR1 is a phloem mobile metal-binding protein necessary for phloem function and root meristem maintenance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The SODIUM POTASSIUM ROOT DEFECTIVE 1 (NaKR1) encodes a soluble metal binding protein that is specifically expressed in companion cells of the phloem. The nakr1-1 mutant phenotype includes high Na+, K+, and Rb+ accumulation in leaves, short roots, and late flowering. Starch accumulation in the leave...

  5. Preconcentration of low levels of americium and plutonium from waste waters by synthetic water-soluble metal-binding polymers with ultrafiltration

    SciTech Connect

    Smith, B.F.; Gibson, R.R.; Jarvinen, G.D.; Robison, T.W.; Schroeder, N.C.; Stalnaker, N.D.

    1997-12-31

    A preconcentration approach to assist in the measurement of low levels of americium and plutonium in waste waters has been developed based on the concept of using water-soluble metal-binding polymers in combination with ultrafiltration. The method has been optimized to give over 90% recovery and accountability from actual waste water.

  6. Metal binding to the N-terminal cytoplasmic domain of the PIB ATPase HMA4 is required for metal transport in Arabidopsis.

    PubMed

    Laurent, Clémentine; Lekeux, Gilles; Ukuwela, Ashwinie A; Xiao, Zhiguang; Charlier, Jean-Benoit; Bosman, Bernard; Carnol, Monique; Motte, Patrick; Damblon, Christian; Galleni, Moreno; Hanikenne, Marc

    2016-03-01

    PIB ATPases are metal cation pumps that transport metals across membranes. These proteins possess N- and C-terminal cytoplasmic extensions that contain Cys- and His-rich high affinity metal binding domains, which may be involved in metal sensing, metal ion selectivity and/or in regulation of the pump activity. The PIB ATPase HMA4 (Heavy Metal ATPase 4) plays a central role in metal homeostasis in Arabidopsis thaliana and has a key function in zinc and cadmium hypertolerance and hyperaccumulation in the extremophile plant species Arabidopsis halleri. Here, we examined the function and structure of the N-terminal cytoplasmic metal-binding domain of HMA4. We mutagenized a conserved CCTSE metal-binding motif in the domain and assessed the impact of the mutations on protein function and localization in planta, on metal-binding properties in vitro and on protein structure by Nuclear Magnetic Resonance spectroscopy. The two Cys residues of the motif are essential for the function, but not for localization, of HMA4 in planta, whereas the Glu residue is important but not essential. These residues also determine zinc coordination and affinity. Zinc binding to the N-terminal domain is thus crucial for HMA4 protein function, whereas it is not required to maintain the protein structure. Altogether, combining in vivo and in vitro approaches in our study provides insights towards the molecular understanding of metal transport and specificity of metal P-type ATPases.

  7. Stimuli-responsive polyaniline coated silica microspheres and their electrorheology

    NASA Astrophysics Data System (ADS)

    Park, Dae Eun; Choi, Hyoung Jin; Vu, Cuong Manh

    2016-05-01

    Silica/polyaniline (PANI) core–shell structured microspheres were synthesized by coating the surface of silica micro-beads with PANI and applied as a candidate inorganic/polymer composite electrorheological (ER) material. The silica micro-beads were initially modified using N-[(3-trimethoxysilyl)-propyl] aniline to activate an aniline functional group on the silica surface for a better PANI coating. The morphology of the PANI coating on the silica surface was examined by scanning electron microscopy and the silica/PANI core–shell structure was confirmed by transmission electron microscopy. The chemical structure of the particles was confirmed by Fourier transform infrared spectroscopy. Rotational rheometry was performed to confirm the difference in the ER properties between pure silica and silica/PANI microsphere-based ER fluids when dispersed in silicone oil.

  8. Stimuli-responsive polyaniline coated silica microspheres and their electrorheology

    NASA Astrophysics Data System (ADS)

    Park, Dae Eun; Choi, Hyoung Jin; Vu, Cuong Manh

    2016-05-01

    Silica/polyaniline (PANI) core-shell structured microspheres were synthesized by coating the surface of silica micro-beads with PANI and applied as a candidate inorganic/polymer composite electrorheological (ER) material. The silica micro-beads were initially modified using N-[(3-trimethoxysilyl)-propyl] aniline to activate an aniline functional group on the silica surface for a better PANI coating. The morphology of the PANI coating on the silica surface was examined by scanning electron microscopy and the silica/PANI core-shell structure was confirmed by transmission electron microscopy. The chemical structure of the particles was confirmed by Fourier transform infrared spectroscopy. Rotational rheometry was performed to confirm the difference in the ER properties between pure silica and silica/PANI microsphere-based ER fluids when dispersed in silicone oil.

  9. Synthesis of silica based porous nanomaterials

    NASA Astrophysics Data System (ADS)

    Mueller, Paul S.

    Silica is one of the most abundant elements on the planet, has flexible bonding properties and generally excellent stability. Because of these properties, silica has been a vital component in technologies ranging from ancient glassware to modern supercomputers. Silica is able to form a wide range of materials both alone and as a component of larger material frameworks. Porous silica based nanomaterials are rapidly growing in importance because of their many applications in a wide variety of fields. This thesis focuses on the synthesis of silica based porous nanomaterials: nanocrystalline zeolites, mesoporous silica nanoparticles, and iron oxide core/shell nanocomposites. The synthetic conditions of these materials were varied in order to maximize efficiency, minimize environmental impact, and produce high quality material with far reaching potential applications. The materials were characterized by physicochemical techniques including Transmission Electron Microscopy, Dynamic Light Scattering, Powder X-Ray Diffraction, Solid State NMR, and Nitrogen Adsorption Isotherms. The materials were evaluated and conditions were controlled to produce high yields of quality nanomaterials and hypothesize methods for further synthetic control. The products will be used in studies involving nanoparticle toxicity, environmental remediation, and drug delivery.

  10. Fungus-mediated biotransformation of amorphous silica in rice husk to nanocrystalline silica.

    PubMed

    Bansal, Vipul; Ahmad, Absar; Sastry, Murali

    2006-11-01

    Rice husk is a cheap agro-based waste material, which harbors a substantial amount of silica in the form of amorphous hydrated silica grains. However, there have been no attempts at harnessing the enormous amount of amorphous silica present in rice husk and its room-temperature biotransformation into crystalline silica nanoparticles. In this study, we address this issue and describe how naturally deposited amorphous biosilica in rice husk can be bioleached and simultaneously biotransformed into high value crystalline silica nanoparticles. We show here that the fungus Fusarium oxysporum rapidly biotransforms the naturally occurring amorphous plant biosilica into crystalline silica and leach out silica extracellularly at room temperature in the form of 2-6 nm quasi-spherical, highly crystalline silica nanoparticles capped by stabilizing proteins; that the nanoparticles are released into solution is an advantage of this process with significant application and commercial potential. Calcination of the silica nanoparticles leads to loss of occluded protein and to an apparently porous structure often of cubic morphology. The room-temperature synthesis of oxide nanomaterials using microorganisms starting from potential cheap agro-industrial waste materials is an exciting possibility and could lead to an energy-conserving and economically viable green approach toward the large-scale synthesis of oxide nanomaterials.

  11. Fungus-mediated biotransformation of amorphous silica in rice husk to nanocrystalline silica.

    PubMed

    Bansal, Vipul; Ahmad, Absar; Sastry, Murali

    2006-11-01

    Rice husk is a cheap agro-based waste material, which harbors a substantial amount of silica in the form of amorphous hydrated silica grains. However, there have been no attempts at harnessing the enormous amount of amorphous silica present in rice husk and its room-temperature biotransformation into crystalline silica nanoparticles. In this study, we address this issue and describe how naturally deposited amorphous biosilica in rice husk can be bioleached and simultaneously biotransformed into high value crystalline silica nanoparticles. We show here that the fungus Fusarium oxysporum rapidly biotransforms the naturally occurring amorphous plant biosilica into crystalline silica and leach out silica extracellularly at room temperature in the form of 2-6 nm quasi-spherical, highly crystalline silica nanoparticles capped by stabilizing proteins; that the nanoparticles are released into solution is an advantage of this process with significant application and commercial potential. Calcination of the silica nanoparticles leads to loss of occluded protein and to an apparently porous structure often of cubic morphology. The room-temperature synthesis of oxide nanomaterials using microorganisms starting from potential cheap agro-industrial waste materials is an exciting possibility and could lead to an energy-conserving and economically viable green approach toward the large-scale synthesis of oxide nanomaterials. PMID:17061888

  12. Engineered Bacterial Metal-binding Proteins for Nanoscale Self-assembly and heavy Metal Tolerance

    NASA Astrophysics Data System (ADS)

    Hall Sedlak, Ruth Amanda

    Implementing biological principles in material synthesis and assembly is one way to expand our abilities to efficiently assemble nanoscale materials and devices. Specifically, recent advances in identifying peptides that bind inorganic materials with high affinity and specificity has spurred investigation of protein models for nanoscale inorganic assembly. This dissertation presents the results of my studies of several E. coli proteins engineered to bind inorganic materials through simple peptide motifs. I demonstrate that these proteins modulate the self-assembly of DNA-based nanostructures and can introduce heavy metal tolerance into metal-sensitive bacteria. Chapter 2 explores use of the engineered F plasmid DNA relaxase/helicase TraI for the self-assembly of complex DNA-protein-gold nanostructures. The full-length protein is engineered with a gold binding motif at an internal permissive site (TraI369GBP1-7x), while a truncated version of TraI is engineered with the same gold binding motif at the C-terminus (TraI361GBP1-7x). Both constructs bind gold nanoparticles while maintaining their DNA binding activity, and transmission electron microscopy reveals TraI369GBP1-7x utilizes its non-specific DNA binding activity to decorate single-stranded and double-stranded DNA with gold nanoparticles. The self assembly principles demonstrated in this work will be fundamental to constructing higher ordered hybrid nanostructures through DNA-protein-nanoparticle interactions. Chapter 3 studies the effects of expressing inorganic binding peptides within cells. I identified a silver binding peptide that, when fused to the periplasmic maltose binding protein, protects E. coli from silver toxicity in batch culture and reduces silver ions to silver nanoparticles within the bacterial periplasm. Engineered metal-ion tolerant microorganisms such as this E. coli could potentially be used in applications ranging from remediation to interrogation of biomolecule-metal interactions in vivo

  13. Silica extraction from geothermal water

    DOEpatents

    Bourcier, William L; Bruton, Carol J

    2014-09-23

    A method of producing silica from geothermal fluid containing low concentration of the silica of less than 275 ppm includes the steps of treating the geothermal fluid containing the silica by reverse osmosis treatment thereby producing a concentrated fluid containing the silica, seasoning the concentrated fluid thereby producing a slurry having precipitated colloids containing the silica, and separating the silica from the slurry.

  14. Incorporation of anti-inflammatory agent into mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rodrigues Braz, Wilson; Lamec Rocha, Natállia; de Faria, Emerson H.; Silva, Márcio L. A. e.; Ciuffi, Katia J.; Tavares, Denise C.; Furtado, Ricardo Andrade; Rocha, Lucas A.; Nassar, Eduardo J.

    2016-09-01

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol-gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol-gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  15. Incorporation of anti-inflammatory agent into mesoporous silica

    NASA Astrophysics Data System (ADS)

    Rodrigues Braz, Wilson; Lamec Rocha, Natállia; de Faria, Emerson H.; Silva, Márcio L. A. e.; Ciuffi, Katia J.; Tavares, Denise C.; Furtado, Ricardo Andrade; Rocha, Lucas A.; Nassar, Eduardo J.

    2016-09-01

    The unique properties of macroporous, mesoporous, and microporous systems, including their ability to accommodate molecules of different sizes inside their pores and to act as drug delivery systems, have been the object of extensive studies. In this work, mesoporous silica with hexagonal structure was obtained by template synthesis via the sol–gel process. The resulting material was used as support to accommodate the anti-inflammatory agent indomethacin. The alkaline route was used to prepare the mesoporous silica; cetyltrimethylammonium bromide was employed as porogenic agent. The silica particles were functionalized with 3-aminopropyltriethoxysilane alkoxide (APTES) by the sol–gel post-synthesis method. Indomethacin was incorporated into the silica functionalized with APTES and into non-functionalized silica. The resulting systems were characterized by x-ray diffraction (XRD), specific area, infrared spectroscopy, and thermal analyses (TGA). XRD attested to formation of mesoporous silica with hexagonal structure. This structure remained after silica functionalization with APTES and incorporation of indomethacin. Typical infrared spectroscopy vibrations and organic material decomposition during TGA confirmed silica functionalization and drug incorporation. The specific surface area and pore volume of the functionalized material incorporated with indomethacin decreased as compared with the specific surface area and pore volume of the non-functionalized silica containing no drug, suggesting both the functionalizing agent and the drug were present in the silica. Cytotoxicity tests conducted on normal fibroblasts (GM0479A) cells attested that the silica matrix containing indomethacin was less toxic than the free drug.

  16. Ab initio Study of Transition metal binding to the Prion Protein

    NASA Astrophysics Data System (ADS)

    Cox, Daniel L.; Singh, Rajiv R. P.; Pan, Jianping

    2004-03-01

    Fundamental understanding of the prion protein (PrP) is of critical public health importance in view of mad cow and chronic wasting diseases. In recent years, it has been shown that the normal form (PrP^c) binds copper^1), and the structure of the copper binding domain has been elaborated. Hypotheses about toxicity associated with binding of other metals (notably manganese) have been put forward, Accordingly, using the ab initio SIESTA density functional theory code^2), we calculated the binding energy E_B(M) of M-(PrP) complexes relative to initially uncomplexed M ions, with M=Cu,Ni,Zn,Mn and (PrP)^* the minimal binding domain. The binding energy trend is E_B(Ni)>E_B(Cu)>E_B(Zn)>E_B(Mn), consistent with recent experiments apart from the surprising stability of Ni. We will also present preliminary results for binding of initially complexed M ions. *-Supported by U.S. DOE, Office of Basic Energy Sciences, Division of Materials Research 1) G.S. Jackson et al., Proc. Nat. Acad. Sci. (USA) 98, 8531 (2001). 2) P. Ordejón, et al., Phys. Rev. B53, R10441 (1996); J.M. Soler et al., J. Phys. Cond. Matt. 14, 2745 (2002).

  17. Synthesis and Characterization of Bionanoparticle-Silica Composites and Mesoporous Silica with Large Pores

    SciTech Connect

    Niu, Z.; Yang, L.; Kabisatpathy, S.; He, J.; Lee, A.; Ron, J.; Sikha, G.; Popov, B.N.; Emrick, T.; Russell, T. P.; Wang. Q.

    2009-03-24

    A sol-gel process has been developed to incorporate bionanoparticles, such as turnip yellow mosaic virus, cowpea mosaic virus, tobacco mosaic virus, and ferritin into silica, while maintaining the integrity and morphology of the particles. The structures of the resulting materials were characterized by transmission electron microscopy, small angle X-ray scattering, and N{sub 2} adsorption-desorption analysis. The results show that the shape and surface morphology of the bionanoparticles are largely preserved after being embedded into silica. After removal of the bionanoparticles by calcination, mesoporous silica with monodisperse pores, having the shape and surface morphology of the bionanoparticles replicated inside the silica, was produced,. This study is expected to lead to both functional composite materials and mesoporous silica with structurally well-defined large pores.

  18. Sulfur and selenium antioxidants: challenging radical scavenging mechanisms and developing structure-activity relationships based on metal binding.

    PubMed

    Zimmerman, Matthew T; Bayse, Craig A; Ramoutar, Ria R; Brumaghim, Julia L

    2015-04-01

    Because sulfur and selenium antioxidants can prevent oxidative damage, numerous animal and clinical trials have investigated the ability of these compounds to prevent the oxidative stress that is an underlying cause of cardiovascular disease, Alzheimer's disease, and cancer, among others. One of the most common sources of oxidative damage is metal-generated hydroxyl radical; however, very little research has focused on determining the metal-binding abilities and structural attributes that affect oxidative damage prevention by sulfur and selenium compounds. In this review, we describe our ongoing investigations into sulfur and selenium antioxidant prevention of iron- and copper-mediated oxidative DNA damage. We determined that many sulfur and selenium compounds inhibit Cu(I)-mediated DNA damage and that DNA damage prevention varies dramatically when Fe(II) is used in place of Cu(I) to generate hydroxyl radical. Oxidation potentials of the sulfur or selenium compounds do not correlate with their ability to prevent DNA damage, highlighting the importance of metal coordination rather than reactive oxygen species scavenging as an antioxidant mechanism. Additional gel electrophoresis, mass spectrometry, and UV-visible studies confirmed sulfur and selenium antioxidant binding to Cu(I) and Fe(II). Ultimately, our studies established that both the hydroxyl-radical-generating metal ion and the chemical environment of the sulfur or selenium significantly affect DNA damage prevention and that metal coordination is an essential mechanism for these antioxidants.

  19. Evaluation of synthetic water-soluble metal-binding polymers with ultrafiltration for selective concentration of americium and plutonium

    SciTech Connect

    Smith, B.F.; Gibson, R.R.; Jarvinen, G.D.; Jones, M.M.; Lu, M.T.; Robison, T.W.; Schroeder, N.C.; Stalnaker, N.

    1997-12-31

    Routine counting methods and ICP-MS are unable to directly measure the new US Department of Energy (DOE) regulatory level for discharge waters containing alpha-emitting radionuclides of 30 pCi/L total alpha or the 0.05 pCi/L regulatory level for Pu or Am activity required for surface waters at the Rocky Flats site by the State of Colorado. This inability indicates the need to develop rapid, reliable, and robust analytical techniques for measuring actinide metal ions, particularly americium and plutonium. Selective separation or preconcentration techniques would aid in this effort. Water-soluble metal-binding polymers in combination with ultrafiltration are shown to be an effective method for selectively removing dilute actinide ions from acidic solutions of high ionic strength. The actinide-binding properties of commercially available water-soluble polymers and several polymers which have been reported in the literature were evaluated. The functional groups incorporated in the polymers were pyrrolidone, amine, oxime, and carboxylic, phosphonic, or sulfonic acid. The polymer containing phosphonic acid groups gave the best results with high distribution coefficients and concentration factors for {sup 241}Am(III) and {sup 238}Pu(III)/(IV) at pH 4 to 6 and ionic strengths of 0.1 to 4.

  20. Metal-binding protein in the pacific oyster, Crassostrea gigas: assessment of the protein as a biochemical environmental indicator

    SciTech Connect

    Imber, B.E.; Thompson, J.A.J.; Ward, S.

    1987-04-01

    In this paper the determination of metal-binding proteins (MBP) in the Pacific Oyster (Crassostrea gigas) is reported. The objectives of this study were to employ a simple, cost-effective method for quantifying MBP and to assess this parameter for possible use as an indicator of identifiable sources of metal input to biological systems. Abnormally high quantities of zinc had been found previously in C. gigas growing in waters adjacent to the Kraft pump mill at Crofton, British Columbia. From 1971 to 1973 oysters near the effluent outfalls were found to have body-burden zinc six to ten times the zinc concentrations found in reference specimens. Zinc dithionite was used in the pulping process at the mill until 1973. Subsequent to a change to sodium dithionite, concentrations of zinc in oysters decreased steadily. A second potential source of contamination is sited directly south of the pulp mill. In this case, leaching of copper and zinc from smelter slag into Osborn Bay has been identified.

  1. Transcriptional Regulation, Metal Binding Properties and Structure of Pden1597, an Unusual Zinc Transport Protein from Paracoccus denitrificans.

    PubMed

    Handali, Melody; Neupane, Durga P; Roychowdhury, Hridindu; Yukl, Erik T

    2015-05-01

    ATP-binding cassette (ABC) transporters of the cluster 9 family are ubiquitous among bacteria and essential for acquiring Zn(2+) and Mn(2+) from the environment or, in the case of pathogens, from the host. These rely on a substrate-binding protein (SBP) to coordinate the relevant metal with high affinity and specificity and subsequently release it to a membrane permease for translocation into the cytoplasm. Although a number of cluster 9 SBP structures have been determined, the structural attributes conferring Zn(2+) or Mn(2+) specificity remain ambiguous. Here we describe the gene expression profile, in vitro metal binding properties, and crystal structure of a new cluster 9 SBP from Paracoccus denitrificans we have called AztC. Although all of our results strongly indicate Zn(2+) over Mn(2+) specificity, the Zn(2+) ion is coordinated by a conserved Asp residue only observed to date as a metal ligand in Mn(2+)-specific SBPs. The unusual sequence properties of this protein are shared among close homologues, including members from the human pathogens Klebsiella pneumonia and Enterobacter aerogenes, and would seem to suggest a subclass of Zn(2+)-specific transporters among the cluster 9 family. In any case, the unusual coordination environment of AztC expands the already considerable range of those available to Zn(2+)-specific SBPs and highlights the presence of a His-rich loop as the most reliable indicator of Zn(2+) specificity.

  2. Structures and metal-binding properties of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center.

    PubMed

    Yokoyama, Hideshi; Fujii, Satoshi

    2014-06-26

    Helicobacter pylori causes severe diseases, such as chronic gastritis, peptic ulcers, and stomach cancers. H. pylori neutrophil-activating protein (HP-NAP) is an iron storage protein that forms a dodecameric shell, promotes the adhesion of neutrophils to endothelial cells, and induces the production of reactive oxygen radicals. HP-NAP belongs to the DNA-protecting proteins under starved conditions (Dps) family, which has significant structural similarities to the dodecameric ferritin family. The crystal structures of the apo form and metal-ion bound forms, such as iron, zinc, and cadmium, of HP-NAP have been determined. This review focused on the structures and metal-binding properties of HP-NAP. These metal ions bind at the di-nuclear ferroxidase center (FOC) by different coordinating patterns. In comparison with the apo structure, metal loading causes a series of conformational changes in conserved residues among HP-NAP and Dps proteins (Trp26, Asp52, and Glu56) at the FOC. HP-NAP forms a spherical dodecamer with 23 symmetry including two kinds of pores. Metal ions have been identified around one of the pores; therefore, the negatively-charged pore is suitable for the passage of metal ions.

  3. Transcriptional Regulation, Metal Binding Properties and Structure of Pden1597, an Unusual Zinc Transport Protein from Paracoccus denitrificans.

    PubMed

    Handali, Melody; Neupane, Durga P; Roychowdhury, Hridindu; Yukl, Erik T

    2015-05-01

    ATP-binding cassette (ABC) transporters of the cluster 9 family are ubiquitous among bacteria and essential for acquiring Zn(2+) and Mn(2+) from the environment or, in the case of pathogens, from the host. These rely on a substrate-binding protein (SBP) to coordinate the relevant metal with high affinity and specificity and subsequently release it to a membrane permease for translocation into the cytoplasm. Although a number of cluster 9 SBP structures have been determined, the structural attributes conferring Zn(2+) or Mn(2+) specificity remain ambiguous. Here we describe the gene expression profile, in vitro metal binding properties, and crystal structure of a new cluster 9 SBP from Paracoccus denitrificans we have called AztC. Although all of our results strongly indicate Zn(2+) over Mn(2+) specificity, the Zn(2+) ion is coordinated by a conserved Asp residue only observed to date as a metal ligand in Mn(2+)-specific SBPs. The unusual sequence properties of this protein are shared among close homologues, including members from the human pathogens Klebsiella pneumonia and Enterobacter aerogenes, and would seem to suggest a subclass of Zn(2+)-specific transporters among the cluster 9 family. In any case, the unusual coordination environment of AztC expands the already considerable range of those available to Zn(2+)-specific SBPs and highlights the presence of a His-rich loop as the most reliable indicator of Zn(2+) specificity. PMID:25787075

  4. Copper chaperone Atox1 interacts with the metal-binding domain of Wilson's disease protein in cisplatin detoxification.

    PubMed

    Dolgova, Nataliya V; Nokhrin, Sergiy; Yu, Corey H; George, Graham N; Dmitriev, Oleg Y

    2013-08-15

    Human copper transporters ATP7B (Wilson's disease protein) and ATP7A (Menkes' disease protein) have been implicated in tumour resistance to cisplatin, a widely used anticancer drug. Cisplatin binds to the copper-binding sites in the N-terminal domain of ATP7B, and this binding may be an essential step of cisplatin detoxification involving copper ATPases. In the present study, we demonstrate that cisplatin and a related platinum drug carboplatin produce the same adduct following reaction with MBD2 [metal-binding domain (repeat) 2], where platinum is bound to the side chains of the cysteine residues in the CxxC copper-binding motif. This suggests the same mechanism for detoxification of both drugs by ATP7B. Platinum can also be transferred to MBD2 from copper chaperone Atox1, which was shown previously to bind cisplatin. Binding of the free cisplatin and reaction with the cisplatin-loaded Atox1 produce the same protein-bound platinum intermediate. Transfer of platinum along the copper-transport pathways in the cell may serve as a mechanism of drug delivery to its target in the cell nucleus, and explain tumour-cell resistance to cisplatin associated with the overexpression of copper transporters ATP7B and ATP7A.

  5. Expression and purification of recombinant proteins in Escherichia coli tagged with a small metal-binding protein from Nitrosomonas europaea.

    PubMed

    Vargas-Cortez, Teresa; Morones-Ramirez, Jose Ruben; Balderas-Renteria, Isaias; Zarate, Xristo

    2016-02-01

    Escherichia coli is still the preferred organism for large-scale production of recombinant proteins. The use of fusion proteins has helped considerably in enhancing the solubility of heterologous proteins and their purification with affinity chromatography. Here, the use of a small metal-binding protein (SmbP) from Nitrosomonas europaea is described as a new fusion protein for protein expression and purification in E. coli. Fluorescent proteins tagged at the N-terminal with SmbP showed high levels of solubility, compared with those of maltose-binding protein and glutathione S-transferase, and low formation of inclusion bodies. Using commercially available IMAC resins charged with Ni(II), highly pure recombinant proteins were obtained after just one chromatography step. Proteins may be purified from the periplasm of E. coli if SmbP contains the signal sequence at the N-terminal. After removal of the SmbP tag from the protein of interest, high-yields are obtained since SmbP is a protein of just 9.9 kDa. The results here obtained suggest that SmbP is a good alternative as a fusion protein/affinity tag for the production of soluble recombinant proteins in E. coli.

  6. Health hazards due to the inhalation of amorphous silica.

    PubMed

    Merget, R; Bauer, T; Küpper, H U; Philippou, S; Bauer, H D; Breitstadt, R; Bruening, T

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic ("thermal" or "fumed") silica, and (3) chemically or physically modified silica. According to the different physicochemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no study

  7. Nonporous Silica Nanoparticles for Nanomedicine Application

    PubMed Central

    Tang, Li; Cheng, Jianjun

    2013-01-01

    Summary Nanomedicine, the use of nanotechnology for biomedical applications, has potential to change the landscape of the diagnosis and therapy of many diseases. In the past several decades, the advancement in nanotechnology and material science has resulted in a large number of organic and inorganic nanomedicine platforms. Silica nanoparticles (NPs), which exhibit many unique properties, offer a promising drug delivery platform to realize the potential of nanomedicine. Mesoporous silica NPs have been extensively reviewed previously. Here we review the current state of the development and application of nonporous silica NPs for drug delivery and molecular imaging. PMID:23997809

  8. Conversion of geothermal waste to commercial products including silica

    DOEpatents

    Premuzic, Eugene T.; Lin, Mow S.

    2003-01-01

    A process for the treatment of geothermal residue includes contacting the pigmented amorphous silica-containing component with a depigmenting reagent one or more times to depigment the silica and produce a mixture containing depigmented amorphous silica and depigmenting reagent containing pigment material; separating the depigmented amorphous silica and from the depigmenting reagent to yield depigmented amorphous silica. Before or after the depigmenting contacting, the geothermal residue or depigmented silica can be treated with a metal solubilizing agent to produce another mixture containing pigmented or unpigmented amorphous silica-containing component and a solubilized metal-containing component; separating these components from each other to produce an amorphous silica product substantially devoid of metals and at least partially devoid of pigment. The amorphous silica product can be neutralized and thereafter dried at a temperature from about 25.degree. C. to 300.degree. C. The morphology of the silica product can be varied through the process conditions including sequence contacting steps, pH of depigmenting reagent, neutralization and drying conditions to tailor the amorphous silica for commercial use in products including filler for paint, paper, rubber and polymers, and chromatographic material.

  9. High purity silica reflective heat shield development

    NASA Technical Reports Server (NTRS)

    Nachtscheim, P. R.; Blome, J. C.

    1976-01-01

    A hyperpure vitreous silica material is being developed for use as a reflective and ablative heat shield for planetary entry. Various purity grades and forms of raw materials were evaluated along with various processing methods. Slip casting of high purity grain was selected as the best processing method, resulting in a highly reflective material in the wavelength bands of interest (the visible and ultraviolet regions). The selected material was characterized with respect to optical, mechanical and physical properties using a limited number of specimens. The process has been scaled up to produce a one-half scale heat shield (18 in. dia.) (45.72 cm) for a Jupiter entry vehicle. This work is now being extended to improve the structural safety factor of the heat shield by making hyperpure silica material tougher through the addition of silica fibers.

  10. Surface modification of HMS material with silica sol leading to a remarkable enhanced catalytic performance of Cu/SiO2

    NASA Astrophysics Data System (ADS)

    Yin, Anyuan; Wen, Chao; Dai, Wei-Lin; Fan, Kangnian

    2011-04-01

    Cu/SiO2 catalysts with different bimodal pore structures adjusted by the ratio of HMS and silica sol were prepared via modified impregnation method. Structure evolutions of the catalyst were systematically characterized by N2-physisorption, X-ray diffraction, H2 temperature-programmed reduction, N2O titration and X-ray photoelectron spectroscopy. The results show that the composite silica supported copper catalysts showed remarkably enhanced catalytic performance in the selective hydrogenation of dimethyl oxalate to ethylene glycol compared to the individual silica supported ones obtained by the same method. The dimethyl oxalate conversion and the ethylene glycol selectivity can reach 100% and 98% at 473 K with 2.5 MPa H2 pressure and 1.5 h-1 liquid hour space velocity of dimethyl oxalate over the optimized Cu/SiO2 catalyst. The remarkably enhanced catalytic performance of Cu/SiO2 catalysts might be attributed to the homogeneous dispersion and uniformity of the active copper species and to the larger copper surface areas attained on the HMS supports with large pore diameters and surface areas.

  11. Silica and Pyroxene in IVA Irons; Possible Formation of the IVA Magma by Impact Melting and Reduction of L-LL-Chondrite Materials Followed by Crystallization and Cooling

    NASA Technical Reports Server (NTRS)

    Wasson, John T.; Matsunami, Yoshiyuki; Rubin, Alan E.

    2006-01-01

    Group IVA is a large magmatic group of iron meteorites. The mean DELTA O-17 (= delta O-17 - 0.52(raised dot) delta O-18) of the silicates is approx. plus or minus 1.2%o, similar to the highest values in L chondrites and the lowest values in LL chondrites; delta O-18 values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (approx. 170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (approx. 1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, Sao Joao Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after approx. 26% crystallization and Steinbach formed after approx. 77% Crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced

  12. Silica and pyroxene in IVA irons; possible formation of the IVA magma by impact melting and reduction of L-LL-chondrite materials followed by crystallization and cooling

    NASA Astrophysics Data System (ADS)

    Wasson, John T.; Matsunami, Yoshiyuki; Rubin, Alan E.

    2006-06-01

    Group IVA is a large magmatic group of iron meteorites. The mean Δ 17O (=δ 17O - 0.52·δ 18O) of the silicates is ˜+1.2‰, similar to the highest values in L chondrites and the lowest values in LL chondrites; δ 18O values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (˜170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (˜1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, São João Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after ˜26% crystallization and Steinbach formed after ˜77% crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced into IVA irons after the initial magma crystallized. Because the

  13. Silica substrate or portion formed from oxidation of monocrystalline silicon

    DOEpatents

    Matzke, Carolyn M.; Rieger, Dennis J.; Ellis, Robert V.

    2003-07-15

    A method is disclosed for forming an inclusion-free silica substrate using a monocrystalline silicon substrate as the starting material and oxidizing the silicon substrate to convert it entirely to silica. The oxidation process is performed from both major surfaces of the silicon substrate using a conventional high-pressure oxidation system. The resulting product is an amorphous silica substrate which is expected to have superior etching characteristics for microfabrication than conventional fused silica substrates. The present invention can also be used to convert only a portion of a monocrystalline silicon substrate to silica by masking the silicon substrate and locally thinning a portion the silicon substrate prior to converting the silicon portion entirely to silica. In this case, the silica formed by oxidizing the thinned portion of the silicon substrate can be used, for example, as a window to provide optical access through the silicon substrate.

  14. FINDSITE-metal: Integrating evolutionary information and machine learning for structure-based metal binding site prediction at the proteome level

    PubMed Central

    Brylinski, Michal; Skolnick, Jeffrey

    2010-01-01

    The rapid accumulation of gene sequences, many of which are hypothetical proteins with unknown function, has stimulated the development of accurate computational tools for protein function prediction with evolution/structure-based approaches showing considerable promise. In this paper, we present FINDSITE-metal, a new threading-based method designed specifically to detect metal binding sites in modeled protein structures. Comprehensive benchmarks using different quality protein structures show that weakly homologous protein models provide sufficient structural information for quite accurate annotation by FINDSITE-metal. Combining structure/evolutionary information with machine learning results in highly accurate metal binding annotations; for protein models constructed by TASSER, whose average Cα RMSD from the native structure is 8.9 Å, 59.5% (71.9%) of the best of top five predicted metal locations are within 4 Å (8 Å) from a bound metal in the crystal structure. For most of the targets, multiple metal binding sites are detected with the best predicted binding site at rank 1 and within the top 2 ranks in 65.6% and 83.1% of the cases, respectively. Furthermore, for iron, copper, zinc, calcium and magnesium ions, the binding metal can be predicted with high, typically 70-90%, accuracy. FINDSITE-metal also provides a set of confidence indexes that help assess the reliability of predictions. Finally, we describe the proteome-wide application of FINDSITE-metal that quantifies the metal binding complement of the human proteome. FINDSITE-metal is freely available to the academic community at http://cssb.biology.gatech.edu/findsite-metal/. PMID:21287609

  15. Engineering a catalytic metal binding site into a calcium-independent phosphatidylinositol-specific phospholipase C leads to enhanced stereoselectivity.

    PubMed

    Kravchuk, Alexander V; Zhao, Li; Bruzik, Karol S; Tsai, Ming-Daw

    2003-03-01

    Eukaryotic phosphatidylinositol-specific phospholipase Cs (PI-PLCs) utilize calcium as a cofactor during catalysis, whereas prokaryotic PI-PLCs use a spatially conserved guanidinium group from Arg69. In this study, we aimed to construct a metal-dependent mutant of a bacterial PI-PLC and characterize the catalytic role of the metal ion, seeking an enhanced understanding of the functional differences between these two positively charged moieties. The following results indicate that a bona fide catalytic metal binding site was created by the single arginine-to-aspartate mutation at position 69: (1) The R69D mutant was activated by Ca(2+), and the activation was specific for R69D, not for other mutants at this position. (2) Titration of R69D with Ca(2+), monitored by (15)N-(1)H HSQC (heteronuclear single quantum coherence) NMR, showed that addition of Ca(2+) to R69D restores the environment of the catalytic site analogous to that attained by the WT enzyme. (3) Upon Ca(2+) activation, the thio effect of the S(P)-isomer of the phosphorothioate analogue (k(O)/k(Sp) = 4.4 x 10(5)) approached a value similar to that of the WT enzyme, suggesting a structural and functional similarity between the two positively charged moieties (Arg69 and Asp69-Ca(2+)). The R(P)-thio effect (k(O)/k(Rp) = 9.4) is smaller than that of the WT enzyme by a factor of 5. Consequently, R69D-Ca(2+) displays higher stereoselectivity (k(Rp)/k(Sp) = 47,000) than WT (k(Rp)/k(Sp) = 7600). (4) Results from additional mutagenesis analyses suggest that the Ca(2+) binding site is comprised of side chains from Asp33, Asp67, Asp69, and Glu117. Our studies provide new insight into the mechanism of metal-dependent and metal-independent PI-PLCs.

  16. Structure and interactions of the C-terminal metal binding domain of Archaeoglobus fulgidus CopA

    SciTech Connect

    Agarwal, S.; Hong, D.; Desai, N.K.; H.Sazinsky, M.; Argüello, J.M.; Rosenzweig, A.C.

    2010-08-13

    The Cu(+)-ATPase CopA from Archaeoglobus fulgidus belongs to the P(1B) family of the P-type ATPases. These integral membrane proteins couple the energy of ATP hydrolysis to heavy metal ion translocation across membranes. A defining feature of P(1B-1)-type ATPases is the presence of soluble metal binding domains at the N-terminus (N-MBDs). The N-MBDs exhibit a conserved ferredoxin-like fold, similar to that of soluble copper chaperones, and bind metal ions via a conserved CXXC motif. The N-MBDs enable Cu(+) regulation of turnover rates apparently through Cu-sensitive interactions with catalytic domains. A. fulgidus CopA is unusual in that it contains both an N-terminal MBD and a C-terminal MBD (C-MBD). The functional role of the unique C-MBD has not been established. Here, we report the crystal structure of the apo, oxidized C-MBD to 2.0 A resolution. In the structure, two C-MBD monomers form a domain-swapped dimer, which has not been observed previously for similar domains. In addition, the interaction of the C-MBD with the other cytoplasmic domains of CopA, the ATP binding domain (ATPBD) and actuator domain (A-domain), has been investigated. Interestingly, the C-MBD interacts specifically with both of these domains, independent of the presence of Cu(+) or nucleotides. These data reinforce the uniqueness of the C-MBD and suggest a distinct structural role for the C-MBD in CopA transport.

  17. Spectral and metal-binding properties of three single-point tryptophan mutants of the human transferrin N-lobe.

    PubMed Central

    He, Q Y; Mason, A B; Lyons, B A; Tam, B M; Nguyen, V; MacGillivray, R T; Woodworth, R C

    2001-01-01

    Human serum transferrin N-lobe (hTF/2N) contains three conserved tryptophan residues, Trp(8), Trp(128) and Trp(264), located in three different environments. The present report addresses the different contributions of the three tryptophan residues to the UV-visible, fluorescence and NMR spectra of hTF/2N and the effect of the mutations at each tryptophan residue on the iron-binding properties of the protein. Trp(8) resides in a hydrophobic box containing a cluster of three phenylalanine side chains and is H bonded through the indole N to an adjacent water cluster lying between two beta-sheets containing Trp(8) and Lys(296) respectively. The fluorescence of Trp(8) may be quenched by the benzene rings. The apparent increase in the rate of iron release from the Trp(8)-->Tyr mutant could be due to the interference of the mutation with the H-bond linkage resulting in an effect on the second shell network. The partial quenching in the fluorescence of Trp(128) results from the nearby His(119) residue. Difference-fluorescence spectra reveal that any protein containing Trp(128) shows a blue shift upon binding metal ion, and the NMR signal of Trp(128) broadens out and disappears upon the binding of paramagnetic metals to the protein. These data imply that Trp(128) is a major fluorescent and NMR reporter group for metal binding, and possibly for cleft closure in hTF/2N. Trp(264) is located on the surface of the protein and does not connect to any functional residues. This explains the facts that Trp(264) is the major contributor to both the absorbance and fluorescence spectra, has a strong NMR signal and the mutation at Trp(264) has little effect on the iron-binding and release behaviours of the protein. PMID:11171122

  18. Intracellular trafficking of the human Wilson protein: the role of the six N-terminal metal-binding sites.

    PubMed Central

    Cater, Michael A; Forbes, John; La Fontaine, Sharon; Cox, Diane; Mercer, Julian F B

    2004-01-01

    The Wilson protein (ATP7B) is a copper-transporting CPx-type ATPase defective in the copper toxicity disorder Wilson disease. In hepatocytes, ATP7B delivers copper to apo-ceruloplasmin and mediates the excretion of excess copper into bile. These distinct functions require the protein to localize at two different subcellular compartments. At the trans-Golgi network, ATP7B transports copper for incorporation into apo-ceruloplasmin. When intracellular copper levels are increased, ATP7B traffics to post-Golgi vesicles in close proximity to the canalicular membrane to facilitate biliary copper excretion. In the present study, we investigated the role of the six N-terminal MBSs (metal-binding sites) in the trafficking process. Using site-directed mutagenesis, we mutated or deleted various combinations of the MBSs and assessed the effect of these changes on the localization and trafficking of ATP7B. Results show that the MBSs required for trafficking are the same as those previously found essential for the copper transport function. Either MBS 5 or MBS 6 alone was sufficient to support the redistribution of ATP7B to vesicular compartments. The first three N-terminal motifs were not required for copper-dependent intracellular trafficking and could not functionally replace sites 4-6 when placed in the same sequence position. Furthermore, the N-terminal region encompassing MBSs 1-5 (amino acids 64-540) was not essential for trafficking, with only one MBS close to the membrane channel, necessary and sufficient to support trafficking. Our findings were similar to those obtained for the closely related ATP7A protein, suggesting similar mechanisms for trafficking between copper-transporting CPx-type ATPases. PMID:14998371

  19. Multiple Metal Binding Domains Enhance the Zn(II) Selectivity of the Divalent Metal Ion Transporter AztA

    SciTech Connect

    Liu, T.; Reyes-Caballero, H.; Li, C.; Scott, R.A.; Giedroc, D.P.

    2009-06-03

    Transition metal-transporting P{sub 1B}-type CPx ATPases play crucial roles in mediating metal homeostasis and resistance in all cells. The degree to which N-terminal metal binding domains (MBDs) confer metal specificity to the transporter is unclear. We show that the two MBDs of the Zn/Cd/Pb effluxing pump Anabaena AztA are functionally nonequivalent, but only with respect to zinc resistance. Inactivation of the a-MBD largely abrogates resistance to high intracellular Zn(II) levels, whereas inactivation of the b-MBD is not as deleterious. In contrast, inactivation of either the a- or b-MBD has little measurable impact on Cd(II) and Pb(II) resistance. The membrane proximal b-MBD binds Zn(II) with a higher affinity than the distal N-terminal a-MBD. Facile Zn(II)-specific intermolecular transfer from the a-MBD to the higher-affinity b-MBD is readily observed by {sup 1}H-{sup 15}N HSQC spectroscopy. Unlike Zn(II), Cd(II) and Pb(II) form saturated 1:1 S{sub 4} or S{sub 3}(O/N) complexes with AztA{sup aHbH}, where a single metal ion bridges the two MBDs. We propose that the tandem MBDs enhance Zn(II)-specific transport, while stabilizing a non-native inter-MBD Cd/Pb cross-linked structure that is a poor substrate and/or regulator for the transporter.

  20. The role of substrate specificity and metal binding in defining the activity and structure of an intracellular subtilisin.

    PubMed

    Gamble, Michael; Künze, Georg; Brancale, Andrea; Wilson, Keith S; Jones, D Dafydd

    2012-01-01

    The dimeric intracellular subtilisin proteases (ISPs) found throughout Gram-positive bacteria are a structurally distinct class of the subtilase family. Unlike the vast majority of subtilisin-like proteases, the ISPs function exclusively within the cell, contributing the majority of observed cellular proteolytic activity. Given that they are active within the cell, little is known about substrate specificity and the role of stress signals such as divalent metal ions in modulating ISP function. We demonstrate that both play roles in defining the proteolytic activity of Bacillus clausii ISP and propose the molecular basis of their effects. Enzyme kinetics reveal that one particular synthetic tetrapeptide substrate, Phe-Ala-Ala-Phe-pNA, is hydrolysed with a catalytic efficiency ∼100-fold higher than any other tested. Heat-denatured whole proteins were found to be better substrates for ISP than the native forms. Substrate binding simulations suggest that the S1, S2 and S4 sites form defined binding pockets. The deep S1 cavity and wide S4 site are fully occupied by the hydrophobic aromatic side-chains of Phe. Divalent metal ions, probably Ca(2+), are proposed to be important for ISP activity through structural changes. The presence of >0.01 mM EDTA inactivates ISP, with CD and SEC suggesting that the protein becomes less structured and potentially monomeric. Removal of Ca(2+) at sites close to the dimer interface and the S1 pocket are thought to be responsible for the effect. These studies provide a new insight into the potential physiological function of ISPs, by reconciling substrate specificity and divalent metal binding to associate ISP with the unfolded protein response under stress conditions. PMID:23650602

  1. Metal binding properties of Escherichia coli YjiA, a member of the metal homeostasis-associated COG0523 family of GTPases.

    PubMed

    Sydor, Andrew M; Jost, Marco; Ryan, Katherine S; Turo, Kaitlyn E; Douglas, Colin D; Drennan, Catherine L; Zamble, Deborah B

    2013-03-12

    GTPases are critical molecular switches involved in a wide range of biological functions. Recent phylogenetic and genomic analyses of the large, mostly uncharacterized COG0523 subfamily of GTPases revealed a link between some COG0523 proteins and metal homeostasis pathways. In this report, we detail the bioinorganic characterization of YjiA, a representative member of COG0523 subgroup 9 and the only COG0523 protein to date with high-resolution structural information. We find that YjiA is capable of binding several types of transition metals with dissociation constants in the low micromolar range and that metal binding affects both the oligomeric structure and GTPase activity of the enzyme. Using a combination of X-ray crystallography and site-directed mutagenesis, we identify, among others, a metal-binding site adjacent to the nucleotide-binding site in the GTPase domain that involves a conserved cysteine and several glutamate residues. Mutations of the coordinating residues decrease the impact of metal, suggesting that metal binding to this site is responsible for modulating the GTPase activity of the protein. These findings point toward a regulatory function for these COG0523 GTPases that is responsive to their metal-bound state.

  2. Uranium incorporation into amorphous silica.

    PubMed

    Massey, Michael S; Lezama-Pacheco, Juan S; Nelson, Joey M; Fendorf, Scott; Maher, Kate

    2014-01-01

    High concentrations of uranium are commonly observed in naturally occurring amorphous silica (including opal) deposits, suggesting that incorporation of U into amorphous silica may represent a natural attenuation mechanism and promising strategy for U remediation. However, the stability of uranium in opaline silicates, determined in part by the binding mechanism for U, is an important factor in its long-term fate. U may bind directly to the opaline silicate matrix, or to materials such as iron (hydr)oxides that are subsequently occluded within the opal. Here, we examine the coordination environment of U within opaline silica to elucidate incorporation mechanisms. Precipitates (with and without ferrihydrite inclusions) were synthesized from U-bearing sodium metasilicate solutions, buffered at pH ∼ 5.6. Natural and synthetic solids were analyzed with X-ray absorption spectroscopy and a suite of other techniques. In synthetic amorphous silica, U was coordinated by silicate in a double corner-sharing coordination geometry (Si at ∼ 3.8-3.9 Å) and a small amount of uranyl and silicate in a bidentate, mononuclear (edge-sharing) coordination (Si at ∼ 3.1-3.2 Å, U at ∼ 3.8-3.9 Å). In iron-bearing synthetic solids, U was adsorbed to iron (hydr)oxide, but the coordination environment also contained silicate in both edge-sharing and corner-sharing coordination. Uranium local coordination in synthetic solids is similar to that of natural U-bearing opals that retain U for millions of years. The stability and extent of U incorporation into opaline and amorphous silica represents a long-term repository for U that may provide an alternative strategy for remediation of U contamination. PMID:24984107

  3. Interactions of silica surfaces

    SciTech Connect

    Vigil, G.; Xu, Z.; Steinberg, S.; Israelachvili, J. . Dept. of Chemical and Nuclear Engineering and Materials Dept.)

    1994-07-01

    Adhesion, friction, and colloidal forces in air and aqueous salt solutions have been measured between various silica surfaces prepared by depositing amorphous but highly smooth silica films on mica. The results show four interesting and interrelated phenomena: (i) the adhesion of silica surfaces in air increases slowly with contact time, especially in humid air where the contacting surfaces become separated by an [approximately]20-[angstrom]-thick layer of hydrated silica or silica gel; (ii) the friction of two silica surfaces exhibits large sticking or stiction spikes, whose magnitude increases in the presence of water and when the surfaces are kept in contact longer before sliding; (iii) the non-DLVO repulsion commonly seen at short range (<40 A) between silica surfaces immersed in aqueous solutions is monotonically repulsive, with no oscillatory component, and is quite unlike theoretical expectations and previous measurements of forces due to solvent structure; (iv) dynamic contact angle measurements reveal time-dependent effects which cannot be due to a fixed surface chemical heterogeneity or roughness. The results indicate that silica surfaces undergo slow structural and chemical changes during interactions with water and with each other. More specifically, the authors propose that the unusual interfacial and colloidal properties of silica are due, not to hydration effects, but to the presence of an [approximately]10-[angstrom]-thick gel-like layer of protruding silanol and silicilic acid groups that grow on the surfaces in the presence of water. These protruding groups react chemically (sinter) with similar groups located on an opposing surface and give rise to the unusual time-dependent adhesion, friction, and non-DLVO forces observed. The proposed mechanism in terms of a surface layer of silica gel is consistent with the known surface chemistry of silica and accounts for the results reported and for other unusual surface and colloidal properties of silica.

  4. Ga[OSi(O(t)Bu)3]3·THF, a thermolytic molecular precursor for high surface area gallium-containing silica materials of controlled dispersion and stoichiometry.

    PubMed

    Dombrowski, James P; Johnson, Gregory R; Bell, Alexis T; Tilley, T Don

    2016-07-01

    The molecular precursor tris[(tri-tert-butoxy)siloxy]gallium, as the tetrahydrofuran adduct Ga[OSi(O(t)Bu)3]3·THF (), was synthesized via the salt metathesis reaction of gallium trichloride with NaOSi(O(t)Bu)3. This complex serves as a model for isolated gallium in a silica framework. Complex decomposes thermally in hydrocarbon solvent, eliminating isobutylene, water, and tert-butanol to generate high surface area gallium-containing silica at low temperatures. When thermal decomposition was performed in the presence of P-123 Pluronic as a templating agent the generated material displayed uniform vermicular pores. Textural mesoporosity was evident in untemplated material. Co-thermolysis of with HOSi(O(t)Bu)3 in the presence of P-123 Pluronic led to materials with Ga : Si ratios ranging from 1 : 3 to 1 : 50, denoted UCB1-GaSi3, UCB1-GaSi10, UCB1-GaSi20 and UCB1-GaSi50. After calcination at 500 °C these materials exhibited decreasing surface areas and broadening pore distributions with increasing silicon content, indicating a loss of template effects. The position and dispersion of the gallium in UCB1-GaSi materials was investigated using (71)Ga MAS-NMR, powder XRD, and STEM/EDS elemental mapping. The results indicate a high degree of gallium dispersion in all samples, with gallium oxide clusters or oligomers present at higher gallium content. PMID:27312519

  5. Ga[OSi(O(t)Bu)3]3·THF, a thermolytic molecular precursor for high surface area gallium-containing silica materials of controlled dispersion and stoichiometry.

    PubMed

    Dombrowski, James P; Johnson, Gregory R; Bell, Alexis T; Tilley, T Don

    2016-07-01

    The molecular precursor tris[(tri-tert-butoxy)siloxy]gallium, as the tetrahydrofuran adduct Ga[OSi(O(t)Bu)3]3·THF (), was synthesized via the salt metathesis reaction of gallium trichloride with NaOSi(O(t)Bu)3. This complex serves as a model for isolated gallium in a silica framework. Complex decomposes thermally in hydrocarbon solvent, eliminating isobutylene, water, and tert-butanol to generate high surface area gallium-containing silica at low temperatures. When thermal decomposition was performed in the presence of P-123 Pluronic as a templating agent the generated material displayed uniform vermicular pores. Textural mesoporosity was evident in untemplated material. Co-thermolysis of with HOSi(O(t)Bu)3 in the presence of P-123 Pluronic led to materials with Ga : Si ratios ranging from 1 : 3 to 1 : 50, denoted UCB1-GaSi3, UCB1-GaSi10, UCB1-GaSi20 and UCB1-GaSi50. After calcination at 500 °C these materials exhibited decreasing surface areas and broadening pore distributions with increasing silicon content, indicating a loss of template effects. The position and dispersion of the gallium in UCB1-GaSi materials was investigated using (71)Ga MAS-NMR, powder XRD, and STEM/EDS elemental mapping. The results indicate a high degree of gallium dispersion in all samples, with gallium oxide clusters or oligomers present at higher gallium content.

  6. Silica, silicosis, and cancer

    SciTech Connect

    Goldsmith, D.F.; Winn, D.M.; Shy, C.M.

    1986-01-01

    These proceedings collect papers on occupational exposure. Topics include: measurement of silica dust, mortality in granite workers, effects of quartz in coal mine dust, pneumoconiosis, and lung cancer.

  7. Development of an improved toughness hyperpure silica reflective heat shield

    NASA Technical Reports Server (NTRS)

    Rusert, E. L.; Hackett, T. L.; Drennan, D. N.

    1979-01-01

    High purity three dimensionally woven silica-silica materials were evaluated for use as a tough reflective heat shield for planetary entry probes. A special weave design was selected to minimize light piping effects through the heat shield thickness. Various weave spacings were evaluated for densification efficiency with an 0.7 micron particle size high purity silica. Spectral hemispherical reflectance was measured from 0.2 to 2.5 microns at room temperature. Reflectance increases due to densification and purity of material were measured. Reflectance of 3D hyperpure silica was higher than 3D astroquartz silica for all wavelengths. Mechanical properties were measured in beam flexure and beam shear tests. Results indicated strengths lower than reported for slip cast fused silica. Low strengths were attributed to low densities achieved through vacuum impregnation.

  8. Grassy Silica Nanoribbons and Strong Blue Luminescence

    NASA Astrophysics Data System (ADS)

    Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng

    2016-09-01

    Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications.

  9. Grassy Silica Nanoribbons and Strong Blue Luminescence

    PubMed Central

    Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng

    2016-01-01

    Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications. PMID:27666663

  10. Designed synthesis of Graphene @titania @mesoporous silica hybrid material as size-exclusive metal oxide affinity chromatography platform for selective enrichment of endogenous phosphopeptides.

    PubMed

    Yao, Jizong; Sun, Nianrong; Deng, Chunhui; Zhang, Xiangming

    2016-04-01

    In this work, a novel size-exclusive metal oxide affinity chromatography (SE-MOAC) platform was built for phosphoproteome research. The operation for preparing graphene @titania @mesoporous silica nanohybrids (denoted as G@TiO2@mSiO2) was facile and easy to conduct by grafting titania nanoparticles on polydopamine (PD)-covered graphene, following a layer of mesoporous silica was coated on the outermost layer. The G@TiO2@mSiO2 nanohybrids exhibited high sensitivity with a low detection limit of 5 amol/μL (a total amount of 1 fmol) and high selectivity for phosphopeptides at a mass ratio of phosphopeptides to non-phosphopeptides (1:1000). The size-exclusive capability of the nanohybrids were also demonstrated by enriching the phosphopeptides from the mixture of Bovine Serum Albumin (BSA), α-casein, and β-casein digests with a high mass ratio (β-casein digests: α-casein: BSA, 1:500:500), which was attributed to the large surface area and ordered mesoporous channels. In addition, the G@TiO2@mSiO2 nanohybrids were employed to capture the endogenous phosphopeptides from human serum successfully. PMID:26838411

  11. Cadmium detoxification strategies in two phytoplankton species: metal binding by newly synthesized thiolated peptides and metal sequestration in granules.

    PubMed

    Lavoie, Michel; Le Faucheur, Séverine; Fortin, Claude; Campbell, Peter G C

    2009-04-01

    The aim of this study was to evaluate whether intracellular detoxification mechanisms could explain, at least partially, the different sensitivity to Cd of two freshwater green algae, Chlamydomonas reinhardtii and Pseudokirchneriella subcapitata. Subcellular Cd distribution and the synthesis of metal-binding thiolated peptides were thus examined in both algae exposed to a range of free [Cd(2+)] from 0.7 to 253 nM. Cadmium partitioning among five subcellular fractions (cellular debris, granules, organelles, heat-denaturable proteins - HDP, and heat-stable proteins - HSP) was determined after differential centrifugation of algal homogenates. Thiolated-peptides, phytochelatins (PC(n)) and precursors, were analyzed by HPLC with pre-column monobromobimane derivatization. Cadmium accumulation per cell was 2-4 times greater for C. reinhardtii than for P. subcapitata, yet C. reinhardtii was more resistant to Cd with an EC(50) of 273 nM Cd(2+) [244-333 nM Cd(2+) CI(95%)]) compared to 127 nM Cd(2+) [111-143 nM Cd(2+) CI(95%)] for P. subcapitata. Although [Cd] generally increased in the organelle fractions when free [Cd(2+)] increased in the experimental media, their relative contributions to the total Cd cellular content decreased, suggesting that partial protection of some metal sensitive sites was achieved by the initiation of cellular detoxification mechanisms. An increase in the proportion of Cd in the granules fraction was observed for C. reinhardtii between 6 and 15 nM Cd(2+) (i.e., at [Cd(2+)]

  12. Investigating the effects of posttranslational adenylylation on the metal binding sites of Escherichia coli glutamine synthetase using lanthanide luminescence spectroscopy.

    PubMed Central

    Reynaldo, L. P.; Villafranca, J. J.; Horrocks, W. D.

    1996-01-01

    Lanthanide luminescence was used to examine the effects of posttranslational adenylylation on the metal binding sites of Escherichia coli glutamine synthetase (GS). These studies revealed the presence of two lanthanide ion binding sites of GS of either adenylylation extrema. Individual emission decay lifetimes were obtained in both H2O and D2O solvent systems, allowing for the determination of the number of water molecules coordinated to each bound Eu3+. The results indicate that there are 4.3 +/- 0.5 and 4.6 +/- 0.5 water molecules coordinated to Eu3+ bound to the n1 site of unadenylylated enzyme, GS0, and fully adenylylated enzyme, GS12, respectively, and that there are 2.6 +/- 0.5 water molecules coordinated to Eu3+ at site n2 for both GS0 and GS12. Energy transfer measurements between the lanthanide donor-acceptor pair Eu3+ and Nd3+, obtained an intermetal distance measurement of 12.1 +/- 1.5 A. Distances between a Tb3+ ion at site n2 and tryptophan residues were also performed with the use of single-tryptophan mutant forms of E. coli GS. The dissociation constant for lanthanide ion binding to site n1 was observed to decrease from Kd = 0.35 +/- 0.09 microM for GS0 to Kd = 0.06 +/- 0.02 microM for GS12. The dissociation constant for lanthanide ion binding to site n2 remained unchanged as a function of adenylylation state; Kd = 3.8 +/- 0.9 microM and Kd = 2.6 +/- 0.7 microM for GS0 and GS12, respectively. Competition experiments indicate that Mn2+ affinity at site n1 decreases as a function of increasing adenylylation state, from Kd = 0.05 +/- 0.02 microM for GS0 to Kd = 0.35 +/- 0.09 microM for GS12. Mn2+ affinity at site n2 remains unchanged (Kd = 5.3 +/- 1.3 microM for GS0 and Kd = 4.0 +/- 1.0 microM for GS12). The observed divalent metal ion affinities, which are affected by the adenylylation state, agrees with other steady-state substrate experiments (Abell LM, Villafranca JJ, 1991, Biochemistry 30:1413-1418), supporting the hypothesis that adenylylation

  13. Apoprotein Structure and Metal Binding Characterization of a de Novo Designed Peptide, α3DIV, that Sequesters Toxic Heavy Metals

    PubMed Central

    Plegaria, Jefferson S.; Dzul, Stephen P.; Zuiderweg, Erik R. P.; Stemmler, Timothy L.; Pecoraro, Vincent L.

    2015-01-01

    De novo protein design is a biologically relevant approach that provides a novel process in elucidating protein folding and modeling the metal centers of metalloproteins in a completely unrelated or simplified fold. An integral step in de novo protein design is the establishment of a well-folded scaffold with one conformation, which is a fundamental characteristic of many native proteins. Here, we report the NMR solution structure of apo α3DIV at pH 7.0, a de novo designed three-helix bundle peptide containing a triscysteine motif (Cys18, Cys28, and Cys67) that binds toxic heavy metals. The structure comprises 1067 NOE restraints derived from multinuclear multidimensional NOESY, as well as 138 dihedral angles (ψ, φ, and χ1). The backbone and heavy atoms of the 20 lowest energy structures have a root mean square deviation from the mean structure of 0.79 (0.16) Å and 1.31 (0.15) Å, respectively. When compared to the parent structure α3D, the substitution of Leu residues to Cys enhanced the α-helical content of α3DIV while maintaining the same overall topology and fold. In addition, solution studies on the metalated species illustrated metal-induced stability. An increase in the melting temperatures was observed for Hg(II), Pb(II), or Cd(II) bound α3DIV by 18–24 °C compared to its apo counterpart. Further, the extended X-ray absorption fine structure analysis on Hg(II)-α3DIV produced an average Hg(II)–S bond length at 2.36 Å, indicating a trigonal T-shaped coordination environment. Overall, the structure of apo α3DIV reveals an asymmetric distorted triscysteine metal binding site, which offers a model for native metalloregulatory proteins with thiol-rich ligands that function in regulating toxic heavy metals, such as ArsR, CadC, MerR, and PbrR PMID:25790102

  14. The role of metal binding and phosphorylation domains in the regulation of cisplatin-induced trafficking of ATP7B.

    PubMed

    Safaei, Roohangiz; Adams, Preston L; Mathews, Ryan A; Manorek, Gerald; Howell, Stephen B

    2013-08-01

    The copper (Cu) exporter ATP7B mediates cellular resistance to cisplatin (cDDP) by increasing drug efflux. ATP7B binds and sequesters cDDP in into secretory vesicles. Upon cDDP exposure ATP7B traffics from the trans-Golgi network (TGN) to the periphery of the cell in a manner that requires the cysteine residues in its metal binding domains (MBD). To elucidate the role of the various domains of ATP7B in its cDDP-induced trafficking we expressed a series of mCherry-tagged variants of ATP7B in HEK293T cells and analyzed their subcellular localization in basal media and after a 1 h exposure to 30 μM cDDP. The wild type ATP7B and a variant in which the cysteines in the CXXC motifs of MBD 1-5 were converted to serines trafficked out of the trans-Golgi (TGN) when exposed to cDDP. Conversion of the cysteines in all 6 of the CXXC motifs to serines, or in only the sixth MBD, rendered ATP7B incapable of trafficking on exposure to cDDP. Truncation of MBD1-5 or MBD1-6 resulted in the loss of TGN localization. Addition of the first 63 amino acids of ATP7B to these variants restored TGN localization to a great extent and enabled the MBD1-5 variant to undergo cDDP-induced trafficking. A variant of ATP7B in which the aspartate 1027 residue in the phosphorylation domain was converted to glutamine localized to the TGN but was incapable of cDDP-induced trafficking. These results demonstrate that the CXXC motif in the sixth MBD and the catalytic activity of ATP7B are required for cDDP-induced trafficking as they are for Cu-induced redistribution of ATP7B; this provides further evidence that cDDP mimics Cu with respect to the molecular mechanisms by they control the subcellular distribution of ATP7B.

  15. The role of metal binding and phosphorylation domains in the regulation of cisplatin-induced trafficking of ATP7B

    PubMed Central

    Safaei, Roohangiz; Adams, Preston L.; Mathews, Ryan A.; Manorek, Gerald; Howell, Stephen B.

    2014-01-01

    The copper (Cu) exporter ATP7B mediates cellular resistance to cisplatin (cDDP) by increasing drug efflux. ATP7B binds and sequesters cDDP in into secretory vesicles. Upon cDDP exposure ATP7B traffics from the trans-Golgi network (TGN) to the periphery of the cell in a manner that requires the cysteine residues in its metal binding domains (MBD). To elucidate the role of the various domains of ATP7B in its cDDP-induced trafficking we expressed a series of mCherry-tagged variants of ATP7B in HEK293T cells and analyzed their subcellular localization in basal media and after a 1 h exposure to 30 μM cDDP. The wild type ATP7B and a variant in which the cysteines in the CXXC motifs of MBD 1-5 were converted to serines trafficked out of the trans-Golgi (TGN) when exposed to cDDP. Conversion of the cysteines in all 6 of the CXXC motifs to serines, or in only the sixth MBD, rendered ATP7B incapable of trafficking on exposure to cDDP. Truncation of MBD1-5 or MBD1-6 resulted in the loss of TGN localization. Addition of the first 63 amino acids of ATP7B to these variants restored TGN localization to a great extent and enabled the MBD1-5 variant to undergo cDDP-induced trafficking. A variant of ATP7B in which the aspartate 1027 residue in the phosphorylation domain was converted to glutamine localized to the TGN but was incapable of cDDP-induced trafficking. These results demonstrate that the CXXC motif in the sixth MBD and the catalytic activity of ATP7B are required for cDDP-induced trafficking as they are for Cu-induced redistribution of ATP7B; this provides further evidence that cDDP mimics Cu with respect to the molecular mechanisms by they control the subcellular distribution of ATP7B. PMID:23803742

  16. Apoprotein Structure and Metal Binding Characterization of a de Novo Designed Peptide, α3DIV, that Sequesters Toxic Heavy Metals.

    PubMed

    Plegaria, Jefferson S; Dzul, Stephen P; Zuiderweg, Erik R P; Stemmler, Timothy L; Pecoraro, Vincent L

    2015-05-12

    De novo protein design is a biologically relevant approach that provides a novel process in elucidating protein folding and modeling the metal centers of metalloproteins in a completely unrelated or simplified fold. An integral step in de novo protein design is the establishment of a well-folded scaffold with one conformation, which is a fundamental characteristic of many native proteins. Here, we report the NMR solution structure of apo α3DIV at pH 7.0, a de novo designed three-helix bundle peptide containing a triscysteine motif (Cys18, Cys28, and Cys67) that binds toxic heavy metals. The structure comprises 1067 NOE restraints derived from multinuclear multidimensional NOESY, as well as 138 dihedral angles (ψ, φ, and χ1). The backbone and heavy atoms of the 20 lowest energy structures have a root mean square deviation from the mean structure of 0.79 (0.16) Å and 1.31 (0.15) Å, respectively. When compared to the parent structure α3D, the substitution of Leu residues to Cys enhanced the α-helical content of α3DIV while maintaining the same overall topology and fold. In addition, solution studies on the metalated species illustrated metal-induced stability. An increase in the melting temperatures was observed for Hg(II), Pb(II), or Cd(II) bound α3DIV by 18-24 °C compared to its apo counterpart. Further, the extended X-ray absorption fine structure analysis on Hg(II)-α3DIV produced an average Hg(II)-S bond length at 2.36 Å, indicating a trigonal T-shaped coordination environment. Overall, the structure of apo α3DIV reveals an asymmetric distorted triscysteine metal binding site, which offers a model for native metalloregulatory proteins with thiol-rich ligands that function in regulating toxic heavy metals, such as ArsR, CadC, MerR, and PbrR.

  17. Method of solidifying waste materials, such as radioactive or toxic materials, contained in aqueous solutions

    SciTech Connect

    Knieper, J.; May, K.; Printz, H.

    1984-07-24

    A method is disclosed of solidifying waste materials, such as radioactive or toxic materials, which are contained in aqueous solutions. To accomplish this solidification, an inorganic, non-metallic binding agent such as gypsum is intermixed with the aqueous solution and a substance such as pumice or ceramic tile which promotes the intermixing of the binding agent and the aqueous solution.

  18. Silica, Silicosis, and Autoimmunity

    PubMed Central

    Pollard, Kenneth Michael

    2016-01-01

    Inhalation of dust containing crystalline silica is associated with a number of acute and chronic diseases including systemic autoimmune diseases. Evidence for the link with autoimmune disease comes from epidemiological studies linking occupational exposure to crystalline silica dust with the systemic autoimmune diseases systemic lupus erythematosus, systemic sclerosis, and rheumatoid arthritis. Although little is known regarding the mechanism by which silica exposure leads to systemic autoimmune disease, there is a voluminous literature on silica exposure and silicosis that may help identify immune processes that precede development of autoimmunity. The pathophysiology of silicosis consists of deposition of silica particles in the alveoli of the lung. Ingestion of these particles by macrophages initiates an inflammatory response, which stimulates fibroblasts to proliferate and produce collagen. Silica particles are encased by collagen leading to fibrosis and the nodular lesions characteristic of the disease. The steps in the development of silicosis, including acute and chronic inflammation and fibrosis, have different molecular and cellular requirements, suggesting that silica-induced inflammation and fibrosis may be mechanistically separate. Significantly, it is unclear whether silica-induced inflammation and fibrosis contribute similarly to the development of autoimmunity. Nonetheless, the findings from human and animal model studies are consistent with an autoimmune pathogenesis that begins with activation of the innate immune system leading to proinflammatory cytokine production, pulmonary inflammation leading to activation of adaptive immunity, breaking of tolerance, and autoantibodies and tissue damage. The variable frequency of these immunological features following silica exposure suggests substantial genetic involvement and gene/environment interaction in silica-induced autoimmunity. However, numerous questions remain unanswered. PMID:27014276

  19. Community Geothermal Technology Program: Silica bronze project. Final report

    SciTech Connect

    Bianchini, H.

    1989-10-01

    Objective was to incorporate waste silica from the HGP-A geothermal well in Pohoiki with other refractory materials for investment casting of bronze sculpture. The best composition for casting is about 50% silica, 25% red cinders, and 25% brick dust; remaining ingredient is a binder, such as plaster and water.

  20. Prevention of iron- and copper-mediated DNA damage by catecholamine and amino acid neurotransmitters, L-DOPA, and curcumin: metal binding as a general antioxidant mechanism.

    PubMed

    García, Carla R; Angelé-Martínez, Carlos; Wilkes, Jenna A; Wang, Hsiao C; Battin, Erin E; Brumaghim, Julia L

    2012-06-01

    Concentrations of labile iron and copper are elevated in patients with neurological disorders, causing interest in metal-neurotransmitter interactions. Catecholamine (dopamine, epinephrine, and norepinephrine) and amino acid (glycine, glutamate, and 4-aminobutyrate) neurotransmitters are antioxidants also known to bind metal ions. To investigate the role of metal binding as an antioxidant mechanism for these neurotransmitters, L-dihydroxyphenylalanine (L-DOPA), and curcumin, their abilities to prevent iron- and copper-mediated DNA damage were quantified, cyclic voltammetry was used to determine the relationship between their redox potentials and DNA damage prevention, and UV-vis studies were conducted to determine iron and copper binding as well as iron oxidation rates. In contrast to amino acid neurotransmitters, catecholamine neurotransmitters, L-DOPA, and curcumin prevent significant iron-mediated DNA damage (IC(50) values of 3.2 to 18 μM) and are electrochemically active. However, glycine and glutamate are more effective at preventing copper-mediated DNA damage (IC(50) values of 35 and 12.9 μM, respectively) than L-DOPA, the only catecholamine to prevent this damage (IC(50) = 73 μM). This metal-mediated DNA damage prevention is directly related to the metal-binding behaviour of these compounds. When bound to iron or copper, the catecholamines, amino acids, and curcumin significantly shift iron oxidation potentials and stabilize Fe(3+) over Fe(2+) and Cu(2+) over Cu(+), a factor that may prevent metal redox cycling in vivo. These results highlight the disparate antioxidant activities of neurotransmitters, drugs, and supplements and highlight the importance of considering metal binding when identifying antioxidants to treat and prevent neurodegenerative disorders. PMID:22450660

  1. The metal-binding properties of the blue crab copper specific CuMT-2: a crustacean metallothionein with two cysteine triplets.

    PubMed

    Serra-Batiste, Montserrat; Cols, Neus; Alcaraz, Luis A; Donaire, Antonio; González-Duarte, Pilar; Vasák, Milan

    2010-06-01

    Most crustacean metallothioneins (MTs) contain 18 Cys residues and bind six divalent metal ions. The copper-specific CuMT-2 (MTC) of the blue crab Callinectes sapidus with 21 Cys residues, of which six are organized in two uncommon Cys-Cys-Cys sequences, represents an exception. However, its metal-binding properties are unknown. By spectroscopic and spectrometric techniques we show that all 21 Cys residues of recombinant MTC participate in the binding of Cu(I), Zn(II), and Cd(II) ions, indicating that both Cys triplets act as ligands. The fully metallated M(8) (II)-MTC (M is Zn, Cd) form possesses high- and low-affinity metal binding sites, as evidenced by the formation of Zn(6)-MTC and Cd(7)-MTC species from M(8) (II)-MTC after treatment with Chelex 100. The NMR characterization of Cd(7)-MTC suggests the presence of a two-domain structure, each domain containing one Cys triplet and encompassing either the three-metal or the four-metal thiolate cluster. Whereas the metal-Cys connectivities in the three-metal cluster located in the N-terminal domain (residues 1-31) reveal a Cd(3)Cys(9) cyclohexane-like structure, the presence of dynamic processes in the C-terminal domain (residues 32-64) precluded the determination of the organization of the four-metal cluster. Absorption and circular dichroism features accompanying the stepwise binding of Cu(I) to MTC suggest that all 21 Cys are involved in the binding of eight to nine Cu(I) ions (Cu(8-9)-MTC). The subsequent generation of Cu(12)-MTC involves structural changes consistent with a decrease in the Cu(I) coordination number. Overall, the metal-binding properties of MTC reported here contribute to a better understanding of the role of Cys triplets in MTs.

  2. Consolidated silica glass from nanoparticles

    SciTech Connect

    Mayerhoefer, Thomas G. Shen Zhijian; Leonova, Ekaterina; Eden, Mattias; Kriltz, Antje; Popp, Juergen

    2008-09-15

    A dense silica glass was prepared by consolidating a highly dispersed silicic acid powder (particle size <10 nm) with the Spark Plasma Sintering (SPS) technique. The glass was characterized by ellipsometry, transmission electron microscopy (TEM), infrared reflectance and transmittance spectroscopy, as well as by Raman, UV-Vis-NIR and solid-state nuclear magnetic resonance (NMR) spectroscopy. The prototypic sample showed a transmittance of about 63% compared to silica glass in the UV-Vis spectral range. Based on the results of infrared transmittance spectroscopy this lower transparency is due to the comparably high water content, which is about 40 times higher than that in silica glass. {sup 1}H magic-angle spinning (MAS) NMR confirmed an increase in hydroxyl groups in the sample prepared by SPS relative to that of the conventional SiO{sub 2} reference glass. Aside from the comparably high water content, we conclude from the similarity of the IR-reflectance and the {sup 29}Si MAS NMR spectra of the SPS sample and the corresponding spectra of the conventionally prepared silica glass, that the short- and medium-range order is virtually the same in both materials. Raman spectroscopy, however, suggests that the number of three- and four-membered rings is significantly smaller in the SPS sample compared to the conventionally prepared sample. Based on these results we conclude that it is possible to prepare glasses by compacting amorphous powders by the SPS process. The SPS process may therefore enable the preparation of glasses with compositions inaccessible by conventional methods. - Graphical abstract: We report the preparation of SiO{sub 2} glass by consolidating a highly dispersed silicic acid powder with the Spark Plasma Sintering (SPS) technique. The glass was characterized by ellipsometry, transmission electron microscopy (TEM), infrared reflectance and transmittance spectroscopy, as well as by Raman-, UV-Vis-NIR- and solid-state nuclear magnetic resonance (NMR

  3. Silica Embedded Metal Hydrides

    SciTech Connect

    Heung, L.K.; Wicks, G.G.

    1998-08-01

    A method to produce silica embedded metal hydride was developed. The product is a composite in which metal hydride particles are embedded in a matrix of silica. The silica matrix is highly porous. Hydrogen gas can easily reach the embedded metal hydride particles. The pores are small so that the metal hydride particles cannot leave the matrix. The porous matrix also protects the metal hydride particles from larger and reactive molecules such as oxygen, since the larger gas molecules cannot pass through the small pores easily. Tests show that granules of this composite can absorb hydrogen readily and withstand many cycles without making fines.

  4. Interactive effects of waterborne metals in binary mixtures on short-term gill-metal binding and ion uptake in rainbow trout (Oncorhynchus mykiss).

    PubMed

    Niyogi, Som; Nadella, Sunita R; Wood, Chris M

    2015-08-01

    Metal binding to fish gills forms the basis of the biotic ligand model (BLM) approach, which has emerged as a useful tool for conducting site-specific water quality assessments for metals. The current BLMs are designed to assess the toxicity of individual metals, and cannot account for the interactive effects of metal mixtures to aquatic organisms including fish. The present study was designed mainly to examine the interactive effects of waterborne metals (Cd, Zn, Cu, Ag, and Ni) in specific binary combinations on short-term (3h) gill-metal binding and essential ion (Ca(2+) and Na(+)) uptake (a physiological index of toxicity) in fish, using juvenile freshwater rainbow trout (Oncorhynchus mykiss) as the model species. We hypothesized that binary mixtures of metals that share a common mode of uptake and toxicity (e.g., Cd and Zn - Ca(2+) antagonists, Cu and Ag - Na(+) antagonists) would reduce the gill binding of each other via competitive interactions and induce less than additive effects on ion transport. In addition, the mixture of metals that have different modes of uptake and toxicity (e.g., Cd and Cu, or Cd and Ni) would not exhibit any interactive effects either on gill-metal binding or ion transport. We found that both Zn and Cu reduced gill-Cd binding and vice versa, however, Ni did not influence gill-Cd binding in fish. Surprisingly, Ag was found to stimulate gill-Cu binding especially at high exposure concentrations, whereas, Cu had no effect on gill-Ag binding. The inhibitory effect of Cd and Zn in mixture on branchial Ca(2+) uptake was significantly greater than that of Cd or Zn alone. Similarly, the inhibitory effect of Cu and Ag in mixture on branchial Na(+) uptake was significantly greater than that of Cu or Ag alone. The inhibitory effects of Cd and Zn mixture on Ca(2+) uptake as well as Cu and Ag mixture on Na(+) uptake were found to follow the principles of simple additivity. In contrast, no significant additive effect on either Ca(2+) or Na

  5. Interactive effects of waterborne metals in binary mixtures on short-term gill-metal binding and ion uptake in rainbow trout (Oncorhynchus mykiss).

    PubMed

    Niyogi, Som; Nadella, Sunita R; Wood, Chris M

    2015-08-01

    Metal binding to fish gills forms the basis of the biotic ligand model (BLM) approach, which has emerged as a useful tool for conducting site-specific water quality assessments for metals. The current BLMs are designed to assess the toxicity of individual metals, and cannot account for the interactive effects of metal mixtures to aquatic organisms including fish. The present study was designed mainly to examine the interactive effects of waterborne metals (Cd, Zn, Cu, Ag, and Ni) in specific binary combinations on short-term (3h) gill-metal binding and essential ion (Ca(2+) and Na(+)) uptake (a physiological index of toxicity) in fish, using juvenile freshwater rainbow trout (Oncorhynchus mykiss) as the model species. We hypothesized that binary mixtures of metals that share a common mode of uptake and toxicity (e.g., Cd and Zn - Ca(2+) antagonists, Cu and Ag - Na(+) antagonists) would reduce the gill binding of each other via competitive interactions and induce less than additive effects on ion transport. In addition, the mixture of metals that have different modes of uptake and toxicity (e.g., Cd and Cu, or Cd and Ni) would not exhibit any interactive effects either on gill-metal binding or ion transport. We found that both Zn and Cu reduced gill-Cd binding and vice versa, however, Ni did not influence gill-Cd binding in fish. Surprisingly, Ag was found to stimulate gill-Cu binding especially at high exposure concentrations, whereas, Cu had no effect on gill-Ag binding. The inhibitory effect of Cd and Zn in mixture on branchial Ca(2+) uptake was significantly greater than that of Cd or Zn alone. Similarly, the inhibitory effect of Cu and Ag in mixture on branchial Na(+) uptake was significantly greater than that of Cu or Ag alone. The inhibitory effects of Cd and Zn mixture on Ca(2+) uptake as well as Cu and Ag mixture on Na(+) uptake were found to follow the principles of simple additivity. In contrast, no significant additive effect on either Ca(2+) or Na

  6. Chitosan modified ordered mesoporous silica as micro-column packing materials for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples.

    PubMed

    Chen, Dahui; Hu, Bin; Huang, Chaozhang

    2009-04-30

    A novel adsorbent of chitosan chemically modified ordered mesoporous silica was synthesized and employed as a solid phase extraction (SPE) material for flow injection (FI) micro-column preconcentration on-line coupled with inductively coupled plasma optical emission spectrometry (ICP-OES) determination of trace heavy metals V, Cu, Pb, Cd and Hg in environmental water samples. The factors affecting separation and preconcentration of target heavy metals such as pH, sample flow rate and volume, eluent concentration and volume, interfering ions were investigated. Under the optimized experimental conditions, an enrichment factor of 20 and sampling frequency of 10h(-1) were obtained. The detection limits of the method for V, Cu, Pb, Cd and Hg were 0.33, 0.30, 0.96, 0.05 and 0.93 ng mL(-1), and the relative standard deviations (RSDs) were 2.8%, 6.7%, 1.8%, 4.0% and 5.3% (n=7, C=10 ng mL(-1)), respectively. The adsorption capacities of chitosan modified ordered mesoporous silica for V, Cu, Pb, Cd, and Hg were found to be 16.3, 21.7, 22.9, 12.2 and 13.5 mg g(-1), respectively. In order to validate the developed method, a certified reference material of GSBZ50009-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values. The proposed method has also been applied to the determination of trace heavy metals in natural water samples with satisfactory results.

  7. Silica nanoporous membranes and their applications

    NASA Astrophysics Data System (ADS)

    Khabibullin, Amir

    This thesis describes the development of novel silica and hybrid nanoporous membranes. Nanoporous membranes are widely used in various applications. This thesis focuses on their potential applications in the energy area, such as fuel cells and lithium batteries, and in separations and ultrafiltration. We use silica colloidal spheres and polymer-modified silica spheres to prepare the membranes in a time-, cost- and material-efficient manner. First, we prepared novel silica nanoporous membranes by pressing silica colloidal spheres followed by sintering. The pore size, the thickness, and the area of the membrane are precisely controlled by experiment parameters. The resulting membranes are mechanically and thermally durable, crack-free, and capable of size-selective transport. Next, to demonstrate the utility of the pressed membranes, described above, the proton-conductive pore-filled silica colloidal membranes were prepared and the fuel cells were constructed using these membranes. We modified these membranes by filling the membrane pores with surface-attached proton-conductive polymer brushes and prepared membrane-electrode assemblies to test fuel cell performance. We studied the proton conductivity and fuel cell performance as a function of the amount of sulfonic groups in the membrane. We also prepared and characterized reversible hybrid nanoporous membranes, self-assembled from solution containing polymer-modified silica colloidal spheres. Here we applied the new concept of noncovalent membranes, where the material is held together via noncovalent interactions of polymer brushes. This enables so-called reversible assembly of the membranes, in which membrane can be assembled in one solvent and dissolved in other. This approach provides advantages in recycling and reusing of the material. This work is one of the first of its kind and it opens a whole new area of research on reversible membranes made of polymer-modified nanoparticles. Finally, we applied our

  8. Fluoride Release from Hollow Silica Microsphere-Containing Dental Restorative Acrylate Resin.

    PubMed

    Ji, Yuqin; Gao, Jun; Yin, Hengbo; Wang, Aili; Jiang, Tingshun; Wu, Gang; Wu, Zhanao

    2015-05-01

    Hollow silica microspheres with mesoporous shells were prepared by the sacrificial template method. Hollow silica microsphere-containing acrylate resin-based dental restoration materials were prepared by using hollow silica microspheres as NaF reservoirs. Fluoride release performances from naked hollow silica microspheres, acrylate resin, and hollow silica microsphere-containing acrylate resin-based dental restorative materials in an artificial saliva were investigated. The results showed that hollow silica microsphere-containing acrylate resin-based dental restorative materials had higher cumulative fluoride release quantities and sustained fluoride release rates than traditional acrylate resin-based dental restorative materials. Fluoride release could be tuned by changing the mesoporous shell thickness of hollow silica microsphere.

  9. Crystalline Silica Primer

    USGS Publications Warehouse

    ,

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  10. In silico design and construction of metal-binding hybrid proteins for specific removal of cadmium based on CS3 pili display on the surface of Escherichia coli.

    PubMed

    Eskandari, Vajiheh; Yakhchali, Bagher; Sadeghi, Mehdi; Karkhane, Ali Asghar

    2013-01-01

    In this study, through a combination of bioinformatics and genetic engineering procedures, high-affinity metal-binding peptides were designed and expressed on the surface of Escherichia coli for selective Cd(2+) adsorption. Putative cadmium-binding motifs were identified by searches against the Prosite database and permissive sites in the major subunit (CstH) of the enterotoxigenic E. coli pili were predicted based on the data derived from modeling of 3D structures, secondary structure prediction and assignment, inspection of protein hydropathy and exposed regions, and also protein interaction sites. The metal-binding motifs were inserted into one permissive site of the CstH (amino acid 38) with the aid of the SOEing PCR technique. The capacity and selectivity of the recombinant bacteria displaying hybrid pili to adsorb cadmium were evaluated with the atomic absorption procedure. The levels of Cd(2+) accumulation in the recombinant E. coli strains were 13.9- and 11.33-fold higher than those in the control strain. Cd(2+) was selectively absorbed from a solution containing equal concentrations of four metals, resulting in more than 90% of the total adsorbed metals being Cd(2+) , showing a relatively high affinity for Cd(2+) over other coexisting metal ions.

  11. In silico design and construction of metal-binding hybrid proteins for specific removal of cadmium based on CS3 pili display on the surface of Escherichia coli.

    PubMed

    Eskandari, Vajiheh; Yakhchali, Bagher; Sadeghi, Mehdi; Karkhane, Ali Asghar

    2013-01-01

    In this study, through a combination of bioinformatics and genetic engineering procedures, high-affinity metal-binding peptides were designed and expressed on the surface of Escherichia coli for selective Cd(2+) adsorption. Putative cadmium-binding motifs were identified by searches against the Prosite database and permissive sites in the major subunit (CstH) of the enterotoxigenic E. coli pili were predicted based on the data derived from modeling of 3D structures, secondary structure prediction and assignment, inspection of protein hydropathy and exposed regions, and also protein interaction sites. The metal-binding motifs were inserted into one permissive site of the CstH (amino acid 38) with the aid of the SOEing PCR technique. The capacity and selectivity of the recombinant bacteria displaying hybrid pili to adsorb cadmium were evaluated with the atomic absorption procedure. The levels of Cd(2+) accumulation in the recombinant E. coli strains were 13.9- and 11.33-fold higher than those in the control strain. Cd(2+) was selectively absorbed from a solution containing equal concentrations of four metals, resulting in more than 90% of the total adsorbed metals being Cd(2+) , showing a relatively high affinity for Cd(2+) over other coexisting metal ions. PMID:23745737

  12. Structure of Human J-type Co-chaperone HscB Reveals a Tetracysteine Metal-binding Domain*S⃞

    PubMed Central

    Bitto, Eduard; Bingman, Craig A.; Bittova, Lenka; Kondrashov, Dmitry A.; Bannen, Ryan M.; Fox, Brian G.; Markley, John L.; Phillips, George N.

    2008-01-01

    Iron-sulfur proteins play indispensable roles in a broad range of biochemical processes. The biogenesis of iron-sulfur proteins is a complex process that has become a subject of extensive research. The final step of iron-sulfur protein assembly involves transfer of an iron-sulfur cluster from a cluster-donor to a cluster-acceptor protein. This process is facilitated by a specialized chaperone system, which consists of a molecular chaperone from the Hsc70 family and a co-chaperone of the J-domain family. The 3.0Å crystal structure of a human mitochondrial J-type co-chaperone HscB revealed an L-shaped protein that resembles Escherichia coli HscB. The important difference between the two homologs is the presence of an auxiliary metal-binding domain at the N terminus of human HscB that coordinates a metal via the tetracysteine consensus motif CWXCX9–13FCXXCXXXQ. The domain is found in HscB homologs from animals and plants as well as in magnetotactic bacteria. The metal-binding site of the domain is structurally similar to that of rubredoxin and several zinc finger proteins containing rubredoxin-like knuckles. The normal mode analysis of HscB revealed that this L-shaped protein preferentially undergoes a scissors-like motion that correlates well with the conformational changes of human HscB observed in the crystals. PMID:18713742

  13. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, N.K.; Brinker, C.J.

    1999-08-10

    A process is described for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film. 11 figs.

  14. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, Narayan K.; Brinker, Charles Jeffrey

    1999-01-01

    A process for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film.

  15. Molecular sieving silica membrane fabrication process

    DOEpatents

    Raman, Narayan K.; Brinker, Charles Jeffrey

    1998-01-01

    A process for producing a molecular sieve silica membrane comprising depositing a hybrid organic-inorganic polymer comprising at least one organic constituent and at least one inorganic constituent on a porous substrate material and removing at least a portion of the at least one organic constituent of the hybrid organic-inorganic polymer, forming a porous film.

  16. Silica-metal core-shell nanostructures.

    PubMed

    Jankiewicz, B J; Jamiola, D; Choma, J; Jaroniec, M

    2012-01-15

    Silica-metal nanostructures consisting of silica cores and metal nanoshells attract a lot of attention because of their unique properties and potential applications ranging from catalysis and biosensing to optical devices and medicine. The important feature of these nanostructures is the possibility of controlling their properties by the variation of their geometry, shell morphology and shell material. This review is devoted to silica-noble metal core-shell nanostructures; specifically, it outlines the main methods used for the preparation and surface modification of silica particles and presents the major strategies for the formation of metal nanoshells on the modified silica particles. A special emphasis is given to the Stöber method, which is relatively simple, effective and well verified for the synthesis of large and highly uniform silica particles (with diameters from 100 nm to a few microns). Next, the surface chemistry of these particles is discussed with a special focus on the attachment of specific organic groups such as aminopropyl or mercaptopropyl groups, which interact strongly with metal species. Finally, the synthesis, characterization and application of various silica-metal core-shell nanostructures are reviewed, especially in relation to the siliceous cores with gold or silver nanoshells. Nowadays, gold is most often used metal for the formation of nanoshells due to its beneficial properties for many applications. However, other metals such as silver, platinum, palladium, nickel and copper were also used for fabrication of core-shell nanostructures. Silica-metal nanostructures can be prepared using various methods, for instance, (i) growth of metal nanoshells on the siliceous cores with deposited metal nanoparticles, (ii) reduction of metal species accompanied by precipitation of metal nanoparticles on the modified silica cores, and (iii) formation of metal nanoshells under ultrasonic conditions. A special emphasis is given to the seed

  17. Silica, silicosis and cancer in Finland.

    PubMed

    Partanen, T; Jaakkola, J; Tossavainen, A

    1995-01-01

    Approximately 100 000 Finnish workers are currently employed in jobs and tasks that may involve exposure to airborne silica dust. The major industries involved are mining and quarrying; production of glass, ceramics, bricks and other building materials; metal industry, particularly iron and steel founding; and construction. Over 1500 cases of silicosis have occurred in Finland since 1935. Tuberculosis has been a frequent complication of silicosis. Results of studies from several countries strongly suggest that silica dust also causes lung cancer. The results of the relevant Finnish epidemiologic and industrial hygiene studies addressing cancer risk and exposure to quartz dust are summarized. PMID:8929699

  18. Silica, silicosis and cancer in Finland.

    PubMed

    Partanen, T; Jaakkola, J; Tossavainen, A

    1995-01-01

    Approximately 100 000 Finnish workers are currently employed in jobs and tasks that may involve exposure to airborne silica dust. The major industries involved are mining and quarrying; production of glass, ceramics, bricks and other building materials; metal industry, particularly iron and steel founding; and construction. Over 1500 cases of silicosis have occurred in Finland since 1935. Tuberculosis has been a frequent complication of silicosis. Results of studies from several countries strongly suggest that silica dust also causes lung cancer. The results of the relevant Finnish epidemiologic and industrial hygiene studies addressing cancer risk and exposure to quartz dust are summarized.

  19. Carbon nanomaterials in silica aerogel matrices

    SciTech Connect

    Hamilton, Christopher E; Chavez, Manuel E; Duque, Juan G; Gupta, Gautam; Doorn, Stephen K; Dattelbaum, Andrew M; Obrey, Kimberly A D

    2010-01-01

    Silica aerogels are ultra low-density, high surface area materials that are extremely good thermal insulators and have numerous technical applications. However, their mechanical properties are not ideal, as they are brittle and prone to shattering. Conversely, single-walled carbon nanotubes (SWCNTs) and graphene-based materials, such as graphene oxide, have extremely high tensile strength and possess novel electronic properties. By introducing SWCNTs or graphene-based materials into aerogel matrices, it is possible to produce composites with the desirable properties of both constituents. We have successfully dispersed SWCNTs and graphene-based materials into silica gels. Subsequent supercritical drying results in monolithic low-density composites having improved mechanical properties. These nanocomposite aerogels have great potential for use in a wide range of applications.

  20. Developing a Process for Commercial Silica Production from Geothermal Brines

    SciTech Connect

    Bourcier, W; Martin, S; Viani, B; Bruton, C

    2001-04-11

    Useful mineral by-products can be produced from geothermal brines. Although silica has many commercial uses, problems remain in producing a marketable product. We are conducting laboratory and modeling studies aimed at optimizing for rubber additive use, the properties of silica precipitates from Salton Sea and Coso-like geothermal fluids, Our goal is to develop a robust technique for producing silicas that have desirable physical and chemical properties for commercial use, while developing a generic understanding of silica precipitation that will allow extraction to be extended to additional fluid types, and to be easily modified to produce new types of marketable silica. Our experiments start with an acidified geothermal fluid similar to those treated by pH modification technology. Silica precipitation is induced by adding base and/or adding Mg or Ca salts to affect the nature of the precipitate. For the analog Salton Sea fluids, adding base alone caused silica to precipitate fairly rapidly. To date, we have characterized precipitates from experiments in which the final pH varied from 4 to 8, where NaOH and Na{sub 2}C0{sub 3} were added as bases, and CaCl{sub 2} and MgCl{sub 2} were added as salts. SEM photos of the silica precipitates from the Salton Sea and Cos0 fluids show that the silica particles are clusters of smaller silica particles down to the resolution of the SEM (about 80-100 nm in diameter). The particle sizes and surface areas of silicas from the Salton Sea and Coso analog brines are similar to the properties of the Degussa silica commonly used as a rubber additive. An evaluation of the strength of the silica-organic bond as tested by dispersion in oil (polybutadiene) was inconclusive. Neither the Degussa materials nor our laboratory precipitates dispersed readily in nor dispersed down to the fundamental particle size. Preliminary NMR data indicates that the Degussa silica has a smaller degree of silica polymerization (a slightly smaller average

  1. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  2. Composite Silica Aerogels Opacified with Titania

    NASA Technical Reports Server (NTRS)

    Paik, Jon-Ah; Sakamoto, Jeffrey; Jones, Steven; Fleurial, Jean-Pierre; DiStefano, Salvador; Nesmith, Bill

    2009-01-01

    A further improvement has been made to reduce the high-temperature thermal conductivities of the aerogel-matrix composite materials described in Improved Silica Aerogel Composite Materials (NPO-44287), NASA Tech Briefs, Vol. 32, No. 9 (September 2008), page 50. Because the contribution of infrared radiation to heat transfer increases sharply with temperature, the effective high-temperature thermal conductivity of a thermal-insulation material can be reduced by opacifying the material to reduce the radiative contribution. Therefore, the essence of the present improvement is to add an opacifying constituent material (specifically, TiO2 powder) to the aerogel-matrix composites.

  3. Silica in alkaline brines

    USGS Publications Warehouse

    Jones, B.F.; Rettig, S.L.; Eugster, H.P.

    1967-01-01

    Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

  4. Silica Synthesis by Sponges: Unanticipated Molecular Mechanism

    NASA Astrophysics Data System (ADS)

    Morse, D. E.; Weaver, J. C.

    2001-12-01

    Oceanic diatoms, sponges and other organisms synthesize gigatons per year of silica from silicic acid, ultimately obtained from the weathering of rock. This biogenic silica exhibits a remarkable diversity of structures, many of which reveal a precision of nanoarchitectural control that exceeds the capabilities of human engineering. In contrast to the conditions of anthropogenic and industrial manufacture, the biological synthesis of silica occurs under mild physiological conditions of low temperatures and pressures and near-neutral pH. In addition to the differentiation between biological and abiotic processes governing silica formation, the biomolecular mechanisms controlling synthesis of these materials may offer insights for the development of new, environmentally benign routes for synthesis of nanostructurally controlled silicas and high-performance polysiloxane composites. We found that the needle-like silica spicules made by the marine sponge, Tethya aurantia, each contain an occluded axial filament of protein composed predominantly of repeating assemblies of three similar subunits we named "silicateins." To our surprise, analysis of the purified protein subunits and the cloned silicatein DNAs revealed that the silicateins are highly homologous to a family of hydrolytic enzymes. As predicted from this finding, we discovered that the silicatein filaments are more than simple, passive templates; they actively catalyze and spatially direct polycondensation to form silica, (as well as the phenyl- and methyl-silsesquioxane) from the corresponding silicon alkoxides at neutral pH and low temperature. Catalytic activity also is exhibited by the silicatein subunits obtained by disaggregation of the protein filaments and those produced from recombinant DNA templates cloned in bacteria. This catalytic activity accelerates the rate-limiting hydrolysis of the silicon alkoxide precursors. Genetic engineering, used to produce variants of the silicatein molecule with

  5. Silica Precipitation and Lithium Sorption

    SciTech Connect

    Jay Renew

    2015-09-20

    This file contains silica precipitation and lithium sorption data from the project. The silica removal data is corrected from the previous submission. The previous submission did not take into account the limit of detection of the ICP-MS procedure.

  6. Laser ablation inductively coupled plasma-mass spectrometry in combination with gel electrophoresis: a new strategy for speciation of metal binding serum proteins

    NASA Astrophysics Data System (ADS)

    Neilsen, J. L.; Abildtrup, A.; Christensen, J.; Watson, P.; Cox, A.; McLeod, C. W.

    1998-02-01

    A new hyphenated technique-crossed immunoelectrophoresis in combination with laser ablation inductively coupled plasma (ICP)-mass spectrometry—for the identification and quantitation of metal binding proteins in blood serum is described. Human serum enriched with Co was subjected to electrophoresis and the agarose gels corresponding to the first and second dimensions were interrogated and analysed using a Nd Yag laser (1064 nm) interfaced to ICP-mass spectrometry. Comparison of the distribution map for Co with the protein distribution map obtained via Coommassie Brilliant Blue staining allowed identification of main Co binding serum proteins. Signals for Co (single ion monitoring, mle 59) were transient in nature and for gels enriched with increasing concentrations of Co, peak area response was linear with concentration. Precision for replicate analyses was 6% R.S.D. and the limit of detection was - 0.29 ng.

  7. Effect of amino acid substitutions in a potential metal-binding site of AnfA on expression from the anfH promoter in Azotobacter vinelandii.

    PubMed

    Premakumar, R; Loveless, T M; Bishop, P E

    1994-10-01

    AnfA, an activator required for transcription of the structural genes encoding nitrogenase 3 (anfHDGK) in Azotobacter vinelandii, has a potential metal-binding site [(S19)H(C21)FTGE(C26)R] in its N terminus. Growth studies and expression of an anfH-lacZ fusion in mutants containing amino acid substitutions in this site indicate that Ser-19 is not required for AnfA activity whereas Cys-21 and Cys-26 are required. Residual expression of the anfH-lacZ fusion in AnfA- mutants was found to be due to activation by VnfA, the activator required for expression of genes encoding nitrogenase 2.

  8. Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

    SciTech Connect

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1997-12-31

    The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented.

  9. Epoxy Grout With Silica Thickener

    NASA Technical Reports Server (NTRS)

    Mcclung, C. E.

    1984-01-01

    Grout cures quickly, even in presence of hydraulic oil. Grout is mixture of aggregate particles, finely-divided silica, epoxy resin, and triethylenetetramine curing agent, with mixture containing about 85 percent silica and aggregate particle sand 15 percent resin and curing agent. Silica is thickening agent and keeps grout from sagging.

  10. [Effect of mutations and modifications of amino acid residues on zinc-induced interaction of the metal-binding domain of β-amyloid with DNA].

    PubMed

    Khmeleva, S A; Mezentsev, Y V; Kozin, S A; Mitkevich, V A; Medvedev, A E; Ivanov, A S; Bodoev, N V; Makarov, A A; Radko, S P

    2015-01-01

    Interaction of intranuclear β-amyloid with DNA is considered to be a plausible mechanism of Alzheimer's disease pathogenesis. The interaction of single- and double-stranded DNA with synthetic peptides was analyzed using surface plasmon resonance. The peptides represent the metal-binding domain of β-amyloid (amino acids 1-16) and its variants with chemical modifications and point substitutions of amino acid residues which are associated with enhanced neurotoxicity of β-amyloid in cell tests. It has been shown that the presence of zinc ions is necessary for the interaction of the peptides with DNA in solution. H6R substitution has remarkably reduced the ability of domain 1-16 to bind DNA. This is in accordance with the supposition that the coordination of a zinc ion by amino acid residues His6, Glu11, His13, and His14 of the β-amyloid metal-binding domain results in the occurrence of an anion-binding site responsible for the interaction of the domain with DNA. Zinc-induced dimerization and oligomerization of domain 1-16 associated with phosphorylation of Ser8 and the presence of unblocked amino- and carboxy-terminal groups have resulted in a decrease of peptide concentrations required for detection of the peptide-DNA interaction. The presence of multiple anion-binding sites on the dimers and oligomers is responsible for the enhancement of the peptide-DNA interaction. A substitution of the negatively charged residue Asp7 for the neutral residue Asn in close proximity to the anion-binding site of the domain 1-16 of Aβ facilitates the electrostatic interaction between this site and phosphates of a polynucleotide chain, which enhances zinc-induced binding to DNA.

  11. Local destabilization of the metal-binding region in human copper-zinc superoxide dismutase by remote mutations is a possible determinant for progression of ALS.

    PubMed

    Hennig, Janosch; Andrésen, Cecilia; Museth, A Katrine; Lundström, Patrik; Tibell, Lena A E; Jonsson, Bengt-Harald

    2015-01-20

    More than 100 distinct mutations in the gene CuZnSOD encoding human copper-zinc superoxide dismutase (CuZnSOD) have been associated with familial amyotrophic lateral sclerosis (fALS), a fatal neuronal disease. Many studies of different mutant proteins have found effects on protein stability, catalytic activity, and metal binding, but without a common pattern. Notably, these studies were often performed under conditions far from physiological. Here, we have used experimental conditions of pH 7 and 37 °C and at an ionic strength of 0.2 M to mimic physiological conditions as close as possible in a sample of pure protein. Thus, by using NMR spectroscopy, we have analyzed amide hydrogen exchange of the fALS-associated I113T CuZnSOD variant in its fully metalated state, both at 25 and 37 °C, where (15)N relaxation data, as expected, reveals that CuZnSOD I113T exists as a dimer under these conditions. The local dynamics at 82% of all residues have been analyzed in detail. When compared to the wild-type protein, it was found that I113T CuZnSOD is particularly destabilized locally at the ion binding sites of loop 4, the zinc binding loop, which results in frequent exposure of the aggregation prone outer β-strands I and VI of the β-barrel, possibly enabling fibril or aggregate formation. A similar study (Museth, A. K., et al. (2009) Biochemistry, 48, 8817-8829) of amide hydrogen exchange at pH 7 and 25 °C on the G93A variant also revealed a selective destabilization of the zinc binding loop. Thus, a possible scenario in ALS is that elevated local dynamics at the metal binding region can result in toxic species from formation of new interactions at local β-strands.

  12. The metallomics approach: use of Fe(II) and Cu(II) footprinting to examine metal binding sites on serum albumins.

    PubMed

    Duff, Michael R; Kumar, Challa V

    2009-11-01

    Metal binding to serum albumins is examined by oxidative protein-cleavage chemistry, and relative affinities of multiple metal ions to particular sites on these proteins were identified using a fast and reliable chemical footprinting approach. Fe(ii) and Cu(ii), for example, mediate protein cleavage at their respective binding sites on serum albumins, in the presence of hydrogen peroxide and ascorbate. This metal-mediated protein-cleavge reaction is used to evaluate the binding of metal ions, Na(+), Mg(2+), Ca(2+), Al(3+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ce(3+) to albumins, and the relative affinities (selectivities) of the metal ions are rapidly evaluated by examining the extent of inhibition of protein cleavage. Four distinct systems Fe(II)/BSA, Cu(II)/BSA, Fe(II)/HSA and Cu(II)/HSA are examined using the above strategy. This metallomics approach is novel, even though the cleavage of serum albumins by Fe(II)/Cu(II) has been reported previously by this laboratory and many others. The protein cleavage products were analyzed by SDS PAGE, and the intensities of the product bands quantified to evaluate the extent of inhibition of the cleavage and thereby evaluate the relative binding affinities of specific metal ions to particular sites on albumins. The data show that Co(II) and Cr(III) showed the highest degree of inhibition, across the table, followed by Mn(II) and Ce(III). Alakali metal ions and alkaline earth metal ions showed very poor affinity for these metal sites on albumins. Thus, metal binding profiles for particular sites on proteins can be obtained quickly and accurately, using the metallomics approach.

  13. A solubility model for amorphous silica in concentrated electrolytes

    SciTech Connect

    Felmy, A.R.; Schroeder, C.C.; Mason, M.J.

    1994-08-01

    Silica is one of the major constituents of the earth`s crust and is ubiquitously present in most natural materials. The solubility of silica and other silica-containing compounds is, therefore, of primary concern in geochemistry and in chemical processing applications where silica scale formation, resulting from changes in temperature and electrolyte composition, can cause problems in process design and operation. This paper describes the development of an aqueous thermodynamic model for accurately predicting the solubility of amorphous silica and other silica-containing compounds in the system Na{sup +}-H{sup +}-Mg{sup 2+}-NO{sub 3}{sup {minus}}-SO{sub 4}{sup 2{minus}}-Cl{sup {minus}}-H{sub 2}O to high concentration and across the temperature range 25--100 C. This model, which utilizes the aqueous thermodynamic model of Pitzer, includes only one dissolved silica species, H{sub 4}SiO{sub 4}(aq), and is valid in neutral to very acidic solutions. The model is parameterized from the extensive set of solubility data in the literature as well as from new experimental data on amorphous silica solubility in HNO{sub 3} and HCl developed as part of this study. The accuracy of the model is tested on solutions more complex than those used in model parameterization.

  14. Abnormal behavior of silica doped with small amounts of aluminum

    PubMed Central

    Liu, Jinling; Wang, Yiguang; An, Linan

    2016-01-01

    Silica is the most abundant mineral in the crust of the Earth. It has been demonstrated that the aluminum concentration in silica plays a key role in determining many properties of silica-based components. Although the alumina-silica system has been intensely studied, the effect of very small amounts of aluminum on the structure and properties of silica remains unclear. We report results of first principles calculations showing that small amounts of aluminum could be metastable when located in the center of Si-O rings without breaking the silica network. In contrast, higher aluminum contents will result in the destruction of the Si-O bonds, leading to the formation of triclusters and a 4-, 5-, and 6-fold Al-O coordination, as observed in previous studies. Based on the silica structure obtained through geometric optimization, the properties of silica doped with small amounts of aluminum were calculated. The results can account for many ‘abnormal’ phenomena experimentally observed. The results benefit most areas such as geosciences, microelectronics, glass industry, and ceramic materials. PMID:27752133

  15. Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

    NASA Astrophysics Data System (ADS)

    Abellán, G.; Carrillo, A. I.; Linares, N.; Serrano, E.; García-Martínez, J.

    2009-08-01

    Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m 2 g -1) and total pore volumes ≥2 cm 3 g -1.

  16. Mesostructured Silica for Optical Functionality, Nanomachines, and Drug Delivery

    PubMed Central

    Klichko, Yaroslav; Liong, Monty; Choi, Eunshil; Angelos, Sarah; Nel, Andre E.; Stoddart, J. Fraser; Tamanoi, Fuyuhiko; Zink, Jeffrey I.

    2009-01-01

    Silica thin films and nanoparticles prepared using sol–gel chemistry are derivatized with active molecules to generate new functional materials. The mild conditions associated with sol–gel processing allow for the incorporation of a range of dopants including organic or inorganic dyes, biomolecules, surfactants, and molecular machines. Silica nanoparticles embedded with inorganic nanocrystals, and films containing living cells have also been synthesized. Silica templated with surfactants to create mesostructure contains physically and chemically different regions that can be selectively derivatized using defined techniques to create dynamic materials. Using two different techniques, donor–acceptor pairs can be doped into separated regions simultaneously and photo-induced electron transfer between the molecules can be measured. Mesoporous silica materials are also useful supports for molecular machines. Machines including snap-tops and nanoimpellers that are designed to control the release of guest molecules trapped within the pores are described. Mesoporous silica nanoparticles are promising materials for drug delivery and other biomedical applications because they are nontoxic and can be taken up by living cells. Through appropriate design and synthesis, multifunctional mesoporous silica nanoparticles for sophisticated bio-applications are created. PMID:19834571

  17. Mesostructured Silica for Optical Functionality, Nanomachines, and Drug Delivery.

    PubMed

    Klichko, Yaroslav; Liong, Monty; Choi, Eunshil; Angelos, Sarah; Nel, Andre E; Stoddart, J Fraser; Tamanoi, Fuyuhiko; Zink, Jeffrey I

    2009-01-01

    Silica thin films and nanoparticles prepared using sol-gel chemistry are derivatized with active molecules to generate new functional materials. The mild conditions associated with sol-gel processing allow for the incorporation of a range of dopants including organic or inorganic dyes, biomolecules, surfactants, and molecular machines. Silica nanoparticles embedded with inorganic nanocrystals, and films containing living cells have also been synthesized. Silica templated with surfactants to create mesostructure contains physically and chemically different regions that can be selectively derivatized using defined techniques to create dynamic materials. Using two different techniques, donor-acceptor pairs can be doped into separated regions simultaneously and photo-induced electron transfer between the molecules can be measured. Mesoporous silica materials are also useful supports for molecular machines. Machines including snap-tops and nanoimpellers that are designed to control the release of guest molecules trapped within the pores are described. Mesoporous silica nanoparticles are promising materials for drug delivery and other biomedical applications because they are nontoxic and can be taken up by living cells. Through appropriate design and synthesis, multifunctional mesoporous silica nanoparticles for sophisticated bio-applications are created.

  18. Nanoindentation studies of nickel zinc ferrite embedded mesoporous silica template

    NASA Astrophysics Data System (ADS)

    Banerjee, S.; Hajra, P.; Mada, M. R.; Bandopadhyay, S.; Chakravorty, D.

    2013-02-01

    Nickel zinc ferrite (NZF) embedded mesoporous silica KIT-6 nanocomposite (NZFMS) was synthesized via impregnation method. The microstructure of the samples was characterized by transmission electron microscopy (TEM). Nanoindentation (NI) studies were carried out on both mesoporous silica (MS) and the nanocomposite NZFMS. It was found that the young's modulus (E) and hardness (H) of the NZFMS were higher than that of the MS. From creep measurement it was observed that the creep-strain rate was greater for NZFMS compared to MS. This arose due to diffusion of Fe3+ ions from nickel zinc ferrite to the silica glass. The results indicate that the NZFMS material shows superplastic behaviour at room temperature.

  19. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development. PMID:26861688

  20. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development.

  1. Polishing-paste-induced silica granuloma of the gingiva.

    PubMed

    Lombardi, T; Kuffer, R; Dubrez, B

    2001-01-01

    Polishing-paste-induced silica granuloma of the gingiva, an uncommon condition, may mimic various local or systemic pathological entities. A 33-year-old woman and a 42-year-old man were referred for a localised refractory gingival inflammation. Clinical diagnoses included allergy, lichen planus and herpes. Biopsy showed well-demarcated non-caseating granulomas, associating epithelioid and Langhans giant cells. Special bacterial and mycological stains were negative. Systemic examination and laboratory tests ruled out sarcoidosis and Crohn's disease. Polarised light revealed birefringent crystalline foreign material. A diagnosis of silica granuloma was made. Both patients had frequent dental hygiene treatment including polishing with abrasive paste, suggesting an iatrogenic implantation of the foreign bodies. Gingival damage can result from the use of some dental materials containing silica. Often asymptomatic, sometimes producing visible lesions, granulomatous gingivitis may mislead into wrong diagnosis and treatment. Old silica granulomas may become symptomatic if the patient contracts sarcoidosis.

  2. Soluble polymers in sol-gel silica

    NASA Astrophysics Data System (ADS)

    Beaudry, Christopher Laurent

    In the last few years, the inherent versatility of sol-gel processing has led to a significant research effort on inorganic/organic materials. One method of incorporating an organic phase into sol-gel silica is dissolving an organic polymer in a tetraethylorthosilicate (TEOS) solution, followed by in situ polymerization of silica in the presence of organic polymer. The first part of the study involved the development of a two-step (acid-base) synthesis procedure to allow systematic control of acidity in TEOS solutions. With this procedure, it was possible to increase the pH of the TEOS solution while correlating the acidity and properties. The properties were the gelation time, syneresis rate, drying behavior, and xerogel pore structure, as determined by nitrogen sorption. Furthermore, controlling the acidity was shown to control the silica xerogel pore structure. In the second part of the study, the two-step procedure was used to synthesize silica/poly(ethylene glycol) (PEG), and silica/poly(vinyl acetate) (PVAc) composite materials. The content of organic polymer and the molecular weight were varied. The gelation time, the syneresis rate, the drying behavior, and the pore structure were determined for compositions with 10% PEG (M.W. 2,000), 5, 10, and 15% PEG (M.W. 3,400), and 10 and 25% PVAc (M.W. 83,000). Other compositions and molecular weights of PEG lead to sedimentation. In the PEG compositions, the tendency to phase separate was correlated with the effects of the processing variables on the segregation strength and polymerization rate. The PVAc compositions did not show any visible phase separation during processing, giving the composite xerogels an appearance similar to pure silica. The property differences between gels with PEG and gels with PVAc show the relative strength of the interactions with silica. Both polymers exhibit hydrogen bonding between the phases. In the case of PEG, hydrogen bonding between the ether oxygens of the polymer and silanol

  3. Drug release from ordered mesoporous silicas.

    PubMed

    Doadrio, Antonio L; Salinas, Antonio J; Sánchez-Montero, José M; Vallet-Regí, M

    2015-01-01

    The state-of-the-art in the investigation of drugs release from Silica-based ordered Mesoporous Materials (SMMs) is reviewed. First, the SMM systems used like host matrixes are described. Then, the model drugs studied until now, including their pharmacological action, structure and the mesoporous matrix employed for each drug, are comprehensively listed. Next, the factors influencing the release of drugs from SMMs and the strategies used to control the drug delivery, specially the chemical functionalization of the silica surface, are discussed. In addition, how all these factors were gathered in a kinetic equation that describes the drug release from the mesoporous matrixes is explained. The new application of molecular modeling and docking in the investigation of the drug delivery mechanisms from SMMs is also presented. Finally, the new approaches under investigation in this field are mentioned including the design of smart stimuli-responsive materials and other recent proposals for a future investigation. PMID:26549760

  4. Viscoelasticity of silica gels

    SciTech Connect

    Scherer, G.W.

    1995-12-01

    The response of silica gels to mechanical loads depends on the properties of the solid phase and the permeability of the network. Understanding this behavior is essential for modeling of stresses developed during drying or heating of gels. The permeability and the mechanical properties are readily determined from a simple beam-bending experiment, by measuring the load relaxation that occurs at constant deflection. Load decay results from movement of the liquid within the network; in addition, there may be viscoelastic relaxation of the network itself. Silica gel is viscoelastic in chemically aggressive media, but in inert liquids (such as ethanol or acetone) it is elastic. Experiments show that the viscoelastic relaxation time decreases as the concentration and pH of the water in the pore liquid increase. During drying, the permeability decreases and the viscosity increases, both exhibiting a power-law dependence on density of the gel network.

  5. Fast Glazing of Alumina/Silica Tiles

    NASA Technical Reports Server (NTRS)

    Creedon, J. F.; Gzowski, E. R.; Wheeler, W. H.

    1986-01-01

    Technique for applying ceramic coating to fibrous silica/alumina insulation tiles prevents cracks and substantially reduces firing time. To reduce thermal stresses in tile being coated, high-temperature, shorttime firing schedule implemented. Such schedule allows coating to mature while substrate remains at relatively low temperature, reducing stress differential between coating and substrate. Technique used to repair tiles with damaged coatings and possibly used in heat-treating objects made of materials having different thermal-expansion coefficients.

  6. Electrical property measurements of metallized flagella-templated silica nanotube networks

    NASA Astrophysics Data System (ADS)

    Jo, Wonjin; Darmawan, Marten; Kim, Jihoon; Ahn, Chi Won; Byun, Doyoung; Baik, Seung Hyun; Kim, Min Jun

    2013-04-01

    We present an improvement in the electrical properties of silica nanotubes by coating metal nanoparticles on their surfaces. The silica nanotubes are formed from bacterial flagella bio-templates having a tubular structure. Successive depositions of metal nanoparticles on the silica nanotubes are performed through easily functionalized silica surfaces. The results show uniform metal nanoparticle sizes and a high surface area coverage. By incorporating gold, palladium and iron oxide nanoparticles, the metallized silica nanotubes gain electrical properties with the potential to create unique nanoelectronic materials. In this study, the metallized silica nanotubes with network structures are aligned and their electrical behaviors are investigated in both dry and wet conditions. The metallized silica nanotubes are found to be electrically conductive along the network structures. The current-voltage characteristics show remarkably improved electrical conductivities depending on the type of metal nanoparticle loading and nanotube network concentration.

  7. Electrical property measurements of metallized flagella-templated silica nanotube networks.

    PubMed

    Jo, Wonjin; Darmawan, Marten; Kim, Jihoon; Ahn, Chi Won; Byun, Doyoung; Baik, Seung Hyun; Kim, Min Jun

    2013-04-01

    We present an improvement in the electrical properties of silica nanotubes by coating metal nanoparticles on their surfaces. The silica nanotubes are formed from bacterial flagella bio-templates having a tubular structure. Successive depositions of metal nanoparticles on the silica nanotubes are performed through easily functionalized silica surfaces. The results show uniform metal nanoparticle sizes and a high surface area coverage. By incorporating gold, palladium and iron oxide nanoparticles, the metallized silica nanotubes gain electrical properties with the potential to create unique nanoelectronic materials. In this study, the metallized silica nanotubes with network structures are aligned and their electrical behaviors are investigated in both dry and wet conditions. The metallized silica nanotubes are found to be electrically conductive along the network structures. The current-voltage characteristics show remarkably improved electrical conductivities depending on the type of metal nanoparticle loading and nanotube network concentration.

  8. The use of Reactive Ion Etching for obtaining “free” silica nano test tubes

    NASA Astrophysics Data System (ADS)

    Buyukserin, Fatih; Martin, Charles R.

    2010-10-01

    Silica nano test tubes are one-dimensional inorganic nanostructures with several biotechnological applications including biosensing, magnetic resonance imaging, and targeted cancer therapeutics. They are generally prepared by sol-gel deposition of silica to nanoporous alumina templates. Preparing samples composed of isolated free silica nano test tubes can be a challenging process due to the conformal coating of silica on the template. This causes the formation of a top-surface silica layer which laterally connects the nano test tubes. Herein, we detailed the use of Reactive Ion Etching to remove this top-surface silica layer which yields free silica nano test tubes with template dissolution. Compared with the mechanical polishing approach, Reactive Ion Etching treatment allows a fine manipulation ability of the surface material at the nanoscale level. When used excessively, Reactive Ion Etching causes an orifice closing phenomenon that may be employed to create novel one-dimensional nanocapsules.

  9. Imprinting Chirality in Silica Nanotubes by N-Stearoyl-serine Template.

    PubMed

    Levi, Gila; Scolnik, Yosef; Mastai, Yitzhak

    2016-09-01

    In this article, we describe the synthesis of imprinted chiral silica nanotubes based on the use of a chiral N-stearoyl l-serine (C18Ser) anionic surfactant as the chiral template. The resulting chiral silica nanotube structures were characterized by electronic microscopy (transmission electron microscopy (TEM) and scanning electron microscopy (SEM)) and nitrogen isotherms that proved the formation of well-ordered silica nanotubes. A C18Ser surfactant template was used for the preparation of the silica nanotubes, due to its effective molecular organization within the silica network. After chemical extraction of the chiral template, the enantioselectivity feature of the silica nanotubes was confirmed by selective adsorption of the enantiomers using circular dichroism (CD) and isothermal titration calorimetry (ITC) measurements. Although these measurements show a relatively low chiral selectivity of the silica nanotubes (ca. 6% enantiomeric excess), the system described here offers new approaches for the application of chiral porous materials in chirality. PMID:27533529

  10. The synthesis and application of two mesoporous silica nanoparticles as drug delivery system with different shape

    NASA Astrophysics Data System (ADS)

    Wang, Jiayi; Wang, Zhuyuan; Chen, Hui; Zong, Shenfei; Cui, Yiping

    2015-05-01

    Mesoporous silica nanospheres(MSNSs) have been obtained utilizing the conventional reverse micelles synthesis method while the mesoporous silica nanorods(MSNRs) have been acquired by means of changing certain parameters. Afterwards, the prepared mesoporous silica nanospheres and nanorods were used as drug carriers to load and release the classical cancer therapeutic drug—DOX. According to the absorption spectra, the encapsulation efficiency of the mesoporous silica nanospheres is almost as high as that of the nanospheres. Different from the familiar encapsulation efficiency, the release characteristic curves of the mesoporous silica nanospheres and nanorods possessed certain differences during the release process. Finally incellular fluorescence imaging was achieved to observe the endocytosis of the mesoporous silica materials. Our results show that although both of the two kinds of nanoparticles possess favourable properties for loading and releasing drugs, the mesoporous silica nanospheres perform better in dispersity and controlled release than the nanorods, which probably endow them the potential as incellular drug delivery system.

  11. Imprinting Chirality in Silica Nanotubes by N-Stearoyl-serine Template.

    PubMed

    Levi, Gila; Scolnik, Yosef; Mastai, Yitzhak

    2016-09-01

    In this article, we describe the synthesis of imprinted chiral silica nanotubes based on the use of a chiral N-stearoyl l-serine (C18Ser) anionic surfactant as the chiral template. The resulting chiral silica nanotube structures were characterized by electronic microscopy (transmission electron microscopy (TEM) and scanning electron microscopy (SEM)) and nitrogen isotherms that proved the formation of well-ordered silica nanotubes. A C18Ser surfactant template was used for the preparation of the silica nanotubes, due to its effective molecular organization within the silica network. After chemical extraction of the chiral template, the enantioselectivity feature of the silica nanotubes was confirmed by selective adsorption of the enantiomers using circular dichroism (CD) and isothermal titration calorimetry (ITC) measurements. Although these measurements show a relatively low chiral selectivity of the silica nanotubes (ca. 6% enantiomeric excess), the system described here offers new approaches for the application of chiral porous materials in chirality.

  12. Mössbauer characterization of the Fe-S center in the catalytic metal binding site of alcohol dehydrogenase

    NASA Astrophysics Data System (ADS)

    Haas, C.; Dietrich, H.; Maret, W.; Zeppezauer, M.; Montiel-Montoya, R.; Bill, E.; Trautwein, A. X.

    1986-02-01

    Iron in its divalent and trivalent form can be substituted in the catalytic zinc site of alcohol dehydrogenase from horse liver (HLADH). Fe-HLADH in either oxidation state does not show enzymatic activity in the oxidation of ethanol. Nevertheless, Mössbauer studies of this material are of considerable interest, because they elucidate the effect of pH and coenzyme-induced conformational changes of the protein on the metal ion. It is of importance to note that zinc itself due to the lack of suitable chromophoric and magnetic properties does not provide any comparable information.

  13. Luminescent Silica Nanoparticles for cancer diagnosis

    PubMed Central

    Montalti, Marco; Petrizza, Luca; Rampazzo, Enrico; Zaccheroni, Nelsi; Marchiò, Serena

    2015-01-01

    Fluorescence imaging techniques are becoming essential in preclinical investigations, and the research of suitable tools for in vivo measurements is gaining more and more importance and attention. Nanotechnology entered the field to try to find solutions for many limitation at the state of the art, and luminescent nanoparticles (NPs) are one of the most promising materials proposed for future diagnostic implementation. NPs constitute also a versatile platform that can allow facile multi-functionalization to perform multimodal imaging or theranostic (simultaneous diagnosis and therapy). In this contribution we have focussed our attention only on dye doped silica or silica-based NPs conjugated with targeting moieties to enable specific cancer cells imaging and differentiation, even if also a few non targeted systems have been cited and discussed for completeness. We have summarized common synthetic approaches to these materials and then surveyed the most recent imaging applications of silica-based nanoparticles in cancer. The field of theranostic is so important and stimulating that, even if it is not the central topic of this paper, we have included some significant examples. We have then concluded with short hints on systems already in clinical trials and examples of specific applications in children tumours. This review tries to describe and discuss, through focussed examples, the great potentialities of these materials in the medical field, with the aim to encourage further research to implement applications that are still rare. PMID:23458621

  14. Modified silica sol coatings for surface enhancement of leather.

    PubMed

    Mahltig, Boris; Vossebein, Lutz; Ehrmann, Andrea; Cheval, Nicolas; Fahmi, Amir

    2012-06-01

    The presented study reports on differently modified silica sols for coating applications on leather. Silica sols are prepared by acidic hydrolysis of tetraethoxysilane and modified by silane compounds with fluorinated and non-fluorinated alkylgroups. In contrast to many earlier investigations regarding sol-gel applications on leather, no acrylic resin is used together with the silica sols when applying on leather. The modified silica particles are supposed to aggregate after application, forming thus a modified silica coating on the leather substrate. Scanning electron microscopy investigation shows that the applied silica coatings do not fill up or close the pores of the leather substrate. However, even if the pores of the leather are not sealed by this sol-gel coating, an improvement of the water repellent and oil repellent properties of the leather substrates are observed. These improved properties of leather by application of modified silica sols can provide the opportunity to develop sol-gel products for leather materials present in daily life.

  15. 21 CFR 182.1711 - Silica aerogel.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Silica aerogel. 182.1711 Section 182.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  16. 21 CFR 582.1711 - Silica aerogel.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  17. 21 CFR 182.1711 - Silica aerogel.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Silica aerogel. 182.1711 Section 182.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  18. 21 CFR 582.1711 - Silica aerogel.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  19. 21 CFR 582.1711 - Silica aerogel.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  20. 21 CFR 182.1711 - Silica aerogel.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Silica aerogel. 182.1711 Section 182.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  1. 21 CFR 582.1711 - Silica aerogel.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  2. 21 CFR 182.1711 - Silica aerogel.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Silica aerogel. 182.1711 Section 182.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  3. 21 CFR 182.1711 - Silica aerogel.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Silica aerogel. 182.1711 Section 182.1711 Food and... GENERALLY RECOGNIZED AS SAFE Multiple Purpose GRAS Food Substances § 182.1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of...

  4. 21 CFR 582.1711 - Silica aerogel.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Silica aerogel. 582.1711 Section 582.1711 Food and....1711 Silica aerogel. (a) Product. Silica aerogel as a finely powdered microcellular silica foam having a minimum silica content of 89.5 percent. (b) (c) Limitations, restrictions, or explanation....

  5. A study of the metal binding capacity of saccharinic acids formed during the alkali catalysed decomposition of cellulosic materials: nickel complexation by glucoisosaccharinic acids and xyloisosaccharinic acids.

    PubMed

    Almond, Michael; Belton, Daniel; Humphreys, Paul N; Laws, Andrew P

    2016-06-01

    The stoichiometry of the metal complexes formed between nickel and the ligand β-glucoisosaccharinic acid (β-GISA) and a racemic mixture of enantiomers of xyloisosaccharinic acid (XISA) has been determined at both neutral and alkaline pHs. Bjerrum plots, Job's plots and conductance measurements indicated that for each of the systems one to one Ni(ligand) complexes were formed at near neutral pHs (<7.5). At intermediate alkaline pHs (7.5-13) there is evidence to support the formation and precipitation of Ni2(ligand)(OH)3 complexes, finally, at high pH (>13) sparingly soluble Ni2(ligand)(OH)4 complexes were formed. The stability constants for the Ni(β-GISA), Ni(α-GISA) and Ni(XISA) complexes formed at neutral pH were determined under identical conditions using polarographic studies. The measured stability constants for Ni(β-GISA) (log10 β = 1.94 ± 0.15) and for Ni(α-GISA)(log10 β = 2.07 ± 0.13) are very similar; the value measured for the Ni(XISA) complex (log10 β = 0.83) was an order of magnitude smaller. The stability constants for the Ni2(Ligand)(OH)4 complexes formed at highly alkaline pHs were determined using the Schubert method. The measured stability constant for Ni2(β-GISA)(OH)4 (log10 β = 30.6 ± 0.5) was an order of magnitude bigger than the value for Ni2(α-GISA)(OH)4 (log10 β = 29.0 ± 0.5) measured under identical conditions. Attempts to measure the stability constant for Ni2(XISA)(OH)4 were unsuccessful; Ni2(XISA)(OH)4 complexes were not present in significant amounts at high pH to allow the log10β value to be determined by the Schubert method. PMID:27107221

  6. The world ocean silica cycle.

    PubMed

    Tréguer, Paul J; De La Rocha, Christina L

    2013-01-01

    Over the past few decades, we have realized that the silica cycle is strongly intertwined with other major biogeochemical cycles, like those of carbon and nitrogen, and as such is intimately related to marine primary production, the efficiency of carbon export to the deep sea, and the inventory of carbon dioxide in the atmosphere. For nearly 20 years, the marine silica budget compiled by Tréguer et al. (1995) , with its exploration of reservoirs, processes, sources, and sinks in the silica cycle, has provided context and information fundamental to study of the silica cycle. Today, the budget needs revisiting to incorporate advances that have notably changed estimates of river and groundwater inputs to the ocean of dissolved silicon and easily dissolvable amorphous silica, inputs from the dissolution of terrestrial lithogenic silica in ocean margin sediments, reverse weathering removal fluxes, and outputs of biogenic silica (especially on ocean margins and in the form of nondiatomaceous biogenic silica). The resulting budget recognizes significantly higher input and output fluxes and notes that the recycling of silicon occurs mostly at the sediment-water interface and not during the sinking of silica particles through deep waters.

  7. Agricultural waste as a source for the production of silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Vaibhav, Vineet; Vijayalakshmi, U.; Roopan, S. Mohana

    2015-03-01

    The major interest of the paper deals with the extraction of silica from four natural sources such as rice husk, bamboo leaves, sugarcane bagasse and groundnut shell. These waste materials in large quantities can create a serious environmental problem. Hence, there is a need to adopt proper strategy to reduce the waste. In the present investigation, all the waste materials are subjected to moisture removal in a hot plate and sintered at 900 °C for 7 h. The sintered powder was treated with 1 M NaOH to form sodium silicate and then with 6 M H2SO4 to precipitate silica. The prepared silica powders were characterized by FT-IR, XRD and SEM-EDAX analysis. The silica recovered from different sources was found to vary between 52% and 78%. Magnesium substituted silica was formed from the groundnut waste and further treatment is required to precipitate silica.

  8. Insight into the evolution, redox, and metal binding properties of dissolved organic matter from municipal solid wastes using two-dimensional correlation spectroscopy.

    PubMed

    He, Xiao-Song; Xi, Bei-Dou; Zhang, Zong-Yong; Gao, Ru-Tai; Tan, Wen-Bing; Cui, Dong-Yu

    2014-12-01

    Two-dimensional correlation spectroscopy was employed to investigate the evolution, redox, and metal binding properties of dissolved organic matter (DOM) from municipal solid wastes (MSWs) during composting. The results showed that the DOM was degraded during composting in the order of aliphatic substances > proteinaceous compounds > cellulose, hemicellulose and lignin, while humic substances transformed during the process in the order of fulvic-like matter > humic-like substances > protein-like matter. The fulvic- and humic-like substances originated from lignin and polysaccharide-like substances with the function groups of CH3, CCH2, CCH, OCH3, OCH, O--C--O, aromatic C, and COO, while the protein-like matter was derived from aliphatic and proteinaceous compounds with the functional groups of CCH3 and N--C==O. The aromatic C and COO were responsible for the oxidation capacity of the MSW-derived DOM, while the O--C--O and COO accounted for the Cu and Zn binding capacity of the DOM.

  9. A New Type of Metal-Binding Site in Cobalt- And Zinc-Containing Adenylate Kinases Isolated From Sulfate-Reducers D. Gigas And D. Desulfuricans ATCC 27774

    SciTech Connect

    Gavel, O.Y.; Bursakov, S.A.; Rocco, G.Di; Trincao, J.; Pickering, I.J.; George, G.N.; Calvete, J.J.; Brondino, C.; Pereira, A.S.; Lampreia, J.; Tavares, P.; Moura, J.J.G.; Moura, I.

    2009-05-18

    Adenylate kinase (AK) mediates the reversible transfer of phosphate groups between the adenylate nucleotides and contributes to the maintenance of their constant cellular level, necessary for energy metabolism and nucleic acid synthesis. The AK were purified from crude extracts of two sulfate-reducing bacteria (SRB), Desulfovibrio (D.) gigas NCIB 9332 and Desulfovibrio desulfuricans ATCC 27774, and biochemically and spectroscopically characterized in the native and fully cobalt- or zinc-substituted forms. These are the first reported adenylate kinases that bind either zinc or cobalt and are related to the subgroup of metal-containing AK found, in most cases, in Gram-positive bacteria. The electronic absorption spectrum is consistent with tetrahedral coordinated cobalt, predominantly via sulfur ligands, and is supported by EPR. The involvement of three cysteines in cobalt or zinc coordination was confirmed by chemical methods. Extended X-ray absorption fine structure (EXAFS) indicate that cobalt or zinc are bound by three cysteine residues and one histidine in the metal-binding site of the 'LID' domain. The sequence {sup 129}Cys-X{sub 5}-His-X{sub 15}-Cys-X{sub 2}-Cys of the AK from D. gigas is involved in metal coordination and represents a new type of binding motif that differs from other known zinc-binding sites of AK. Cobalt and zinc play a structural role in stabilizing the LID domain.

  10. Crystal Structure of Phosphatidylglycerophosphatase (PGPase), a Putative Membrane-Bound Lipid Phosphatase, Reveals a Novel Binuclear Metal Binding Site and Two Proton Wires

    SciTech Connect

    Kumaran,D.; Bonnano, J.; Burley, S.; Swaminathan, S.

    2006-01-01

    Phosphatidylglycerophosphatase (PGPase), an enzyme involved in lipid metabolism, catalyzes formation of phosphatidylglycerol from phosphatidylglycerophosphate. Phosphatidylglycerol is a multifunctional phospholipid, found in the biological membranes of many organisms. Here, we report the crystal structure of Listeria monocytogenes PGPase at 1.8 Angstroms resolution. PGPase, an all-helical molecule, forms a homotetramer. Each protomer contains an independent active site with two metal ions, Ca{sup 2+} and Mg{sup 2+}, forming a hetero-binuclear center located in a hydrophilic cavity near the surface of the molecule. The binuclear center, conserved ligands, metal-bound water molecules, and an Asp-His dyad form the active site. The catalytic mechanism of this enzyme is likely to proceed via binuclear metal activated nucleophilic water. The binuclear metal-binding active-site environment of this structure should provide insights into substrate binding and metal-dependent catalysis. A long channel with inter-linked linear water chains, termed 'proton wires', is observed at the tetramer interface. Comparison of similar water chain structures in photosynthetic reaction centers (RCs), Cytochrome f, gramicidin, and bacteriorhodopsin, suggests that PGPase may conduct protons via proton wires.

  11. A cysteine-rich metal-binding domain from rubella virus non-structural protein is essential for viral protease activity and virus replication.

    PubMed

    Zhou, Yubin; Tzeng, Wen-Pin; Ye, Yiming; Huang, Yun; Li, Shunyi; Chen, Yanyi; Frey, Teryl K; Yang, Jenny J

    2009-01-15

    The protease domain within the RUBV (rubella virus) NS (non-structural) replicase proteins functions in the self-cleavage of the polyprotein precursor into the two mature proteins which form the replication complex. This domain has previously been shown to require both zinc and calcium ions for optimal activity. In the present study we carried out metal-binding and conformational experiments on a purified cysteine-rich minidomain of the RUBV NS protease containing the putative Zn(2+)-binding ligands. This minidomain bound to Zn(2+) with a stoichiometry of approximately 0.7 and an apparent dissociation constant of <500 nM. Fluorescence quenching and 8-anilinonaphthalene-1-sulfonic acid fluorescence methods revealed that Zn(2+) binding resulted in conformational changes characterized by shielding of hydrophobic regions from the solvent. Mutational analyses using the minidomain identified residues Cys(1175), Cys(1178), Cys(1225) and Cys(1227) were required for the binding of Zn(2+). Corresponding mutational analyses using a RUBV replicon confirmed that these residues were necessary for both proteolytic activity of the NS protease and viability. The present study demonstrates that the CXXC(X)(48)CXC Zn(2+)-binding motif in the RUBV NS protease is critical for maintaining the structural integrity of the protease domain and essential for proteolysis and virus replication. PMID:18795894

  12. Cd2+ and the N-terminal metal-binding domain protect the putative membranous CPC motif of the Cd2+-ATPase of Listeria monocytogenes.

    PubMed Central

    Bal, Nathalie; Wu, Chen Chou; Catty, Patrice; Guillain, Florent; Mintz, Elisabeth

    2003-01-01

    CadA, the Cd(2+)-ATPase of Listeria monocytogenes, contains four cysteine residues: two in the CTNC (Cys-Thr-Asn-Cys) sequence in the cytoplasmic metal-binding domain (MBD), and two in the CPC (Cys-Pro-Cys) sequence in the membrane domain. Taking advantage of DeltaMBD, a truncated version of CadA that lacks the MBD but which still acts as a functional Cd(2+)-ATPase [Bal, Mintz, Guillain and Catty (2001) FEBS Lett. 506, 249-252], we analysed the role of the membrane cysteine residues (studied using DeltaMBD) separately from that of the cysteine residues of the MBD, which were studied using full-length CadA. The role of the cysteines was assessed by reacting DeltaMBD and CadA with N -ethylmaleimide (NEM), an SH-specific reagent, in the presence or absence of Cd(2+). We show here that (i) in both DeltaMBD and CadA, the cysteine residues in the CPC motif are essential for phosphorylation; (ii) in both proteins, Cd(2+) protects against alkylation by NEM; and (iii) in the absence of Cd(2+), the MBD of CadA also protects against alkylation by NEM. Our results suggest that the CPC motif is present in the membrane Cd(2+) transport site(s) and that the MBD protects these site(s). PMID:12383056

  13. Micron-size metal-binding hydrogel particles improve germination and radicle elongation of Australian metallophyte grasses in mine waste rock and tailings.

    PubMed

    Guterres, J; Rossato, L; Pudmenzky, A; Doley, D; Whittaker, M; Schmidt, S

    2013-03-15

    Metal contamination of landscapes as a result of mining and other industrial activities is a pervasive problem worldwide. Metal contaminated soils often lack effective vegetation cover and are prone to contaminant leaching and dispersion through erosion, leading to contamination of the environment. Metal-binding hydrogel particle amendments could ameliorate mine wastes prior to planting and enhance seedling emergence. In this study, micron-size thiol functional cross-linked acrylamide polymer hydrogel particles (X3) were synthesised and tested in laboratory-scale experiments on phytotoxic mine wastes to determine their capacity to: (i) increase substrate water holding capacity (WHC); (ii) reduce metal availability to plants to below the phytotoxicity threshold; and (iii) enhance germination characteristics and early radicle development of two Australian metallophyte grasses under limiting and non-limiting water conditions. Addition of X3 to mine wastes significantly increased their WHC and lowered toxic soluble metal concentrations in mine waste leachates. Germination percentages and radicle elongation of both grasses in wastes were significantly increased. Highest germination percentages and greater radicle development recorded in X3 amended wastes under water limited conditions suggests that X3 was able to ameliorate metal toxicity to radicles, and provide moisture, which improved the imbibition and consequent germination of the seeds. PMID:23416872

  14. Cadmium, metal-binding proteins, and growth in bluegill (Lepomis macrochirus) exposed to contaminated sediments from the upper Mississippi River basin

    USGS Publications Warehouse

    Cope, W.G.; Wiener, J.G.; Steingraeber, M.T.; Atchison, G.J.

    1994-01-01

    We exposed juvenile bluegill (Lepomis macrochirus) to ~1000 mg·L-1 of continuously suspended river sediment in a 28-d test with six treatments (randomized block with one sediment-free control and five sediments ranging from 1.3 to 21.4 μg Cd·g dry weight-1). Each treatment had three replicates, each with 25 fish. Growth was reduced by exposure to suspended sediment, probably due to physical effects of sediment on feeding and to toxicity in the treatment with the greatest concentrations of metals. Mean whole-body concentrations of cadmium (0.04–0.14 μg wet weight-1) were correlated with cadmium concentration in filtered water (8–72 ng·L-1), suspended sediment (0.61–16.8 μg·L-1), and bulk sediment. The concentration of hepatic nonthionein cytosolic cadmium (cadmium not bound by metal-binding proteins, MBP) in fish exposed to the two most contaminated sediments exceeded that in controls. The mean concentration of hepatic MBP was correlated with cadmium concentration in filtered water, suspended sediment, bulk sediment, and whole fish. Whole-body cadmium concentration was the most sensitive indicator of cadmium exposure, with lowest observed effect concentrations of 1.9 μg Cd·L-1 for suspended sediment and 13 ng Cd·L-1 for filtered water. Sediment-associated cadmium was less available than waterborne cadmium for uptake by fish.

  15. Crystal Structures of Apo and Metal-Bound Forms of the UreE Protein from Helicobacter pylori: Role of Multiple Metal Binding Sites

    SciTech Connect

    Shi, Rong; Munger, Christine; Asinas, Abdalin; Benoit, Stephane L.; Miller, Erica; Matte, Allan; Maier, Robert J.; Cygler, Miroslaw

    2010-10-22

    The crystal structure of the urease maturation protein UreE from Helicobacter pylori has been determined in its apo form at 2.1 {angstrom} resolution, bound to Cu{sup 2+} at 2.7 {angstrom} resolution, and bound to Ni{sup 2+} at 3.1 {angstrom} resolution. Apo UreE forms dimers, while the metal-bound enzymes are arranged as tetramers that consist of a dimer of dimers associated around the metal ion through coordination by His102 residues from each subunit of the tetramer. Comparison of independent subunits from different crystal forms indicates changes in the relative arrangement of the N- and C-terminal domains in response to metal binding. The improved ability of engineered versions of UreE containing hexahistidine sequences at either the N-terminal or C-terminal end to provide Ni{sup 2+} for the final metal sink (urease) is eliminated in the H102A version. Therefore, the ability of the improved Ni{sup 2+}-binding versions to deliver more nickel is likely an effect of an increased local concentration of metal ions that can rapidly replenish transferred ions bound to His102.

  16. Fabrication of keratin-silica hydrogel for biomedical applications.

    PubMed

    Kakkar, Prachi; Madhan, Balaraman

    2016-09-01

    In the recent past, keratin has been fabricated into different forms of biomaterials like scaffold, gel, sponge, film etc. In lieu of the myriad advantages of the hydrogels for biomedical applications, a keratin-silica hydrogel was fabricated using tetraethyl orthosilicate (TEOS). Textural analysis shed light on the physical properties of the fabricated hydrogel, inturn enabling the optimization of the hydrogel. The optimized keratin-silica hydrogel was found to exhibit instant springiness, optimum hardness, with ease of spreadability. Moreover, the hydrogel showed excellent swelling with highly porous microarchitecture. MTT assay and DAPI staining revealed that keratin-silica hydrogel was biocompatible with fibroblast cells. Collectively, these properties make the fabricated keratin-silica hydrogel, a suitable dressing material for biomedical applications.

  17. In situ synthesis of polysulfides covalently bonded to silica.

    PubMed

    Ossenkamp, Gabriel C; Kemmitt, Tim; Johnston, Jim H

    2002-05-15

    Silanol groups, triple bond SiOH, on the surface of silica were esterified with unsaturated alcohols and long-chain alcohols bearing thiol groups. The modified silicas obtained were used as substrates for a vulcanization-analogous reaction with sulfur catalyzed by zinc dimethyldithiocarbamate. Surface-esterified thiols could be smoothly converted to bridged polysulfides bonded to the silica surface, whereas the use of surface-esterified unsaturated alcohols led to removal of the surface-esterified alcohol from the silica surface. The materials were characterized by solid-state NMR and thermal and microanalytical analysis. The linking of surface-esterified alkenols and thiols by sulfide bridges was investigated by a numerical model for a flat surface. This showed that for a typical density of 3-4 micromol/m(2) surface groups, a statistical maximum of 70-75% of groups could be linked by S(n) bridges (n=2-4). PMID:16290622

  18. Quantification of residual stress from photonic signatures of fused silica

    NASA Astrophysics Data System (ADS)

    Cramer, K. Elliott; Hayward, Maurice; Yost, William T.

    2014-02-01

    A commercially available grey-field polariscope (GFP) instrument for photoelastic examination is used to assess impact damage inflicted upon the outer-most pane of Space Shuttle windows made from fused silica. A method and apparatus for calibration of the stress-optic coefficient using four-point bending is discussed. The results are validated on known material (acrylic) and are found to agree with literature values to within 6%. The calibration procedure is then applied to fused-silica specimens and the stress-optic coefficient is determined to be 2.43 ± 0.54 × 10-12 Pa-1. Fused silica specimens containing impacts artificially made at NASA's Hypervelocity Impact Technology Facility (HIT-F), to simulate damage typical during space flight, are examined. The damage sites are cored from fused silica window carcasses and examined with the GFP. The calibrated GFP measurements of residual stress patterns surrounding the damage sites are presented.

  19. Stable and responsive fluorescent carbon nanotube silica gels

    SciTech Connect

    Dattelbaum, Andrew M; Gupta, Gautam; Doorn, Stephen K; Duque, Juan G

    2010-05-03

    Here we report a general route to prepare silica nanocomposite gels doped with fluorescent single walled carbon nanotubes (SWNT). We show that tetramethylorthosilicate (TMOS) vapors can be used to gel an aqueous suspension of surfactant-wrapped SWNT while maintaining fluorescence from the semiconducting nanotubes. The vapor phase silica process is performed at room temperature and is simple, reproducible, relatively quick, and requires no dilution of SWNT dispersions. However, exposure of aqueous SWNT suspensions to TMOS vapors resulted in an acidification of the suspension prior to gelation that caused a decrease in the emission signal from sodium dodecylsulfate (SDS) wrapped SWNT. We also show that although the SWNT are encapsulated in silica the emission signal from the encapsulated SWNT may be attenuated by exposing the nanocomposites to small aromatic molecules known to mitigate SWNT emission. These results demonstrate a new route for the preparation of highly luminescent SWNT/silica composite materials that are potentially useful for future sensing applications.

  20. Pentalysine clusters mediate silica targeting of silaffins in Thalassiosira pseudonana.

    PubMed

    Poulsen, Nicole; Scheffel, André; Sheppard, Vonda C; Chesley, Patrick M; Kröger, Nils

    2013-07-12

    The biological formation of inorganic materials (biomineralization) often occurs in specialized intracellular vesicles. Prominent examples are diatoms, a group of single-celled eukaryotic microalgae that produce their SiO2 (silica)-based cell walls within intracellular silica deposition vesicles (SDVs). SDVs contain protein-based organic matrices that control silica formation, resulting in species specifically nanopatterned biosilica, an organic-inorganic composite material. So far no information is available regarding the molecular mechanisms of SDV biogenesis. Here we have investigated by fluorescence microscopy and subcellular membrane fractionation the intracellular transport of silaffin Sil3. Silaffins are a group of phosphoproteins constituting the main components of the organic matrix of diatom biosilica. We demonstrate that the N-terminal signal peptide of Sil3 mediates import into a specific subregion of the endoplasmic reticulum. Additional segments from the mature part of Sil3 are required to reach post-endoplasmic reticulum compartments. Further transport of Sil3 and incorporation into the biosilica (silica targeting) require protein segments that contain a high density of modified lysine residues and phosphoserines. Silica targeting of Sil3 is not dependent on a particular peptide sequence, yet a lysine-rich 12-14-amino acid peptide motif (pentalysine cluster), which is conserved in all silaffins, strongly promotes silica targeting. The results of the present work provide the first insight into the molecular mechanisms for biogenesis of mineral-forming vesicles from an eukaryotic organism.

  1. Twisted and tubular silica structures by anionic surfactant fibers encapsulation.

    PubMed

    Chekini, Mahshid; Guénée, Laure; Marchionni, Valentina; Sharma, Manish; Bürgi, Thomas

    2016-09-01

    Organic molecules imprinting can be used for introducing specific properties and functionalities such as chirality to mesoporous materials. Particularly organic self-assemblies can work as a scaffold for templating inorganic materials such as silica. During recent years chiral imprinting of anionic surfactant for fabrication of twisted rod-like silica structures assisted by co-structuring directing agent were thoroughly investigated. The organic self-assemblies of anionic surfactants can also be used for introducing other shapes in rod-like silica structures. Here we report the formation of amphiphilic N-miristoyl-l-alanine self-assemblies in aqueous solution upon stirring and at presence of l-arginine. These anionic surfactant self-assemblies form fibers that grow by increasing the stirring duration. The fibers were studied using transmission electron microscopy, infra-red spectroscopy and vibrational circular dichroism. Addition of silica precursor 1,2-bis(triethoxysilyl)ethylene and co-structuring directing agent N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride at different stages of fibers' growth leads to formation of different silica structures. By controlling stirring duration, we obtained twisted tubular silica structures as a result of fibers encapsulation. We decorated these structures with gold nanoparticles by different methods and measured their optical activity.

  2. Adsorption of mycotoxins in beverages onto functionalized mesoporous silicas

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mycotoxins, natural toxins produced by fungi, are a global concern as contaminates of agricultural commodities. Exposure to these toxins can be reduced by the use of binding materials. Templated mesoporous silicas are promising materials with favorable adsorptive properties for dyes, ions, and toxin...

  3. New insight into mesoporous silica for nano metal-organic framework.

    PubMed

    Kondo, Atsushi; Takanashi, Shinji; Maeda, Kazuyuki

    2012-10-15

    A micropore- and mesopore-integrated material was synthesized by using a mesoporous silica and a metal-organic framework (MOF). The composite was composed of nano MOF crystals and mesoporous silica showing high porosity based on the intrinsic micropores of MOF and mesopores of mesoporous silica and additional pore spaces that should be from the void between nano MOF crystals. The composite shows higher adsorption rate of ethanol at 303 K than that of the bulk MOF.

  4. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

    1999-01-01

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

  5. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

    2008-05-06

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

  6. Mesoporous-silica films, fibers, and powders by evaporation

    DOEpatents

    Bruinsma, P.J.; Baskaran, S.; Bontha, J.R.; Liu, J.

    1999-07-13

    This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s). 24 figs.

  7. Bright photoluminescent hybrid mesostructured silica nanoparticles.

    PubMed

    Miletto, Ivana; Bottinelli, Emanuela; Caputo, Giuseppe; Coluccia, Salvatore; Gianotti, Enrica

    2012-07-28

    Bright photoluminescent mesostructured silica nanoparticles were synthesized by the incorporation of fluorescent cyanine dyes into the channels of MCM-41 mesoporous silica. Cyanine molecules were introduced into MCM-41 nanoparticles by physical adsorption and covalent grafting. Several photoluminescent nanoparticles with different organic loadings have been synthesized and characterized by X-ray powder diffraction, high resolution transmission electron microscopy and nitrogen physisorption porosimetry. A detailed photoluminescence study with the analysis of fluorescence lifetimes was carried out to elucidate the cyanine molecules distribution within the pores of MCM-41 nanoparticles and the influence of the encapsulation on the photoemission properties of the guests. The results show that highly stable photoluminescent hybrid materials with interesting potential applications as photoluminescent probes for diagnostics and imaging can be prepared by both methods. PMID:22706523

  8. Synthesis, characterisation and application of silica-magnetite nanocomposites

    NASA Astrophysics Data System (ADS)

    Bruce, Ian J.; Taylor, James; Todd, Michael; Davies, Martin J.; Borioni, Enrico; Sangregorio, Claudio; Sen, Tapas

    2004-12-01

    Silica-magnetite composites were prepared for eventual applications in biomolecular separations (nucleic acids). Their production on large scale has been optimised and they have been extensively characterised in a physical and chemical context. They perform at least as well, if not better than a commercially available equivalent at adsorbing and eluting DNA. Several methods for the preparation of magnetite were compared in order to select one, which produced particles, possessing high magnetic susceptibility, low rate of sedimentation and good chemical stability. Of the main methods studied: (i) oxidative hydrolysis of iron(II) sulphate in alkaline media, (ii) alkaline hydrolysis of iron(II) and iron(III) chloride solutions, and (iii) precipitation from iron(II) and iron(III) chloride solutions by hydrolysis of urea, method (i) produced the 'best' magnetite particles. Silica-magnetite composites were prepared using the 'best' magnetite, and, for comparison, two methods for depositing silica were used to coat the silica onto magnetite nanoparticles, from silicic acid at pH 10 and by acid hydrolysis of tetraethoxysilane (TEOS) at 90 °C. The best method for yielding silica-magnetite composites that worked well in DNA adsorption and elution proved to be that involving silicic acid and this material could be made in 20 g batch sizes. Silica-magnetite composites from the two methods proved to have distinct and different physical and chemical properties. All magnetite and silica-magnetite samples were fully characterised for their relative chemical composition using Fourier-transform infrared, XRF and thermo-gravimetric analysis. Their physical characteristics were determined using scanning electron microscopy and N2 adsorption and Mossbauer spectroscopy was used to confirm the identity of the iron oxides produced. Selected samples were comparatively tested for their ability to adsorb, and subsequently elute, 2-deoxyguanosine-5-monophosphate (GMP) and its non

  9. Silica Fillers for elastomer Reinforement

    SciTech Connect

    Kohls, D.J.; Schaefer, D.W.

    2012-09-10

    This article summarizes recent work on the structure of precipitated silica used in the reinforcement of elastomers. Silica has a unique morphology, consisting of multiple structural levels that can be controlled through processing. The ability to control and characterize the multiple structures of precipitated silica is an example of morphological engineering for reinforcement applications. In this summary of some recent research efforts using precipitated silica, small-angle scattering techniques are described and their usefulness for determining the morphology of silica in terms of primary particles, aggregates, and agglomerates are discussed. The structure of several different precipitated silica powders is shown as well as the mechanical properties of elastomers reinforced with these silica particles. The study of the mechanical properties of filled elastomer systems is a challenging and exciting topic for both fundamental science and industrial application. It is known that the addition of hard particulates to a soft elastomer matrix results in properties that do not follow a straightforward rule of mixtures. Research efforts in this area have shown that the properties of filled elastomers are influenced by the nature of both the filler and the matrix, as well as the interactions between them. Several articles have reviewed the influence of fillers like silica and carbon black on the reinforcement of elastomers. In general, the structure-property relationships developed for filled elastomers have evolved into the following major areas: Filler structure, hydrodynamic reinforcement, and interactions between fillers and elastomers.

  10. Interfacial engineering for silica nanocapsules.

    PubMed

    Wibowo, David; Hui, Yue; Middelberg, Anton P J; Zhao, Chun-Xia

    2016-10-01

    Silica nanocapsules have attracted significant interest due to their core-shell hierarchical structure. The core domain allows the encapsulation of various functional components such as drugs, fluorescent and magnetic nanoparticles for applications in drug delivery, imaging and sensing, and the silica shell with its unique properties including biocompatibility, chemical and physical stability, and surface-chemistry tailorability provides a protection layer for the encapsulated cargo. Therefore, significant effort has been directed to synthesize silica nanocapsules with engineered properties, including size, composition and surface functionality, for various applications. This review provides a comprehensive overview of emerging methods for the manufacture of silica nanocapsules, with a special emphasis on different interfacial engineering strategies. The review starts with an introduction of various manufacturing approaches of silica nanocapsules highlighting surface engineering of the core template nanomaterials (solid nanoparticles, liquid droplets, and gas bubbles) using chemicals or biomolecules which are able to direct nucleation and growth of silica at the boundary of two-phase interfaces (solid-liquid, liquid-liquid, and gas-liquid). Next, surface functionalization of silica nanocapsules is presented. Furthermore, strategies and challenges of encapsulating active molecules (pre-loading and post-loading approaches) in these capsular systems are critically discussed. Finally, applications of silica nanocapsules in controlled release, imaging, and theranostics are reviewed. PMID:27522646

  11. Performance of Silica Gel in the Role of Residual Air Drying

    NASA Technical Reports Server (NTRS)

    Jan, Darrell L.; Hogan, John A.; Koss, Brian; Palmer, Gary H.; Richardson, Justine; Linggi, Paul

    2014-01-01

    Removal of carbon dioxide (CO2) is a necessary step in air revitalization and is often accomplished with sorbent materials. Since moisture competes with CO2 in sorbent materials, it is necessary to remove the water first. This is typically accomplished in two stages: bulk removal and residual drying. Silica gel is used as the bulk drying material in the Carbon Dioxide Removal Assembly (CDRA) in operation on ISS. There has been some speculation that silica gel may also be capable of serving as the residual drying material. This paper will describe test apparatus and procedures for determining the performance of silica gel in residual air drying.

  12. Silica uptake from nanoparticles and silica condensation state in different tissues of Phragmites australis.

    PubMed

    Schaller, Jörg; Brackhage, Carsten; Paasch, Silvia; Brunner, Eike; Bäucker, Ernst; Dudel, E Gert

    2013-01-01

    Silicon is described as beneficial for grasses by enhancing yield and fitness via a considerable contribution to pathogen, drought, and pest resistance. Silicic acid is the predominant form for uptake and transport within the plant and will precipitate in leaves. But it is unknown whether polymeric nanosilicon compounds in its synthetic form, with an increasing concentration in aquatic environments, can be suitable for plant nutrition. Therefore, we investigated the uptake, transport, and deposition of silicic acid/silica within plants using synthetic nanosilica. Our results show a significant difference in silicon (Si) content within the different tissues of Phragmites australis. The nanosilica had been dissolved prior to the uptake by plants. The chemical form of Si during uptake was not traceable. A significant enhancement in the condensation state of the silica was found from root to leaves especially from culm to leaf tips visible by the increasing content of Q(4)-groups in the NMR spectra. We conclude that synthetic nanosilica has the same quality as source for the beneficial element Si like natural silica. Since the condensation state is described to control silica solubility, we suggest that different condensation states within the plant may result in different remobilization of silicon during decomposition of the plant material. PMID:23178503

  13. Synthesis of microforsterite using derived-amorphous-silica of silica sands

    NASA Astrophysics Data System (ADS)

    Nurbaiti, Upik; Triwikantoro, Zainuri, Mochamad; Pratapa, Suminar

    2016-04-01

    Synthesis of microforsterite (Mg2SiO4) has been successfully done by a simple method benefiting of the local silica sands from Tanah Laut, Indonesia. The starting material was amorphous silica powder which was processed using coprecipitation method from the sands. The silica powder was obtained from a series of stages of the purification process of the sands, namely magnetic separation, grinding and soaking with HCl. The microforsterite synthesis followed the reaction of stoichiometric mole ratio mixing of 1:2 of the amorphous silica and MgO powders with 3 wt% addion of PVA as a catalyst.The mixture was calcined at temperatures between 1150-1400°C with 4 hours holding time. XRD data showed that calcination at a temperature of 1150°C for 4 hours was optimum where the weight fraction of forsterite can reach as much as 93 wt% with MgO as the secondary phase and without MgSiO3. SEM photograph of the microforsterite showed tapered morphology with a relatively homogeneous distribution.

  14. Effects of copper and cadmium on ion transport and gill metal binding in the Amazonian teleost tambaqui (Colossoma macropomum) in extremely soft water.

    PubMed

    Matsuo, Aline Y O; Wood, Chris M; Val, Adalberto L

    2005-09-30

    Metal toxicity in fish is expected to be most severe in soft waters because of the low availability of cations (particularly Ca(2+)) to out-compete the metal forms for binding sites on the gills. Natural waters in the Amazon basin are typically soft due to regional geochemistry, but few studies have focused on metal toxicity in fish native to the basin. We assessed the ionoregulatory effects of waterborne copper (Cu) and cadmium (Cd) on tambaqui (Colossoma macropomum) in extremely soft water (10 micromoll(-1) Ca(2+)). Tambaqui had a very high tolerance to Cu (50-400 microgl(-1)), as indicated by a complete lack of inhibition of Na(+) uptake and an ability to gradually recover over 6h from elevated diffusive Na(+) losses caused by Cu. The insensitivity of active Na(+) influx to Cu further supports the notion that Amazonian fish may have a unique Na(+) transport system. Addition of 5-10 mgCl(-1) of dissolved organic matter (DOM) did not prevent initial (0-3h) negative Na(+) balance in tambaqui exposed to Cu. Exposure to 40 mgCl(-1) DOM prevented Na(+) losses in tambaqui even at 400 microgl(-1) Cu, probably because most Cu was complexed to DOM. Tambaqui exposed to waterborne Cd (10-80 microgl(-1)) experienced an average of 42% inhibition in whole body Ca(2+) uptake relative to controls within 3h of exposure to the metal. Inhibition of Ca(2+) uptake increased over time and, at 24h, Ca(2+) uptake was suppressed by 51% and 91% in fish exposed to 10 and 80 microgl(-1) Cd, respectively. Previous acclimation of fish to either elevated [Ca(2+)] or elevated [DOM] proved to be very effective in protecting against acute short-term metal accumulation at the gills of tambaqui in soft water (in the absence of the protective agent during metal exposure), suggesting a conditioning effect on gill metal binding physiology. PMID:16051381

  15. Cadmium, metal-binding proteins, and growth in bluegill (Lepomis macrochirus

    USGS Publications Warehouse

    Cope, W. Gregory; Wiener, James G.; Steingraeber, Mark T.; Atchison, Gary J.

    1994-01-01

    We exposed juvenile bluegill (Lepomis macrochirus) to ~1000 mg∙L−1 of continuously suspended river sediment in a 28-d test with six treatments (randomized block with one sediment-free control and five sediments ranging from 1.3 to 21.4 μg Cd∙g dry weight−1). Each treatment had three replicates, each with 25 fish. Growth was reduced by exposure to suspended sediment, probably due to physical effects of sediment on feeding and to toxicity in the treatment with the greatest concentrations of metals. Mean whole-body concentrations of cadmium (0.04–0.14 μg∙g wet weight−1) were correlated with cadmium concentration in filtered water (8–72 ng∙L−1), suspended sediment (0.61–16.8 μg∙L−1), and bulk sediment. The concentration of hepatic nonthionein cytosolic cadmium (cadmium not bound by metal-binding proteins, MBP) in fish exposed to the two most contaminated sediments exceeded that in controls. The mean concentration of hepatic MBP was correlated with cadmium concentration in filtered water, suspended sediment, bulk sediment, and whole fish. Whole-body cadmium concentration was the most sensitive indicator of cadmium exposure, with lowest observed effect concentrations of 1.9 μg Cd∙L−1 for suspended sediment and 13 ng Cd∙L−1 for filtered water. Sediment-associated cadmium was less available than waterborne cadmium for uptake by fish.

  16. Intrinsic disorder and metal binding in UreG proteins from Archae hyperthermophiles: GTPase enzymes involved in the activation of Ni(II) dependent urease.

    PubMed

    Miraula, Manfredi; Ciurli, Stefano; Zambelli, Barbara

    2015-06-01

    Urease is a Ni(II) enzyme present in every domain of life, in charge for nitrogen recycling through urea hydrolysis. Its activity requires the presence of two Ni(II) ions in the active site. These are delivered by the concerted action of four accessory proteins, named UreD, UreF, UreG and UreE. This process requires protein flexibility at different levels and some disorder-to-order transition events that coordinate the mechanism of protein-protein interaction. In particular, UreG, the GTPase in charge of nucleotide hydrolysis required for urease activation, presents a significant degree of intrinsic disorder, existing as a conformational ensemble featuring characteristics that recall a molten globule. Here, the folding properties of UreG were explored in Archaea hyperthermophiles, known to generally feature significantly low level of structural disorder in their proteome. UreG proteins from Methanocaldococcus jannaschii (Mj) and Metallosphaera sedula (Ms) were structurally and functionally analyzed by integrating circular dichroism, NMR, light scattering and enzymatic assays. Metal-binding properties were studied using isothermal titration calorimetry. The results indicate that, as the mesophilic counterparts, both proteins contain a significant amount of secondary structure but maintain a flexible fold and a low GTPase activity. As opposed to other UreGs, secondary structure is lost at high temperatures (68 and 75 °C, respectively) with an apparent two-state mechanism. Both proteins bind Zn(II) and Ni(II), with affinities two orders of magnitude higher for Zn(II) than for Ni(II). No major modifications of the average conformational ensemble are observed, but binding of Zn(II) yields a more compact dimeric form in MsUreG. PMID:25846143

  17. Metal Binding Specificity of the MntABC Permease of Neisseria gonorrhoeae and Its Influence on Bacterial Growth and Interaction with Cervical Epithelial Cells▿ †

    PubMed Central

    Lim, Karen H. L.; Jones, Christopher E.; vanden Hoven, Rachel N.; Edwards, Jennifer L.; Falsetta, Megan L.; Apicella, Michael A.; Jennings, Michael P.; McEwan, Alastair G.

    2008-01-01

    mntABC from Neisseria gonorrhoeae encodes an ABC permease which includes a periplasmic divalent cation binding receptor protein of the cluster IX family, encoded by mntC. Analysis of an mntC mutant showed that growth of N. gonorrhoeae could be stimulated by addition of either manganese(II) or zinc(II) ions, suggesting that the MntABC system could transport both ions. In contrast, growth of the mntAB mutant in liquid culture was possible only when the medium was supplemented with an antioxidant such as mannitol, consistent with the view that ion transport via MntABC is essential for protection of N. gonorrhoeae against oxidative stress. Using recombinant MntC, we determined that MntC binds Zn2+ and Mn2+ with almost equal affinity (dissociation constant of ∼0.1 μM). Competition assays with the metallochromic zinc indicator 4-(2-pyridylazo)resorcinol showed that MntC binds Mn2+ and Zn2+ at the same binding site. Analysis of the N. gonorrhoeae genome showed that MntC is the only Mn/Zn metal binding receptor protein cluster IX in this bacterium, in contrast to the situation in many other bacteria which have systems with dedicated Mn and Zn binding proteins as part of distinctive ABC cassette permeases. Both the mntC and mntAB mutants had reduced intracellular survival in a human cervical epithelial cell model and showed reduced ability to form a biofilm. These data suggest that the MntABC transporter is of importance for survival of Neisseria gonorrhoeae in the human host. PMID:18426887

  18. A silica gel based method for extracting insect surface hydrocarbons.

    PubMed

    Choe, Dong-Hwan; Ramírez, Santiago R; Tsutsui, Neil D

    2012-02-01

    Here, we describe a novel method for the extraction of insect cuticular hydrocarbons using silica gel, herein referred to as "silica-rubbing". This method permits the selective sampling of external hydrocarbons from insect cuticle surfaces for subsequent analysis using gas chromatography-mass spectrometry (GC-MS). The cuticular hydrocarbons are first adsorbed to silica gel particles by rubbing the cuticle of insect specimens with the materials, and then are subsequently eluted using organic solvents. We compared the cuticular hydrocarbon profiles that resulted from extractions using silica-rubbing and solvent-soaking methods in four ant and one bee species: Linepithema humile, Azteca instabilis, Camponotus floridanus, Pogonomyrmex barbatus (Hymenoptera: Formicidae), and Euglossa dilemma (Hymenoptera: Apidae). We also compared the hydrocarbon profiles of Euglossa dilemma obtained via silica-rubbing and solid phase microextraction (SPME). Comparison of hydrocarbon profiles obtained by different extraction methods indicates that silica rubbing selectively extracts the hydrocarbons that are present on the surface of the cuticular wax layer, without extracting hydrocarbons from internal glands and tissues. Due to its surface specificity, efficiency, and low cost, this new method may be useful for studying the biology of insect cuticular hydrocarbons.

  19. Construction of a multi-functional cryogenic propellant tank with cross-linked silica aerogel

    NASA Astrophysics Data System (ADS)

    Reinheimer, Preston Glenn

    Aerogels are low-density nanostructured porous materials, whose practical applications have been limited by their poor mechanical properties. Crosslinking the nanoparticle building blocks of silica aerogels with polymeric tethers increases both the modulus and the strength significantly. The polymer coating preserves the mesoporous structure of the silica framework while retaining its low thermal conductivity. The uniqueness of crosslinked silica aerogel has load carrying capabilities in which are determined in tensile, compression and flexural bending tests. Crosslinked silica aerogel testing displays specific compressive strength of 389000 Nm/Kg. Ballistic testing of crosslinked silica aerogel also corroborates its mechanical properties displaying a ballistic limit up to 80 m/s. Its thermal conductivity at 0.041 W/mK supports the use of crosslinked silica aerogel in cryogenic fuel cell applications. Manufacturing practices have been evaluated to obtain an optimal process which reduces time, money and difficulty.

  20. A research on the radiation shielding effects of clay, silica fume and cement samples

    NASA Astrophysics Data System (ADS)

    Akbulut, Suat; Sehhatigdiri, Arvin; Eroglu, Hayrettin; Çelik, Semet

    2015-12-01

    Nowadays, as the application areas of nuclear technology increases, protection from radiation has become even more important. Especially, the importance of radiation-shielding is important for the environment and employees which are in close proximity. Clays can be used as additives for shielding the radioactive materials. In this study, the shielding properties of micronize clay-white cement, clay-silica fume, gypsum, gypsum-silica fume, cement, white cement, cement-silica fume, white cement-gypsum, white cement-silica fume, red mud-silica fume, silica fume and red mud at different energy levels were examined. Additionally, compaction and unconfined compression tests were carried out on the samples. The results of clays and other samples were compared with each other. As a result, it was found that clays, especially clay-white cement mixture were superior than other samples in radioactive shielding.

  1. Reactivity characteristics of nanoscale zerovalent iron--silica composites for trichloroethylene remediation.

    PubMed

    Zheng, Tonghua; Zhan, Jingjing; He, Jibao; Day, Christopher; Lu, Yunfeng; McPherson, Gary L; Piringer, Gerhard; John, Vijay T

    2008-06-15

    Spherical silica particles containing nanoscale zerovalent iron were synthesized through an aerosol-assisted process. These particles are effective for groundwater remediation, with the environmentally benign silica particles serving as effective carriers for nanoiron transport. Incorporation of iron into porous sub-micrometer silica particles protects ferromagnetic iron nanoparticles from aggregation and may increase their subsurface mobility. Additionally, the presence of surface silanol groups on silica particles allows control of surface properties via silanol modification using organic functional groups. Aerosolized silica particles with functional alkyl moieties, such as ethyl groups on the surface, clearly adsorb solubilized trichloroethylene (TCE) in water. These materials may therefore act as adsorbents which have coupled reactivity characteristics. The nanoscale iron/silica composite particles with controlled surface properties have the potential to be efficiently applied for in situ source depletion and in the design of permeable reactive barriers.

  2. A new microporous polymorph of silica isomorphous to zeolite MCM-22

    SciTech Connect

    Camblor, M.A.; Corell, C.; Corma, A.

    1996-10-01

    A zeolite-like silica polymorph was prepared and given the descriptor, ITQ-1. The synthesis of this silica and high Si/Al aluminosilicates is described. The structure of the these materials was studied by X-ray diffraction and NMR.

  3. Bimodal mesoporous silica with bottleneck pores.

    PubMed

    Reber, M J; Brühwiler, D

    2015-11-01

    Bimodal mesoporous silica consisting of two sets of well-defined mesopores is synthesized by a partial pseudomorphic transformation of an ordered mesoporous starting material (SBA-15 type). The introduction of a second set of smaller mesopores (MCM-41 type) establishes a pore system with bottlenecks that restricts the access to the core of the bimodal mesoporous silica particles. The particle size and shape of the starting material are retained, but micropores present in the starting material disappear during the transformation, leading to a true bimodal mesoporous product. A varying degree of transformation allows the adjustment of the pore volume contribution of the two mesopore domains. Information on the accessibility of the mesopores is obtained by the adsorption of fluorescence-labeled poly(amidoamine) dendrimers and imaging by confocal laser scanning microscopy. This information is correlated with nitrogen sorption data to provide insights regarding the spatial distribution of the two mesopore domains. The bimodal mesoporous materials are excellent model systems for the investigation of cavitation effects in nitrogen desorption isotherms. PMID:26399172

  4. HVI Ballistic Limit Characterization of Fused Silica Thermal Panes

    NASA Technical Reports Server (NTRS)

    Miller, J. E.; Bohl, W. D.; Christiansen, E. L.; Davis, B. A.; Deighton, K. D.

    2015-01-01

    Fused silica window systems are used heavily on crewed reentry vehicles, and they are currently being used on the next generation of US crewed spacecraft, Orion. These systems improve crew situational awareness and comfort, as well as, insulating the reentry critical components of a spacecraft against the intense thermal environments of atmospheric reentry. Additionally, these materials are highly exposed to space environment hazards like solid particle impacts. This paper discusses impact studies up to 10 km/s on a fused silica window system proposed for the Orion spacecraft. A ballistic limit equation that describes the threshold of perforation of a fuse silica pane over a broad range of impact velocities, obliquities and projectile materials is discussed here.

  5. Microwave attenuation of multiwalled carbon nanotube-fused silica composites

    SciTech Connect

    Xiang Changshu; Pan Yubai; Liu Xuejian; Sun Xingwei; Shi Xiaomei; Guo Jingkun

    2005-09-19

    Multiwalled carbon nanotubes (MWCNTs) were used to convert radome materials to microwave absorbing materials. Dense MWCNT-fused silica composites were prepared by hot-pressing technique. The composites exhibit high complex permittivities at X-band frequencies, depending on the content of MWCNTs. The value of the loss tangent increases three orders over pure fused silica only by incorporating 2.5 vol % MWCNTs into the composites. The average magnitude of microwave transmission reaches -33 dB at 11-12 GHz in the 10 vol % MWCNT-fused silica composites, which indicates the composites have excellent microwave attenuation properties. The attenuation properties mainly originate from the electric loss of MWCNTs by the motion of conducting electrons.

  6. Immobilized lipid-bilayer materials

    DOEpatents

    Sasaki, Darryl Y.; Loy, Douglas A.; Yamanaka, Stacey A.

    2000-01-01

    A method for preparing encapsulated lipid-bilayer materials in a silica matrix comprising preparing a silica sol, mixing a lipid-bilayer material in the silica sol and allowing the mixture to gel to form the encapsulated lipid-bilayer material. The mild processing conditions allow quantitative entrapment of pre-formed lipid-bilayer materials without modification to the material's spectral characteristics. The method allows for the immobilization of lipid membranes to surfaces. The encapsulated lipid-bilayer materials perform as sensitive optical sensors for the detection of analytes such as heavy metal ions and can be used as drug delivery systems and as separation devices.

  7. Silica Debris Disk Evidence for Giant Planet Forming Impacts

    NASA Astrophysics Data System (ADS)

    Lisse, C.

    2014-04-01

    Giant impacts are major formation events in the history of our solar system. The final assembly of the planets, as we understand it, had to include massive fast collision events as the planets grew to objects with large escape velocities or in regions of high Keplerian velocities (Chambers 2004; Kenyon & Bromley 2004a,b, 2006; Fegley & Schaefer 2005). These massive impact events should create large amounts of glassy silica material derived from the rapid melting, vaporization, and refreezing of normal silicate rich primitive rocky material. We report here the detection of 4 bright silica-rich debris disks in the Spitzer IRS spectral archive, and the possible identification of 7 others. The stellar types of the system primaries span from A5V to G0V, their ages are 10 - 100 Myr, and the dust is warm, 280 - 480 K, and is located between 1.5 and 6 AU, well inside the systems' terrestrial planet regions. The minimum amount of detected 0.1 - 20 dust mass ranges from 10^21 - 10^23 kg; assuming < 10% dust formation efficiency (Benz 2009, 2011) this implies collisions involving impactors massing at least 10^22 - 10^24 kg, i.e. from Moon to Earth mass. We find possible trends in the mineralogy of the silica, with predominantly amorphous silica found in the 2 younger systems, and crystalline silica in the older systems. We speculate this is due higher velocity impacts found in younger, hotter systems, coupled with the effects of energetic photon annealing of small amorphous silica grains. All of these measures are consistent with the creation of silica rich rubble, or construction debris, during the terrestrial planet formation era of giant impacts.

  8. Quartz/fused silica chip carriers

    NASA Technical Reports Server (NTRS)

    1992-01-01

    The primary objective of this research and development effort was to develop monolithic microwave integrated circuit (MMIC) packaging which will operate efficiently at millimeter-wave frequencies. The packages incorporated fused silica as the substrate material which was selected due to its favorable electrical properties and potential performance improvement over more conventional materials for Ka-band operation. The first step towards meeting this objective is to develop a package that meets standard mechanical and thermal requirements using fused silica and to be compatible with semiconductor devices operating up to at least 44 GHz. The second step is to modify the package design and add multilayer and multicavity capacity to allow for application specific integrated circuits (ASIC's) to control multiple phase shifters. The final step is to adapt the package design to a phased array module with integral radiating elements. The first task was a continuation of the SBIR Phase 1 work. Phase 1 identified fused silica as a viable substrate material by demonstrating various plating, machining, and adhesion properties. In Phase 2 Task 1, a package was designed and fabricated to validate these findings. Task 2 was to take the next step in packaging and fabricate a multilayer, multichip module (MCM). This package is the predecessor to the phased array module and demonstrates the ability to via fill, circuit print, laminate, and to form vertical interconnects. The final task was to build a phased array module. The radiating elements were to be incorporated into the package instead of connecting to it with wire or ribbon bonds.

  9. Biofunctionalization of carbon nanostructures through enzyme immobilization in colloidal silica

    NASA Astrophysics Data System (ADS)

    Goulet, Evan M.

    Multi-walled carbon nanotubes (MWNT) and carbon nanopipettes (CNP) provide interesting high aspect ratio scaffolds on which to base functionally gradient materials. In this dissertation, we present a general method for the production of an enzymatically active composite material based on MWNTs. Polyethyleneimine (PEI) was applied to purified MWNTs, generating a positive electrostatic potential on the MWNTs. This positive potential was used to apply negatively charged colloidal silica particle in the presence of a high concentration of enzyme. The silica coating continued to grow via localized condensation of silica particles driven by the buffered saline conditions, immobilizing the enzyme within the coating. The mesoporous nanostructure was characterized via transmission electron microscopy. Optical spectroscopy experiments on the material employed as an active suspension showed that the immobilized enzymes horseradish peroxidase (HRP) and tyrosinase (TV) retained their activity upon incorporation into the material. Using HRP as a model enzyme, it was determined that the MWNT-HRP-Silica material showed similar pH and temperature dependencies in activity to those of free HRP in solution. An examination of the Michaelis-Menten kinetics showed that the material had a slightly higher value of KM than did free HRP. The MWNT-HRP-Silica material was also employed as an active filter membrane, which allowed us to explore the reusable nature of the material. We were able to show the denaturation of the filter due to the loss of Ca2+ cations at low pH and then restore the activity by soaking the filter membrane in 1 mM CaCl2. The MWNT-HRP-Silica material was used to modify a carbon microelectrode and produce a functioning electrochemical sensor for H2O2 . Utilizing cyclic voltammetry, the sensor was shown to have a linear response in limiting current versus concentration of H2O2 of 4.26 pA/microM. We also determined a lower detection limit of 0.67 microM H2O2. CNPs were

  10. Temperature and moisture dependence of dielectric constant for silica aerogels

    SciTech Connect

    Hrubesh, L.H., LLNL

    1997-03-01

    The dielectric constants of silica aerogels are among the lowest measured for any solid material. The silica aerogels also exhibit low thermal expansion and are thermally stable to temperatures exceeding 500{degrees}C. However, due to the open porosity and large surface areas for aerogels, their dielectric constants are strongly affected by moisture and temperature. This paper presents data for the dielectric constants of silica aerogels as a function of moisture content at 25{degrees}C, and as a function of temperature, for temperatures in the range from 25{degrees}C to 450{degrees}C. Dielectric constant data are also given for silica aerogels that are heat treated in dry nitrogen at 500{degrees}C, then cooled to 25{degrees}C for measurements in dry air. All measurements are made on bulk aerogel spheres at 22GHz microwave frequency, using a cavity perturbation method. The results of the dependence found here for bulk materials can be inferred to apply also to thin films of silica aerogels having similar nano-structures and densities.

  11. New porous polycaprolactone-silica composites for bone regeneration.

    PubMed

    Plazas Bonilla, Clara E; Trujillo, Sara; Demirdögen, Bermali; Perilla, Jairo E; Murat Elcin, Y; Gómez Ribelles, José L

    2014-07-01

    Polycaprolactone porous membranes were obtained by freeze extraction of dioxane from polycaprolactone-dioxane solid solutions. Porosities as high as 90% with interconnected structures were obtained by this technique. A silica phase was synthesized inside the pores of the polymer membrane by sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica precursor and catalyzed in acidic and basic conditions. Two different morphologies of the inorganic phase were obtained depending on the type of catalyst. In acid catalyzed sol-gel reaction, a homogeneous layer of silica was deposited on the pores, and discrete microspheres were synthesized on the pore walls when a basic catalyst was used. The morphology of the inorganic phase influenced the mechanical and thermal behavior, as well as the hydrophilic character of the composites. Bioactivity of the porous materials was tested in vitro by measuring the deposition of hydroxyapatite on the surfaces of the porous composite membranes. Polycaprolactone/silica composites revealed a superior bioactivity performance compared with that of the pure polymer; evidenced by the characteristic cauliflower structures on the material surface, increase in weight and Ca/P ratio of the hydroxyapatite layer. Also, the acid catalyzed composites presented better bioactivity than the base catalyzed composites, evidencing the importance in the morphology of the silica phase.

  12. Prediction of rigid silica based insulation conductivity

    NASA Technical Reports Server (NTRS)

    Williams, Stanley D.; Curry, Donald M.

    1993-01-01

    A method is presented for predicting the thermal conductivity of low density, silica based fibrous insulators. It is shown that the method can be used to extend data values to the upper material temperature limits from those obtained from the test data. It is demonstrated that once the conductivity is accurately determined by the analytical model the conductivity for other atmospheres can be predicted. The method is similar to that presented by previous investigators, but differs significantly in the contribution due to gas and internal radiation.

  13. Nanocomposite hydrogels for cartilage tissue engineering: mesoporous silica nanofibers interlinked with siloxane derived polysaccharide.

    PubMed

    Buchtová, Nela; Réthoré, Gildas; Boyer, Cécile; Guicheux, Jérôme; Rambaud, Frédéric; Vallé, Karine; Belleville, Philippe; Sanchez, Clément; Chauvet, Olivier; Weiss, Pierre; Le Bideau, Jean

    2013-08-01

    Injectable materials for mini-invasive surgery of cartilage are synthesized and thoroughly studied. The concept of these hybrid materials is based on providing high enough mechanical performances along with a good medium for chondrocytes proliferation. The unusual nanocomposite hydrogels presented herein are based on siloxane derived hydroxypropylmethylcellulose (Si-HPMC) interlinked with mesoporous silica nanofibers. The mandatory homogeneity of the nanocomposites is checked by fluorescent methods, which show that the silica nanofibres dispersion is realized down to nanometric scale, suggesting an efficient immobilization of the silica nanofibres onto the Si-HPMC scaffold. Such dispersion and immobilization are reached thanks to the chemical affinity between the hydrophilic silica nanofibers and the pendant silanolate groups of the Si-HPMC chains. Tuning the amount of nanocharges allows tuning the resulting mechanical features of these injectable biocompatible hybrid hydrogels. hASC stem cells and SW1353 chondrocytic cells viability is checked within the nanocomposite hydrogels up to 3 wt% of silica nanofibers.

  14. The Influence of Block Copolymers on the Rheology of Silica-Filled Polyisoprene

    NASA Astrophysics Data System (ADS)

    Gurovich, Daniel; Macosko, Christopher; Tirrell, Matthew

    2000-03-01

    The properties of filled polymeric materials depend on the balance between filler-filler and polymer-filler interactions. Polar surfaces of silica particles interact strongly with like polar surfaces, but not with the polyisoprene (PI) matrix. Thus, silica is difficult to disperse in polyisoprene, and the resulting dispersions tend to agglomerate upon aging. Polydimethyl siloxane (PDMS) strongly adsorbs onto silica surfaces via hydrogen bonds. Therefore, a PDMS-PI block copolymer is expected to anchor to a silica surface via its PDMS block and modify polymer-filler interactions. In the present work, precipitated silica, polyisoprene, and PDMS-PI copolymer are mixed in different formulations. The dynamic rheological properties of the resulting materials are measured, and the low-frequency storage modulus is used to assess filler-filler networking. The state of dispersion is visualized by transmission electron microscopy. The effects of aging on dispersions of different formulations are compared.

  15. Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica.

    PubMed

    Ji, Yazhou; Caskey, Christopher; Richards, Ryan M

    2015-01-01

    As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

  16. Toughening Mechanisms in Silica-Filled Epoxy Nanocomposites

    NASA Astrophysics Data System (ADS)

    Patel, Binay S.

    Epoxies are widely used as underfill resins throughout the microelectronics industry to mechanically couple and protect various components of flip-chip assemblies. Generally rigid materials largely surround underfill resins. Improving the mechanical and thermal properties of epoxy resins to better match those of their rigid counterparts can help extend the service lifetime of flip-chip assemblies. Recently, researchers have demonstrated that silica nanoparticles are effective toughening agents for lightly-crosslinked epoxies. Improvements in the fracture toughness of silica-filled epoxy nanocomposites have primarily been attributed to two toughening mechanisms: particle debonding with subsequent void growth and matrix shear banding. Various attempts have been made to model the contribution of these toughening mechanisms to the overall fracture energy observed in silica-filled epoxy nanocomposites. However, disparities still exist between experimental and modeled fracture energy results. In this dissertation, the thermal, rheological and mechanical behavior of eight different types of silica-filled epoxy nanocomposites was investigated. Each nanocomposite consisted of up to 10 vol% of silica nanoparticles with particle sizes ranging from 20 nm to 200 nm, with a variety of surface treatments and particle structures. Fractographical analysis was conducted with new experimental approaches in order to accurately identify morphological evidence for each proposed toughening mechanism. Overall, three major insights into the fracture behavior of real world silica-filled epoxy nanocomposites were established. First, microcracking was observed as an essential toughening mechanism in silica-filled epoxy nanocomposites. Microcracking was observed on the surface and subsurface of fractured samples in each type of silica-filled epoxy nanocomposite. The additional toughening contribution of microcracking to overall fracture energy yielded excellent agreement between experimental

  17. Modulation of microporous/mesoporous structures in self-templated cobalt-silica

    NASA Astrophysics Data System (ADS)

    Martens, Dana L.; Wang, David K.; Motuzas, Julius; Smart, Simon; da Costa, João C. Diniz

    2015-01-01

    Finite control of pore size distributions is a highly desired attribute when producing porous materials. While many methodologies strive to produce such materials through one-pot strategies, oftentimes the pore structure requires post-treatment modification. In this study, modulation of pore size in cobalt-silica systems was investigated by a novel, non-destructive, self-templated method. These systems were produced from two cobalt-containing silica starting materials which differed by extent of condensation. These starting materials, sol (SG') and xerogel (XG'), were mixed with pure silica sol to produce materials containing 5-40 mol% Co. The resultant SG-series materials exhibited typical attributes for cobalt-silica systems: mesoporous characteristics developed at high cobalt concentrations, coinciding with Co3O4 formation; whereas, in the XG-series materials, these mesoporous characteristics were extensively suppressed. Based on an examination of the resultant materials a mechanism describing the pore size formation and modulation of the two systems was proposed. Pore size modulation in the XG-series was caused, in part, by the cobalt source acting as an autogenous template for the condensation of the silica network. These domains could be modified when wetted, allowing for the infiltration and subsequent condensation of silica oligomers into the pre-formed, mesoporous cages, leading to a reduction in the mesoporous content of the final product.

  18. Formation of hook-shaped and straight silica wires by a thermal vapor method

    NASA Astrophysics Data System (ADS)

    Tao, Chuanyi; Li, Xueming; Yang, Wenjing

    2011-12-01

    Hook-shaped and straight silica wires have been successfully synthesized on silicon wafer through a simple thermal vapor method with or without assistance of Al, respectively. The hook-shaped silica wires have amorphous structures with nearly 100 μm long and about 4 μm in average diameters, while the straight silica wires are hundreds of micrometers long and approximately 50-300 nm in diameters. The composition analysis revealed that larger Al/SiOx islands can form on the silicon substrate with Al catalysts, whereas tiny silica clusters form without Al catalysts. They could act as the nucleation centers for the growth of silica wires with different shapes. The formation process of hook-shaped silica microwire results from a thermal gradient on the silicon substrate. The thermal gradient may be caused by the cold gas flowing during the process or other factors that lead to uneven temperature. On the contrary, straight growth of silica submicrowire is unacted on the thermal gradient factor due to the tiny silica clusters as nucleation centers. The present simple and low-cost process of producing hook-shaped and straight silica wires in bulk may lead to potential applications in catalysts, electrode materials, biosensing, etc.

  19. Silica particles cause NADPH oxidase–independent ROS generation and transient phagolysosomal leakage

    PubMed Central

    Joshi, Gaurav N.; Goetjen, Alexandra M.; Knecht, David A.

    2015-01-01

    Chronic inhalation of silica particles causes lung fibrosis and silicosis. Silica taken up by alveolar macrophages causes phagolysosomal membrane damage and leakage of lysosomal material into the cytoplasm to initiate apoptosis. We investigated the role of reactive oxygen species (ROS) in this membrane damage by studying the spatiotemporal generation of ROS. In macrophages, ROS generated by NADPH oxidase 2 (NOX2) was detected in phagolysosomes containing either silica particles or nontoxic latex particles. ROS was only detected in the cytoplasm of cells treated with silica and appeared in parallel with an increase in phagosomal ROS, as well as several hours later associated with mitochondrial production of ROS late in apoptosis. Pharmacological inhibition of NOX activity did not prevent silica-induced phagolysosomal leakage but delayed it. In Cos7 cells, which do not express NOX2, ROS was detected in silica-containing phagolysosomes that leaked. ROS was not detected in phagolysosomes containing latex particles. Leakage of silica-containing phagolysosomes in both cell types was transient, and after resealing of the membrane, endolysosomal fusion continued. These results demonstrate that silica particles can generate phagosomal ROS independent of NOX activity, and we propose that this silica-generated ROS can cause phagolysosomal leakage to initiate apoptosis. PMID:26202463

  20. Morphological and electronic properties of ultrathin crystalline silica epilayers on a Mo(112) substrate

    NASA Astrophysics Data System (ADS)

    Schroeder, T.; Giorgi, J. B.; Bäumer, M.; Freund, H.-J.

    2002-10-01

    Ultrathin crystalline silica layers grown on a Mo(112) substrate have been shown to be a useful silica model oxide support in surface science model catalyst studies. As the oxide support material plays an important role in the catalytic process, a multitechnique surface science study is presented to characterize the morphological and electronic properties of the heteroepitaxial system SiO2/Mo(112). The long-range order of the silica epilayer which grows commensurate with a c(2×2) surface unit mesh on the Mo(112) substrate is studied by low-energy electron diffraction (LEED). The defect structure of the silica epilayer is characterized in a spot profile analysis (SPA)-LEED study. Antiphase domain boundaries split the silica epilayer into an array of silica crystal grains whose average size and shape is determined. Aiming to prepare flat silica surfaces, the change in the surface roughness with progress in the film preparation is monitored in a combined SPA-LEED and scanning tunneling microscopy (STM) study and seen to influence also the Si-O stretching frequency in the infrared-reflection-absorption spectroscopy spectra. In STM images of the final silica film an average surface roughness of about 1 Å is detected. It is possible to visualize the silica film unit cell periodicity. A combined anger electron spectroscopy and ultraviolet photoelectron spectroscopy valence band study confirms the silica film stoichiometry and the growth of a 4:2 coordinated silica polymorph on the Mo(112) surface. These various surface science studies allow us to propose models for the growth and structure of the silica epilayer on the Mo(112) surface.

  1. Silica-based mesoporous nanoparticles for controlled drug delivery

    PubMed Central

    Kwon, Sooyeon; Singh, Rajendra K; Perez, Roman A; Abou Neel, Ensanya A

    2013-01-01

    Drug molecules with lack of specificity and solubility lead patients to take high doses of the drug to achieve sufficient therapeutic effects. This is a leading cause of adverse drug reactions, particularly for drugs with narrow therapeutic window or cytotoxic chemotherapeutics. To address these problems, there are various functional biocompatible drug carriers available in the market, which can deliver therapeutic agents to the target site in a controlled manner. Among the carriers developed thus far, mesoporous materials emerged as a promising candidate that can deliver a variety of drug molecules in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles are widely used as a delivery reagent because silica possesses favourable chemical properties, thermal stability and biocompatibility. Currently, sol-gel-derived mesoporous silica nanoparticles in soft conditions are of main interest due to simplicity in production and modification and the capacity to maintain function of bioactive agents. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release. The properties of mesopores, including pore size and porosity as well as the surface properties, can be altered depending on additives used to fabricate mesoporous silica nanoparticles. Active surface enables functionalisation to modify surface properties and link therapeutic molecules. The tuneable mesopore structure and modifiable surface of mesoporous silica nanoparticle allow incorporation of various classes of drug molecules and controlled delivery to the target sites. This review aims to present the state of knowledge of currently available drug delivery system and identify properties of an ideal drug carrier for specific application, focusing on mesoporous silica nanoparticles. PMID:24020012

  2. AN EXAMINATION OF THE CYTOTOXIC EFFECTS OF SILICA ON MACROPHAGES

    PubMed Central

    Allison, A. C.; Harington, J. S.; Birbeck, M.

    1966-01-01

    Effects of silica, diamond dust, and carrageenan on mouse macrophages were studied by phase-contrast cine-micrography, electron microscopy, histochemical techniques for lysosomal enzymes and measurements of the release of lysosomal enzymes into the culture medium. All added materials were rapidly taken up into phagosomes, to which lysosomes became attached. In all cases lysosomal enzymes were discharged into the phagosomes to form secondary lysosomes. Within 24 hr most of the silica particles and enzyme had escaped from the secondary lysosomes and lysosomal enzymes were found in the culture media. Most macrophages were killed by this time. With nontoxic particles (diamond dust, aluminium-coated silica, or silica in the presence of the protective agent polyvinyl-pyridine-N-oxide, PVPNO) ingested particles and lysosomal enzymes were retained within the secondary lysosomes for a much longer time, and cytotoxic effects were considerably delayed or absent altogether. It is concluded that silica particles are toxic because they are efficiently taken up by macrophages and can then react relatively rapidly with the membranes surrounding the secondary lysosomes. The particles and lytic enzymes can then escape into the cytoplasm, producing general damage, and thence into the culture medium. It is suggested that hydrogen bonding of silicic acid with lipid and protein constituents of the membrane accounts for the induced permeability. Protective agents such as PVPNO are retamed in lysosomes and preferentially form hydrogen bonds with silicic acid. Carrageenan is demonstrable within macrophages by its metachromatic reaction. It brings about release of enzymes from secondary lysosomes, but much more slowly than does silica. Silica released from killed macrophages is as cytotoxic as the original preparation. It is suggested that repeated cycles of macrophage killing in vivo leads to the mobilization of fibroblasts and fibrogenesis characterizing the disease silicosis. PMID

  3. Synthesis and structural evolution of mesoporous silica silver nanocomposites

    NASA Astrophysics Data System (ADS)

    Armelao, L.; Bottaro, G.; Campostrini, R.; Gialanella, S.; Ischia, M.; Poli, F.; Tondello, E.

    2007-04-01

    Mesoporous silica materials were prepared by a sol-gel procedure using Si(OCH2CH3)4 (TEOS) as the silica source and the non-ionic alkyl-poly(ethyleneoxide) oligomer Brij76 as the structure-directing agent. Pure inorganic hexagonal-like mesostructured SiO2 powders were obtained after annealing, performed in air between 400 and 600 °C. Upon calcination, the organic template was removed and silica networks with a different amount of Si-OH groups as well as porous features were prepared. Ag-SiO2 nanocomposites were obtained by metallation of the mesoporous silica powders with aqueous solutions of silver acetate. Ag+ ions were chemically grafted on the silica pores by taking advantage of the basic character of acetate anions and the acidic properties of Si-OH groups. Different silver concentrations were achieved on the mesostructured silica powders, depending on their former annealing treatment. For all samples the formation of silver nanoclusters occurred spontaneously at room temperature. Monodispersed, spherical Ag crystallites, with an average diameter of a few nanometres, were obtained starting from the 400 °C-treated silica, whereas clusters with different sizes (3-20 nm) and irregular shapes were grown for metallation of the 600 °C-heated SiO2 matrix. The sample's chemical composition was studied by x-ray photoelectron spectroscopy (XPS) and x-ray excited Auger electron spectroscopy (XE-AES), whereas the porous features were investigated by N2 BET adsorption. Information concerning structure and microstructure was obtained by x-ray diffraction (XRD) and transmission electron microscopy (TEM).

  4. Evaluation of silica nanoparticle binding to major human blood proteins

    NASA Astrophysics Data System (ADS)

    Hata, Katsutomo; Higashisaka, Kazuma; Nagano, Kazuya; Mukai, Yohei; Kamada, Haruhiko; Tsunoda, Shin-ichi; Yoshioka, Yasuo; Tsutsumi, Yasuo

    2014-12-01

    Nanomaterials are used for various biomedical applications because they are often more effective than conventional materials. Recently, however, it has become clear that the protein corona that forms on the surface of nanomaterials when they make contact with biological fluids, such as blood, influences the pharmacokinetics and biological responses induced by the nanomaterials. Therefore, when evaluating nanomaterial safety and efficacy, it is important to analyze the interaction between nanomaterials and proteins in biological fluids and to evaluate the effects of the protein corona. Here, we evaluated the interaction of silica nanoparticles, a commonly used nanomaterial, with the human blood proteins albumin, transferrin, fibrinogen, and IgG. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis showed that the amount of albumin, transferrin, and IgG binding to the silica particles increased as the particle size decreased under conditions where the silica particle mass remained the same. However, under conditions in which the specific surface area remained constant, there were no differences in the binding of human plasma proteins to the silica particles tested, suggesting that the binding of silica particles with human plasma proteins is dependent on the specific surface area of the silica particles. Furthermore, the amount of albumin, transferrin, and IgG binding to silica nanoparticles with a diameter of 70 nm (nSP70) and a functional amino group was lower than that with unmodified nSP70, although there was no difference in the binding between nSP70 with the surface modification of a carboxyl functional group and nSP70. These results suggest that the characteristics of nanomaterials are important for binding with human blood proteins; this information may contribute to the development of safe and effective nanomaterials.

  5. Multifunctional clickable and protein-repellent magnetic silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Estupiñán, Diego; Bannwarth, Markus B.; Mylon, Steven E.; Landfester, Katharina; Muñoz-Espí, Rafael; Crespy, Daniel

    2016-01-01

    Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the introduced surface functionality. Herein, organosilane chemistry is employed to produce magnetic silica nanoparticles bearing differing amounts of amino and alkene functional groups on their surface as orthogonally addressable chemical functionalities. Simultaneously, a short-chain zwitterion is added to decrease the non-specific adsorption of biomolecules on the nanoparticles surface. The multifunctional particles display reduced protein adsorption after incubation in undiluted fetal bovine serum as well as in single protein solutions (serum albumin and lysozyme). Besides, the particles retain their capacity to selectively react with biomolecules. Thus, they can be covalently bio-functionalized with an antibody by means of orthogonal click reactions. These features make the described multifunctional silica nanoparticles a promising system for the study of surface interactions with biomolecules, targeting, and bio-sensing.Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the

  6. Composites of silica with immobilized cholinesterase incorporated into polymeric shell

    NASA Astrophysics Data System (ADS)

    Payentko, Victoriya; Matkovsky, Alexander; Matrunchik, Yulia

    2015-02-01

    Synthetic approaches for new nanocomposite materials with relatively high cholinesterase activity have been developed. The peculiarity of the formation of such systems is the introduction of cholinesterase into polymer with subsequent incorporation on the ready-made silica particles and into the polysiloxane matrixes during sol-gel synthesis. Evaluation of the cholinesterase activity has been fulfilled through the imitation of the acetylcholine chloride decomposition reaction. Values of activity for cholinesterase nanocomposites demonstrated in this work are higher than those for the native cholinesterase. The higher activity of cholinesterase contained in nanocomposites was found for those prepared using highly dispersed silica.

  7. Using Nucleation Theory to Understand the Dissolution Kinetics of Vitreous and Biogenic Silica: The Paradox of the Silica Polymorphs

    NASA Astrophysics Data System (ADS)

    Han, N.; de Yoreo, J. J.; Wallace, A. F.; Dove, P. M.

    2006-12-01

    Recent studies of the global biogeochemistry are refocusing on the demineralization kinetics of biogenic silicas—amorphous silicas produced by marine phytoplankton, sponges and terrestrial plants. Amorphous silica lacks the crystalline order that can be studied with classical terrace, ledge, and kink-based models of crystal growth and dissolution. Despite variations in Si-O-Si bond lengths and angles, all of these materials share the same fundamental chemical unit, silica tetrahedron. Silica tetrahedra on quartz surfaces have distinct hydration chemistries with two predominant types of sites available for reaction with water: gamma species have a higher degree of connectivity with the mineral surface via binding to three bridging oxygens while beta groups are bonded to two bridging oxygens. Surface groups of amorphous silica have the same coordinations as gamma and beta species in quartz. Support for the idea that crystalline and amorphous SiO2 exhibit similar dissolution and growth reaction pathways are found in rate data reported for the synthetic and biogenic amorphous silicas and quartz. Previous studies show that the `bulk' rate of silica production by quartz and amorphous silica is enhanced 50- 100 fold when alkaline or alkaline earth cations are introduced to otherwise pure solutions. Our recent study of quartz dissolution found this `salt effect' arises by a transition from dissolution at preexisting step edges and dislocation defects (detachment of beta species) to the homogeneous nucleation of vacancy islands across the entire surface (plucking of gamma species) in CaCl2 and NaCl solutions. This transition to homogeneous nucleation results in an exponential dependence of quartz dissolution rate on increasing chemical driving force (undersaturation) that is explained by the classical nucleation theory that was developed for crystal growth. We pose the question of why amorphous silica should also be enhanced 100-fold by electrolytes. From a mechanistic

  8. New support for high-performance liquid chromatography based on silica coated with alumina particles.

    PubMed

    Silveira, José Leandro R; Dib, Samia R; Faria, Anizio M

    2014-01-01

    A new material based on silica coated with alumina nanoparticles was proposed for use as a chromatographic support for reversed-phase high-performance liquid chromatography. Alumina nanoparticles were synthesized by a sol-gel process in reversed micelles composed of sodium bis(2-ethylhexyl)sulfosuccinate, and the support material was formed by the self-assembly of alumina layers on silica spheres. Spectroscopic and (29)Si nuclear magnetic resonance results showed evidence of chemical bonds between the alumina nanoparticles and the silica spheres, while morphological characterizations showed that the aluminized silica maintained the morphological properties of silica desired for chromatographic purposes after alumina incorporation. Stability studies indicated that bare silica showed high dissolution (~83%), while the aluminized silica remained practically unchanged (99%) after passing one liter of the alkaline mobile phase, indicating high stability under alkaline conditions. The C18 bonded aluminized silica phase showed great potential for use in high-performance liquid chromatography to separate basic molecules in the reversed-phase mode.

  9. Surface Patterning of Silica Nanostructures Using Bio-Inspired Templates and Directed Synthesis

    SciTech Connect

    Coffman, Elizabeth A; Melechko, Anatoli Vasilievich; Allison, David P; Simpson, Michael L; Doktycz, Mitchel John

    2004-01-01

    Natural systems excel in directing the synthesis of inorganic materials for various functional purposes. One of the best-studied systems is silica synthesis, as occurs in diatoms and marine sponges. Various biological and synthetic polymers have been shown to template and catalyze silica formation from silicic acid precursors. Here, we describe the use of poly-l-lysine to promote the synthesis of silica in neutral, aqueous solution and when immobilized onto a silicon support structure under similar conditions. Either reagent jetting or conventional photolithography techniques can be used to pattern the templating polymer. Spots created by reagent jetting led to the creation of silica structures in the shape of a ring that may be a result of the spotting process. Photolithographically defined poly-l-lysine spots led to thin laminate structures after exposure to a dilute aqueous silicic acid solution. The laminate structures were nanostructured and highly interconnected. Photolithographic patterning of (3-aminopropyl)trimethoxysilane, a reagent that mimics the lysine functional group, led to similar silica coatings even though low-molecular-weight materials do not rapidly promote silica synthesis in solution. This result highlights the importance of functional-group arrangement for templating and promoting the synthesis of inorganic materials. The described surface-patterning techniques offer a route to integrate conventional silicon-patterning technologies with biologically based material synthesis. Such combined fabrication techniques enable controlled assembly over multiple length scales and an approach to understanding interfacial silica synthesis, as occurs in natural systems.

  10. Environmentally-Friendly Geopolymeric Binders Made with Silica

    NASA Astrophysics Data System (ADS)

    Erdogan, S. T.

    2013-12-01

    Portland cement (PC) is the ubiquitous binding material for constructions works. It is a big contributor to global warming and climate change since its production is responsible for 5-10 % of all anthropogenic CO2 emissions. Half of this emission arises from the calcination of calcareous raw materials and half from kiln fuel burning and cement clinker grinding. Recently there have been efforts to develop alternative binders with lower greenhouse gas emissions. One such class of binders is geopolymers, formed by activating natural or waste materials with suitable alkaline or acidic solutions. These binders use natural or industrial waste raw materials with a very low CO2 footprint from grinding of the starting materials, and some from the production of the activating chemicals. The total CO2 emissions from carefully formulated mixtures can be as low as 1/10th - 1/5th of those of PC concrete mixtures with comparable properties. While use of industrial wastes as raw materials is environmentally preferable, the variability of their chemical compositions over time renders their use difficult. Use of natural materials depletes resources but can have more consistent properties and can be more easily accepted. Silica sand is a natural material containing very high amounts of quartz. Silica fume is a very fine waste from silicon metal production that is mostly non-crystalline silica. This study describes the use of sodium hydroxide and sodium silicate solutions to yield mortars with mechanical properties comparable to those of portland cement mortars and with better chemical and thermal durability. Strength gain is slower than with PC mixtures at room temperature but adequate ultimate strength can be achieved with curing at slightly elevated temperatures in less than 24 h. The consistency of the chemical compositions of these materials and their abundance in several large, developing countries makes silica attractive for producing sustainable concretes with reduced carbon

  11. Mechanical and Thermal Characterization of Silica Nanocomposites

    NASA Astrophysics Data System (ADS)

    Cunningham, Anthony Lamar

    Polymer nanocomposites are a class of materials containing nanoparticles with a large interfacial surface area. Only a small quantity of nanoparticles are needed to provide superior multifunctional properties; such as mechanical, thermal, electrical, and moisture absorption properties in polymers. Nanoparticles tend to agglomerate, so special techniques are required for homogeneous distribution. Nanosilica is now readily available as colloidal sols, for example; Nanopox RTM F400 (supplied by Evonik Nanoresins AG, Germany). The nanoparticles are first synthesized from aqueous sodium silicate solution, and then undergo a surface modification process with organosilane and matrix exchange. F400 contains 40%wt silica nanoparticles colloidally dispersed in a DGEBA epoxy resin. The mean particle diameter is about 20 nm with a narrow distribution range of about 5 to 35 nm. The objectives of this study are to develop a reproducible processing method for nanosilica enhanced resin systems used in the manufacturing of fiber reinforced composites that will be characterized for mechanical and thermal properties. Research has concluded that shows improvements in the properties of the matrix material when processed in loading variations of 0 to 25%wt silica nanoparticles. The loadings were also used to manufacture fiberglass reinforced nanocomposite laminates and also tested for mechanical and thermal properties.

  12. Epoxy Crosslinked Silica Aerogels (X-Aerogels)

    NASA Technical Reports Server (NTRS)

    fabrizio, Eve; Ilhan, Faysal; Meador, Mary Ann; Johnston, Chris; Leventis, Nicholas

    2004-01-01

    NASA is interested in the development of strong lightweight materials for the dual role of thermal insulator and structural component for space vehicles; freeing more weight for useful payloads. Aerogels are very-low density materials (0.010 to 0.5 g/cc) that, due to high porosity (meso- and microporosity), can be, depending on the chemical nature of the network, ideal thermal insulators (thermal conductivity approx. 15 mW/mK). However, aerogels are extremely fragile. For practical application of aerogels, one must increase strength without compromising the physical properties attributed to low density. This has been achieved by templated growth of an epoxy polymer layer that crosslinks the "pearl necklace" network of nanoparticles: the framework of a typical silica aerogel. The requirement for conformal accumulation of the epoxy crosslinker is reaction both with the surface of silica and with itself. After cross-linking, the strength of a typical aerogel monolith increases by a factor of 200, in the expense of only a 2-fold increase in density. Strength is increased further by coupling residual unreacted epoxides with diamine.

  13. Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.

    2008-01-01

    Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.

  14. High Resolution, Single-Step Patterning of Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Bertino, M. F.; Hund, J. F.; Sosa, J.; Zhang, G.; Sotiriou-Leventis, C.; Leventis, N.; Tokuhiro, A. T.; Terry, J.

    2003-01-01

    Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag' ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 x 70 km, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed of Ag clusters with a size of several pm, separated by thin layers of silica.

  15. Controlled release of chlorhexidine from amorphous microporous silica.

    PubMed

    Verraedt, E; Pendela, M; Adams, E; Hoogmartens, J; Martens, J A

    2010-02-25

    A new system for the controlled release of the antiseptic chlorhexidine is presented. Amorphous microporous silica (AMS) excipient material was synthesized via an acid catalyzed sol-gel method and shaped as powder or coating. Chlorhexidine diacetate was introduced into the pores of the AMS silica via the incipient wetness impregnation method. This silica reservoir maintained a slow release of chlorhexidine over more than 7days. Chlorhexidine release was controlled by configurational diffusion in the AMS pores having free diameters of less than 1nm. The release of chlorhexidine was fine tuned by adapting particle size and pore diameter. Controlled release of chlorhexidine from an AMS coating on silicon wafer was demonstrated. PMID:19804804

  16. Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

    SciTech Connect

    Abellan, G.; Carrillo, A.I.; Linares, N.; Serrano, E.

    2009-08-15

    Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m{sup 2} g{sup -1}) and total pore volumes >=2 cm{sup 3} g{sup -1}. - Graphical abstract: Hierarchical bimodal porous silica and its carbon replica prepared by nanocasting.

  17. Mesoporous silica nanoparticles in target drug delivery system: A review

    PubMed Central

    Bharti, Charu; Nagaich, Upendra; Pal, Ashok Kumar; Gulati, Neha

    2015-01-01

    Due to lack of specification and solubility of drug molecules, patients have to take high doses of the drug to achieve the desired therapeutic effects for the treatment of diseases. To solve these problems, there are various drug carriers present in the pharmaceuticals, which can used to deliver therapeutic agents to the target site in the body. Mesoporous silica materials become known as a promising candidate that can overcome above problems and produce effects in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles (MSNs) are widely used as a delivery reagent because silica possesses favorable chemical properties, thermal stability, and biocompatibility. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release of the target site. The properties of mesoporous, including pore size, high drug loading, and porosity as well as the surface properties, can be altered depending on additives used to prepare MSNs. Active surface enables functionalization to changed surface properties and link therapeutic molecules. They are used as widely in the field of diagnosis, target drug delivery, bio-sensing, cellular uptake, etc., in the bio-medical field. This review aims to present the state of knowledge of silica containing mesoporous nanoparticles and specific application in various biomedical fields. PMID:26258053

  18. Oxidation and Volatilization of Silica-Formers in Water Vapor

    NASA Technical Reports Server (NTRS)

    Opila, E. J.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

  19. Quantification of Residual Stress from Photonic Signatures of Fused Silica

    NASA Technical Reports Server (NTRS)

    Cramer, K. Elliott; Hayward, Maurice; Yost, William E.

    2013-01-01

    A commercially available grey-field polariscope (GFP) instrument for photoelastic examination is used to assess impact damage inflicted upon the outer-most pane of Space Shuttle windows made from fused silica. A method and apparatus for calibration of the stress-optic coefficient using four-point bending is discussed. The results are validated on known material (acrylic) and are found to agree with literature values to within 6%. The calibration procedure is then applied to fused-silica specimens and the stress-optic coefficient is determined to be 2.43 +/- 0.54 x 10(exp -12)/Pa. Fused silica specimens containing impacts artificially made at NASA's Hypervelocity Impact Technology Facility (HIT-F), to simulate damage typical during space flight, are examined. The damage sites are cored from fused silica window carcasses and examined with the GFP. The calibrated GFP measurements of residual stress patterns surrounding the damage sites are presented. Keywords: Glass, fused silica, photoelasticity, residual stress

  20. Removal of formaldehyde from air using functionalized silica supports.

    PubMed

    Ewlad-Ahmed, Abdunaser M; Morris, Michael A; Patwardhan, Siddharth V; Gibson, Lorraine T

    2012-12-18

    This paper demonstrates the use of functionalized meso-silica materials (MCM-41 or SBA-15) as adsorbents for formaldehyde (H₂CO) vapor from contaminated air. Additionally new green nanosilica (GNs) materials were prepared via a bioinspired synthesis route and were assessed for removal of H₂CO from contaminated indoor air. These exciting new materials were prepared via rapid, 15 min, environmentally friendly synthesis routes avoiding any secondary pollution. They provided an excellent platform for functionalization and extraction of H₂CO demonstrating similar performance to the conventional meso-silica materials. To the authors' knowledge this is the first reported practical application of this material type. Prior to trapping, all materials were functionalized with amino-propyl groups which led to chemisorption of H₂CO; removing it permanently from air. No retention of H₂CO was achieved with nonfunctionalized material and it was observed that best extraction performance required a dynamic adsorption setup when compared to passive application. These results demonstrate the first application of GNs as potential adsorbents and functionalized meso-silica for use in remediation of air pollution in indoor air.

  1. Removal of formaldehyde from air using functionalized silica supports.

    PubMed

    Ewlad-Ahmed, Abdunaser M; Morris, Michael A; Patwardhan, Siddharth V; Gibson, Lorraine T

    2012-12-18

    This paper demonstrates the use of functionalized meso-silica materials (MCM-41 or SBA-15) as adsorbents for formaldehyde (H₂CO) vapor from contaminated air. Additionally new green nanosilica (GNs) materials were prepared via a bioinspired synthesis route and were assessed for removal of H₂CO from contaminated indoor air. These exciting new materials were prepared via rapid, 15 min, environmentally friendly synthesis routes avoiding any secondary pollution. They provided an excellent platform for functionalization and extraction of H₂CO demonstrating similar performance to the conventional meso-silica materials. To the authors' knowledge this is the first reported practical application of this material type. Prior to trapping, all materials were functionalized with amino-propyl groups which led to chemisorption of H₂CO; removing it permanently from air. No retention of H₂CO was achieved with nonfunctionalized material and it was observed that best extraction performance required a dynamic adsorption setup when compared to passive application. These results demonstrate the first application of GNs as potential adsorbents and functionalized meso-silica for use in remediation of air pollution in indoor air. PMID:23181357

  2. Bioactive and biodegradable silica biomaterial for bone regeneration.

    PubMed

    Wang, Shunfeng; Wang, Xiaohong; Draenert, Florian G; Albert, Olga; Schröder, Heinz C; Mailänder, Volker; Mitov, Gergo; Müller, Werner E G

    2014-10-01

    containing implants and implants, composed of a 1:1 mixture of silica-containing microspheres and silicatein-containing microspheres, show an enhanced regeneration of bone tissue around the microspheres, compared to the control implants containing only β-TCP. The formation of new bone induced by the microspheres is also evident from measurements of the stiffness/reduced Young's modulus of the regenerated bone tissue. The reduced Young's modulus of the regenerating bone tissue around the implants was markedly higher for the silica-containing microspheres (1.1MPa), and even more for the 1:1 mixture of the silica- and silicatein-containing microspheres (1.4MPa), compared to the β-TCP microsphere controls (0.4MPa). We propose that based on their morphogenetic activity on bone-forming cells in vitro and the results of the animal experiments presented here, silica/biosilica-based scaffolds are promising materials for bone repair/regeneration.

  3. High temperature thermographic measurements of laser heated silica

    SciTech Connect

    Elhadj, S; Yang, S T; Matthews, M J; Cooke, D J; Bude, J D; Johnson, M; Feit, M; Draggoo, V; Bisson, S E

    2009-11-02

    In situ spatial and temporal surface temperature profiles of CO{sub 2} laser-heated silica were obtained using a long wave infrared (LWIR) HgCdTe camera. Solutions to the linear diffusion equation with volumetric and surface heating are shown to describe the temperature evolution for a range of beam powers, over which the peak surface temperature scales linearly with power. These solutions were used with on-axis steady state and transient experimental temperatures to extract thermal diffusivity and conductivity for a variety of materials, including silica, spinel, sapphire, and lithium fluoride. Experimentally-derived thermal properties agreed well with reported values and, for silica, thermal conductivity and diffusivity are shown to be approximately independent of temperature between 300 and 2800K. While for silica our analysis based on a temperature independent thermal conductivity is shown to be accurate, for other materials studied this treatment yields effective thermal properties that represent reasonable approximations for laser heating. Implementation of a single-wavelength radiation measurement in the semi-transparent regime is generally discussed, and estimates of the apparent temperature deviation from the actual outer surface temperature are also presented. The experimental approach and the simple analysis presented yield surface temperature measurements that can be used to validate more complex physical models, help discriminate dominant heat transport mechanisms, and to predict temperature distribution and evolution during laser-based material processing.

  4. Efficient HPLC purification of endohedral metallofullerenes on a porphyrin-silica stationary phase

    SciTech Connect

    Xiao, Jie; Savina, M.R.; Martin, G.B.; Francis, A.H.; Meyerhoff, M.E. )

    1994-10-05

    Endohedral metallofullrenes are among the most fascinating materials to emerge from ongoing efforts to produce and characterize closed-cage carbon compounds. In this paper, we describe the use of a new tetraphenylporphyrin-silica support material for efficient HPLC purification of the metallofullerenes from crude soot extract. The true single-stage separation from pyridine extracts demonstrates the unique chemical selectivity exhibited by employing [pi]-electron-rich tetraphenylporphyrin-silica stationary phases in chemical purifications. 18 refs., 3 figs.

  5. Luminescent studies of fluorescent chromophore-doped silica aerogels for flat panel display applications

    SciTech Connect

    Glauser, S.A.C.; Lee, H.W.H.

    1997-04-01

    The remarkable optical and electronic properties of doped and undoped silica aerogels establish their utility as unique, mulitfunctional host materials for fluorescent dyes and other luminescent materials for display and imaging applications. We present results on the photoluminescence, absorption, and photoluminescence excitation spectra of undoped silica aerogels and aerogels doped with Er{sup 3+}, rhodamine 6G (R6G), and fluorescein. 4 refs., 12 figs.

  6. The Toxicity of Precipitated Silica

    PubMed Central

    Byers, P. D.; Gage, J. C.

    1961-01-01

    The proportion of respirable particles in dust clouds generated from three samples of precipitated silica has been shown to range between one-quarter and one-third by weight. After a single intratracheal dose of the silicas to rats, chemical analysis shows a progressive disappearance of silica from the lungs, though it is still detectable after 12 months. Some silica appears in the liver and kidneys but in two of the three samples none remains after 12 months. The nature and duration of the lung lesions produced in rats after a single intratracheal injection are described. A mild degree of fibrosis was observed which showed a steady regression with time and was to some extent influenced by the nature of the silica injected. The lesions showed little resemblance to those arising from quartz and were more akin to those produced by non-fibrogenic dusts. Recommendations are made for the precautions to be taken during the industrial handling of these dusts. Images PMID:13875292

  7. Performance of concrete incorporating colloidal nano-silica

    NASA Astrophysics Data System (ADS)

    Zeidan, Mohamed Sabry

    Nanotechnology, as one of the most modern fields of science, has great market potential and economic impact. The need for research in the field of nanotechnology is continuously on the rise. During the last few decades, nanotechnology was developing rapidly into many fields of applied sciences, engineering and industrial applications, especially through studies of physics, chemistry, medicine and fundamental material science. These new developments may be attributed to the fact that material properties and performance can be significantly improved and controlled through nano-scale processes and nano-structures. This research program aims at 1) further understanding the behavior of cementitious materials when amended on the nano-scale level and 2) exploring the effect of this enhancement on the microstructure of cement matrix. This study may be considered as an important step towards better understanding the use of nano-silica in concrete. The main goal of the study is to investigate the effect of using colloidal nano-silica on properties of concrete, including mechanical properties, durability, transport properties, and microstructure. The experimental program that was conducted included a laboratory investigation of concrete mixtures in which nano-silica was added to cement or to a combination of cement and Class F fly ash. Various ratios of nano-silica were used in concrete mixtures to examine the extent and types of improvements that could be imparted to concrete. The conducted experimental program assessed these improvements in terms of reactivity, mechanical properties, and durability of the mixtures under investigation. Advanced testing techniques---including mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM)---were used to investigate the effect of nano-silica on the microstructure of the tested mixtures. In addition, the effect of nano-silica on the alkali-silica reaction (ASR) was examined using various techniques, including testing

  8. Study of silica templates in the rice husk and the carbon-silica nanocomposites produced from rice husk

    NASA Astrophysics Data System (ADS)

    Larichev, Yu. V.; Yeletsky, P. M.; Yakovlev, V. A.

    2015-12-01

    Carbon-silica nanocomposites obtained by rice husk carbonization in a fluidized-bed reactor using a deep oxidation copper-chromium catalyst were studied. Dispersion characteristics of the silica phase in these systems were determined by small-angle X-ray scattering (SAXS) using the full contrast technique. SiO2 was found in the initial rice husk as compact nanoparticles having a wide size distribution. This distribution consists of a narrow fraction with particle sizes from 1 to 7 nm and a wider fraction with particle sizes from 8 to 22 nm. Oxidative heat treatment of rice husk in a fluidized bed in the presence of the catalyst decreased the fraction of small SiO2 particles and increased the fraction of large ones. It was demonstrated that the particle size of silica in the carbon matrix can be determined selectively for deliberate design of porous carbon materials with desired properties.

  9. Silica nanorod-array films with very low refractive indices.

    PubMed

    Xi, J Q; Kim, Jong Kyu; Schubert, E F

    2005-07-01

    The refractive-index contrast is an important figure of merit for dielectric multilayer structures, optical resonators, and photonic crystals. This represents a strong driving force for novel materials that have refractive indices lower than those of conventional optically transparent materials. Silica nanorod-array dielectric films with unprecedented low refractive indices of 1.08 are demonstrated and shown to have viable optical properties including enhanced reflectivity of a single-pair distributed Bragg reflector.

  10. Reactivity of biogenic silica: Surface versus bulk charge density

    NASA Astrophysics Data System (ADS)

    Loucaides, Socratis; Behrends, Thilo; Van Cappellen, Philippe

    2010-01-01

    Acid-base titrations were carried out at three different ionic strengths (0.01, 0.1 and 0.7 M NaCl) on a range of marine and continental biosiliceous materials. The large variability in electrical charging behavior of the various materials is consistent with the existence of two pools of ionizable groups, one on the outer surface of and the other within the silica particles. The relative amounts of internal and external silanols were estimated by fitting a two-site complexation model to excess proton versus pH curves obtained at the different ionic strengths. For fresh diatom frustules and phytoliths, as well as recently deposited biosiliceous sediments, the abundance of internal silanols was of the same order of magnitude as, or exceeded, that of silanols on the external surface. Older biosiliceous materials exhibited lower proportions of internal groups, while a decrease in the relative amount of internal silanols was also observed for diatom frustules artificially aged in seawater. The existence of internal ionizable functional groups explains measured charge densities of biogenic silicas that largely exceed the theoretical site density of silica surfaces. Variations in the relative abundance of internal versus surface silanols further explain the non-uniform dependence of electrical charging on ionic strength, the lack of correlation between total charge density and dissolution kinetics, and the variable 950 cm -1 peak intensity in the infrared spectra of biogenic silicas. Dissolution rates correlate positively with the external charge, rather than the total charge build-up, as expected if dissolution only involves the removal of silicate units from the external surfaces of the particles. The progressive reduction with time of the internal to external silanol concentration ratio represents one of the mechanisms altering the material properties that affect the recycling and preservation of biogenic silica in earth surface environments.

  11. Novel nanocomposites from spider silk–silica fusion (chimeric) proteins

    PubMed Central

    Wong Po Foo, Cheryl; Patwardhan, Siddharth V.; Belton, David J.; Kitchel, Brandon; Anastasiades, Daphne; Huang, Jia; Naik, Rajesh R.; Perry, Carole C.; Kaplan, David L.

    2006-01-01

    Silica skeletal architectures in diatoms are characterized by remarkable morphological and nanostructural details. Silk proteins from spiders and silkworms form strong and intricate self-assembling fibrous biomaterials in nature. We combined the features of silk with biosilica through the design, synthesis, and characterization of a novel family of chimeric proteins for subsequent use in model materials forming reactions. The domains from the major ampullate spidroin 1 (MaSp1) protein of Nephila clavipes spider dragline silk provide control over structural and morphological details because it can be self-assembled through diverse processing methods including film casting and fiber electrospinning. Biosilica nanostructures in diatoms are formed in aqueous ambient conditions at neutral pH and low temperatures. The R5 peptide derived from the silaffin protein of Cylindrotheca fusiformis induces and regulates silica precipitation in the chimeric protein designs under similar ambient conditions. Whereas mineralization reactions performed in the presence of R5 peptide alone form silica particles with a size distribution of 0.5–10 μm in diameter, reactions performed in the presence of the new fusion proteins generate nanocomposite materials containing silica particles with a narrower size distribution of 0.5–2 μm in diameter. Furthermore, we demonstrate that composite morphology and structure could be regulated by controlling processing conditions to produce films and fibers. These results suggest that the chimeric protein provides new options for processing and control over silica particle sizes, important benefits for biomedical and specialty materials, particularly in light of the all aqueous processing and the nanocomposite features of these new materials. PMID:16769898

  12. Effect of molecular weight of poly(epsilon-caprolactone) on interpenetrating network structure, apatite-forming ability, and degradability of poly(epsilon-caprolactone)/silica nano-hybrid materials.

    PubMed

    Rhee, Sang-Hoon

    2003-05-01

    The effect of molecular weight of poly(epsilon-caprolactone) (PCL) on the bioactivity of a PCL/silica nano-hybrid containing calcium salt was investigated. Two hybrids were prepared with low and high molecular weight PCLs, respectively, through a sol-gel method. Their bioactivities were evaluated using a simulated body fluid (SBF), which had almost the same ion concentrations with human blood plasma. Fast and uniform nucleation and growth of the apatite crystals were observed to occur all through the hybrid surface when low molecular weight PCL was used, while slow and random nucleation and growth of the apatite crystals were observed to occur when high molecular weight PCL was used, after soaking for 3 days in the SBF. This phenomenon was explained in terms of the distribution and dispersion of silica phase in the hybrid and the ionic activity product of the apatite in the SBF, which were dependent on the free volume and degradation rate of non-bioactive PCL phase, respectively.

  13. Amorphous silica-like carbon dioxide.

    PubMed

    Santoro, Mario; Gorelli, Federico A; Bini, Roberto; Ruocco, Giancarlo; Scandolo, Sandro; Crichton, Wilson A

    2006-06-15

    Among the group IV elements, only carbon forms stable double bonds with oxygen at ambient conditions. At variance with silica and germania, the non-molecular single-bonded crystalline form of carbon dioxide, phase V, only exists at high pressure. The amorphous forms of silica (a-SiO2) and germania (a-GeO2) are well known at ambient conditions; however, the amorphous, non-molecular form of CO2 has so far been described only as a result of first-principles simulations. Here we report the synthesis of an amorphous, silica-like form of carbon dioxide, a-CO2, which we call 'a-carbonia'. The compression of the molecular phase III of CO2 between 40 and 48 GPa at room temperature initiated the transformation to the non-molecular amorphous phase. Infrared spectra measured at temperatures up to 680 K show the progressive formation of C-O single bonds and the simultaneous disappearance of all molecular signatures. Furthermore, state-of-the-art Raman and synchrotron X-ray diffraction measurements on temperature-quenched samples confirm the amorphous character of the material. Comparison with vibrational and diffraction data for a-SiO2 and a-GeO2, as well as with the structure factor calculated for the a-CO2 sample obtained by first-principles molecular dynamics, shows that a-CO2 is structurally homologous to the other group IV dioxide glasses. We therefore conclude that the class of archetypal network-forming disordered systems, including a-SiO2, a-GeO2 and water, must be extended to include a-CO2. PMID:16778885

  14. Protein-templated biomimetic silica nanoparticles.

    PubMed

    Jackson, Erienne; Ferrari, Mariana; Cuestas-Ayllon, Carlos; Fernández-Pacheco, Rodrigo; Perez-Carvajal, Javier; de la Fuente, Jesús M; Grazú, Valeria; Betancor, Lorena

    2015-03-31

    Biomimetic silica particles can be synthesized as a nanosized material within minutes in a process mimicked from living organisms such as diatoms and sponges. In this work, we have studied the effect of bovine serum albumin (BSA) as a template to direct the synthesis of silica nanoparticles (NPs) with the potential to associate proteins on its surface. Our approach enables the formation of spheres with different physicochemical properties. Particles using BSA as a protein template were smaller (∼250-380 nm) and were more monodisperse than those lacking the proteic core (∼700-1000 nm) as seen by dynamic light scattering (DLS), scanning electron microscopy (SEM), and environmental scanning electron microscopy (ESEM) analysis. The absence of BSA during synthesis produced silica nanoparticles without any porosity that was detectable by nitrogen adsorption, whereas particles containing BSA developed porosity in the range of 4 to 5 nm which collapsed on the removal of BSA, thus producing smaller pores. These results were in accordance with the pore size calculated by high-resolution transmission electron microscopy (HTEM). The reproducibility of the BSA-templated nanoparticle properties was determined by analyzing four batches of independent synthesizing experiments that maintained their properties. The high positive superficial charge of the nanoparticles facilitated adsorption under mild conditions of a range of proteins from an E. coli extract and a commercial preparation of laccase from Trametes versicolor. All of the proteins were quantitatively desorbed. Experiments conducted showed the reusability of the particles as supports for the ionic adsorption of the biomolecules. The protein loading capacity of the BSA-based biomimetic particles was determined using laccase as 98.7 ± 6.6 mg·g(-1) of particles.

  15. Biologically Inspired Flagella-Templated Silica Nanotubes

    NASA Astrophysics Data System (ADS)

    Jo, Wonjin

    The desire and need for various types of nanostructures have been met with challenges of feasibility, reproducibility, and long fabrication time. To work towards improved bottom-up methods of nanofabrication, bacterial flagella are particularly attractive bio-templates for nanotubes due to their tubular structures and small inner and outer diameters. In this work, flagella isolated from Salmonella typhimurium are used as bio-templates to fabricate silica mineralized nanotubes. The process involves as well-controlled hydrolysis and condensation reaction with aminopropyltriethoxysilane (APTES), followed by the addition of tetraethoxysilane (TEOS). By controlling the concentration of TEOS and the reaction time, a simple and precise method is developed for creating silica-minera