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Sample records for 3-mercaptopropyl trimethoxysilane mptms

  1. Morphology and conductivity of Au films on polydimethylsiloxane using (3-mercaptopropyl)trimethoxysilane (MPTMS) as an adhesion promoter

    NASA Astrophysics Data System (ADS)

    Osmani, Bekim; Deyhle, Hans; Weiss, Florian M.; Töpper, Tino; Karapetkova, Maria; Leung, Vanessa; Müller, Bert

    2016-04-01

    Dielectric elastomer actuators (DEA) are often referred to as artificial muscles due to their high specific continuous power, which is comparable to that of human skeletal muscles, and because of their millisecond response time. We intend to use nanometer-thin DEA as medical implant actuators and sensors to be operated at voltages as low as a few tens of volts. The conductivity of the electrode and the impact of its stiffness on the stacked structure are key to the design and operation of future devices. The stiffness of sputtered Au electrodes on polydimethylsiloxane (PDMS) was characterized using AFM nanoindentation techniques. 2500 nanoindentations were performed on 10 x 10 μm2 regions at loads of 100 to 400 nN using a spherical tip with a radius of (522 +/- 2) nm. Stiffness maps based on the Hertz model were calculated using the Nanosurf Flex-ANA system. The low adhesion of Au to PDMS has been reported in the literature and leads to the formation of Au-nanoclusters. The size of the nanoclusters was (25 +/- 10) nm and can be explained by the low surface energy of PDMS leading to a Volmer-Weber growth mode. Therefore, we propose (3-mercaptopropyl)trimethoxysilane (MPTMS) as a molecular adhesive to promote the adhesion between the PDMS and Au electrode. A beneficial side effect of these self-assembling monolayers is the significant improvement of the electrode's conductivity as determined by four-point probe measurements. Therefore, the application of a soft adhesive layer for building a dielectric elastomer actuator appears promising.

  2. Sulfonic acid-functionalized hybrid organic-inorganic proton exchange membranes synthesized by sol-gel using 3-mercaptopropyl trimethoxysilane (MPTMS)

    NASA Astrophysics Data System (ADS)

    Mosa, J.; Durán, A.; Aparicio, M.

    2015-11-01

    Organic/inorganic hybrid membranes based on (3-glycidoxypropyl) trimethoxysilane (GPTMS) and 3-mercaptopropyl trimethoxysilane (MPTMS) have been prepared by sol-gel method and organic polymerisation, as candidate materials for proton exchange membranes in direct alcohol fuel cell (DMFC) applications. The -SH groups of MPTMS are oxidized to sulfonic acid groups, which are attributed to enhance the proton conductivity of hybrid membranes. FTIR, XPS and contact angle were used to characterize and confirm the hybrid structure and oxidation reaction progress. Membranes characterization also includes ion exchange capacity, water uptake, methanol permeability and proton conductivity to confirm their applicability in fuel cells. All the membranes were homogeneous and thermally and chemically resistant. In particular, the hybrid membranes demonstrated proton conductivities as high as 0.16 S cm-1 at high temperature, while exhibiting a low methanol permeability as compared to Nafion®. These results are associated with proton conducting paths through the silica pseudo-PEO network in which sulfonic acid groups work as proton donor.

  3. Removal of nickel and cadmium heavy metals using nanofiber membranes functionalized with (3-mercaptopropyl)trimethoxysilane (TMPTMS).

    PubMed

    Zahabi, Saeed Reza; Hosseini Ravandi, Seyed Abdolkarim; Allafchian, Alireza

    2016-08-01

    Functionalized nanofibrous membranes have been produced via electrospinning with a polymer solution of 19% (w/w) of nylon 66 prepared in a formic acid/chloroform mixture (75:25 v/v). The optimum parameters of electrospinning, like voltage, flow rate, tip and collector distances, were achieved and produced nanofiber membranes with a thickness of 287 nm. Then the nanofiber membranes were functionalized by (3-mercaptopropyl)trimethoxysilane (TMPTMS) at various amounts. Three different initial concentrations of metal ions and three different levels of pH were chosen. The effect of filtration process parameters such as the initial concentration of metal solution, pH of the solution, and the amount of functionalizer trimethoxysilane (TMPTMS) on the adsorption was studied. In surveying filtration process parameters, the results showed that metal ion rejection increased by increasing the pH of the solution and decreased by increasing the initial concentration of the effluent. By increasing the amount of functionalizer, removal efficiency increased. The results showed that the maximum efficiency of absorption of cadmium and nickel were 93.0 and 97.6%, respectively, and the filtering mechanism of the membrane is the blocking pores type. The adsorption data of cadmium and nickel ions fitted particularly well with the Freundlich isotherm. PMID:27441858

  4. An ultra-sensitive nanoarray chip based on single-molecule sandwich immunoassay and TIRFM for protein detection in biologic fluids.

    PubMed

    Lee, Seungah; Cho, Nam-Pyo; Kim, Jung Dong; Jung, Hyungil; Kang, Seong Ho

    2009-05-01

    This paper describes a single-molecule sandwich immunoassay method that utilizes total internal reflection fluorescence microscopy (TIRFM) at the single-molecule level for nanoarray protein chip applications. Nanoarray patterning of a biotin-probe with a spot diameter of 179 +/- 1 nm was performed successfully on a (3-mercaptopropyl)trimethoxysilane (MPTMS)-coated glass substrate by atomic force microscopy (AFM). The formation of biotin patterns was confirmed directly by observing the heights of bound streptavidin and biotin-antibody on glass substrates using an AFM in contact mode. Target protein molecules (or antigen) at the zepto-molar (zM) concentration level (x 10(-21) M) were detected on MPTMS-coated glass nanoarray protein chips by TIRFM. Finally, cytokine clinical samples (i.e. TNF-alpha and IL-1alpha) as cancer marker protein molecules were applied to nanoarray protein chips, and detection limits were at 600 zM.

  5. Rapid removal of Hg(II) from aqueous solutions using thiol-functionalized Zn-doped biomagnetite particles.

    PubMed

    He, Feng; Wang, Wei; Moon, Ji-Won; Howe, Jane; Pierce, Eric M; Liang, Liyuan

    2012-08-01

    The surfaces of Zn-doped biomagnetite nanostructured particles were functionalized with (3-mercaptopropyl)trimethoxysilane (MPTMS) and used as a high-capacity and collectable adsorbent for the removal of Hg(II) from water. Fourier transform infrared spectroscopy (FTIR) confirmed the attachment of MPTMS on the particle surface. The crystallite size of the Zn-doped biomagnetite was ∼17 nm, and the thickness of the MPTMS coating was ∼5 nm. Scanning transmission electron microscopy and dynamic light scattering analyses revealed that the particles formed aggregates in aqueous solution with an average hydrodynamic size of 826 ± 32 nm. Elemental analyses indicate that the chemical composition of the biomagnetite is Zn(0.46)Fe(2.54)O(4), and the loading of sulfur is 3.6 mmol/g. The MPTMS-modified biomagnetite has a calculated saturation magnetization of 37.9 emu/g and can be separated from water within a minute using a magnet. Sorption of Hg(II) to the nanostructured particles was much faster than other commercial sorbents, and the Hg(II) sorption isotherm in an industrial wastewater follows the Langmuir model with a maximum capacity of ∼416 mg/g, indicating two -SH groups bonded to one Hg. This new Hg(II) sorbent was stable in a range of solutions, from contaminated water to 0.5 M acid solutions, with low leaching of Fe, Zn, Si, and S (<10%).

  6. Electron beam initiated grafting of methacryloxypropyl-trimethoxysilane to fused silica glass

    NASA Astrophysics Data System (ADS)

    Shmykov, A. Yu.; Mjakin, S. V.; Vasiljeva, I. V.; Filippov, V. N.; Vylegzhanina, M. E.; Sukhanova, T. E.; Kurochkin, V. E.

    2009-04-01

    The effect of electron beam pretreatment of fused silica glass upon its surface functional composition and possibility for subsequent immobilization of methacryloxypropyl-trimethoxysilane (MOPTMS) layer is studied using FTIR spectroscopy and adsorption of acid-base indicators. The content of Brensted acidic centers (silanol groups) on the irradiated fused silica surface is found to follow an "oscillatory" trend as function of the absorbed dose below 100 kGy at electron beam processing due to the alternating reactions of hydroxylation (probably as a result of Si-O-Si bond disruption and interaction with radiolyzed physically adsorbed water) and thermal dehydration/dehydroxylation at radiation heating. The best conditions for MOPTMS layer formation are based on the increased acidity of both silica surface (formation of acidic hydroxyls) and the reaction medium (MOPTMS deposition from acetic acid solution). The optimal value of absorbed dose at electron beam processing providing the highest efficiency of MOPTMS grafting is 50 kGy at accelerated electron energy 700 keV. Electron beam pretreatment of fused silica surface is shown to provide more efficient MOPTMS immobilization in comparison with conventional chemical and thermal grafting procedures. The obtained results are promising for the enhancement of the processes for the production of fused silica glass capillaries for electrochromatography and electrophoresis at the stage of an intermediate bifunctional layer formation required for the subsequent deposition of specific polymer coatings.

  7. Preparation and characterization of highly cross-linked polyimide aerogels based on polyimide containing trimethoxysilane side groups.

    PubMed

    Pei, Xueliang; Zhai, Wentao; Zheng, Wenge

    2014-11-11

    In this study, highly cross-linked and completely imidized polyimide aerogels were prepared from polyimide containing trimethoxysilane side groups, which was obtained as the condensation product of polyimide containing acid chloride side groups and 3-aminopropyltrimethoxysilane. After adding water and acid catalyst, the trimethoxysilane side groups hydrolyzed and condensed one another, and a continuous increase in the complex viscosities of the polyimide solutions with time was observed. The formed polyimide gels were dried by freeze-drying from tert-butyl alcohol to obtain polyimide aerogels, which consisted of a three-dimensional network of polyimide fibers tangled together. By varying the solution concentration of the polyimide containing trimethoxysilane side groups, polyimide aerogels with different densities (ranging from 0.19 to 0.42 g/cm(3)) were obtained. The resulting polyimide aerogels had small pore diameter (ranging from 20.7 to 58.3 nm), high surface area (ranging from 310 to 344 m(2)/g), high 5% weight loss temperature in air (at about 440 °C), and an excellent mechanical property. In addition, the glass transition temperature (349 °C) of the polyimide aerogels was much higher than that (210 °C) of the corresponding linear polyimide. So, even after being heated at 300 °C for 30 min, the porous structure of the polyimide aerogels was not completely destroyed. PMID:25340747

  8. Injection of synthesized FePt nanoparticles in hole-patterns for bit patterned media

    NASA Astrophysics Data System (ADS)

    Hachisu, Takuma; Sato, Wataru; Ishizuka, Shugo; Sugiyama, Atsushi; Mizuno, Jun; Osaka, Tetsuya

    2012-02-01

    FePt nanoparticles of uniform sizes, compositions, and crystal structures can be obtained by chemical synthesis. Additionally, the nanoparticles can be well dispersed by the adsorption of a surfactant on the nanoparticle surface. Previously, the immobilization of FePt nanoparticles on a thermal oxide Si substrate was carried out by chemical synthesis, utilizing the Pt-S bonding between the -SH functional group in (3-mercaptopropyl)trimethoxysilane, MPTMS and Pt in FePt nanoparticles. However, controlling FePt nanoparticle arrays by this synthesis method was very difficult. In the present study, we attempted to control the distortion of the arrangement of FePt nanoparticles using an MPTMS layer modified with a silane coupling reaction and a geometrical structure prepared by ultraviolet nanoimprint lithography (UV-NIL). In this study, the hole-patterns used for the geometrical structure on Si(1 0 0) were 200 nm wide, 40 nm deep, and had a 500 nm pitch. The 5.6 nm FePt nanoparticles were used to coat the hole-patterns by using a picoliter pipette. An XHR-SEM image clearly revealed that the FePt nanoparticles were successfully arranged as a single layer with an average pitch of 10.0 nm by Pt-S bonding in the hole-patterns on Si(1 0 0).

  9. Proton conducting sol-gel sulfonated membranes produced from 2-allylphenol, 3-glycidoxypropyl trimethoxysilane and tetraethyl orthosilicate

    NASA Astrophysics Data System (ADS)

    Mosa, J.; Durán, A.; Aparicio, M.

    An important research area in proton exchange membrane fuel cells (PEMFC) is devoted to the development of low cost membranes able to work at temperatures higher than 100 °C. In this work, homogeneous, transparent and crack-free hybrid membranes have been synthesized using tetraethyl orthosilicate (TEOS), 3-glycidoxipropyl trimethoxysilane (GPTMS) and 2-allylphenol (AP) as precursors. The synthesis of proton conducting membranes was performed by a post-sulfonation method using trimethylsilyl chlorosulfonate as a mild sulfonating agent. The water retention properties provided by sulfonate and hydroxyl groups and the high porosity leads to relatively high proton conductivity (maximum values around 1.3 × 10 -3 S cm -1 at 140 °C and 100% RH) for membranes treated at 180 °C and sulfonated for 2 h.

  10. Aqueous route to facile, efficient and functional silica coating of metal nanoparticles at room temperature

    NASA Astrophysics Data System (ADS)

    Shah, Kwok Wei; Sreethawong, Thammanoon; Liu, Shu-Hua; Zhang, Shuang-Yuan; Tan, Li Sirh; Han, Ming-Yong

    2014-09-01

    Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields.Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also

  11. New electrorheological fluid obtained from mercaptosilsesquioxane-modified silicate suspensions.

    PubMed

    Marins, Jéssica A; Dahmouche, Karim; Soares, Bluma G

    2013-01-01

    Ormosil based on mercaptosilsesquioxane-modified silicate (SiO2/SSQ-SH) particle was prepared by sol-gel process involving a co-condensation of the hydrolyzed 3-mercaptopropyl-trimethoxysilane (MPTMS) and tetraetoxysilane (TEOS). The resulting material was characterized by (29)Si solid nuclear magnetic resonance spectroscopy ((29)Si NMR), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FEG-SEM) and small angle X-ray scattering (SAXS). The (SiO2/SSQ-SH) particle presents a hierarchical structure, extending from micro to nanoscale and consisting of three structural levels. This SiO2/SSQ-SH particle was used for the first time as the dispersed phase in silicone oil suspension to develop a new electro-rheological fluid with a very good response under the action of electrical field from 1 to 4 kV/mm, whose values are comparable to those exhibited by other conventional ER fluids, under the influence of electric field. PMID:25428054

  12. Titanium dental implants surface-immobilized with gold nanoparticles as osteoinductive agents for rapid osseointegration.

    PubMed

    Heo, Dong Nyoung; Ko, Wan-Kyu; Lee, Hak Rae; Lee, Sang Jin; Lee, Donghyun; Um, Soong Ho; Lee, Jung Haeng; Woo, Yi-Hyung; Zhang, Lijie Grace; Lee, Deok-Won; Kwon, Il Keun

    2016-05-01

    Gold nanoparticles (GNPs) are quite attractive materials for use as osteogenic agents due to their potential effects on the stimulation of osteoblast differentiation. In this study, an osseo-integrated titanium (Ti) implant surface coated with GNPs was used for promotion of bone regeneration. We prepared a silanized Ti surface by chemical treatment of (3-Mercaptopropyl) trimethoxysilane (MPTMS) and immobilized the GNP layer (Ti-GNP) on their surfaces via Au-S bonding. The GNP layer is uniformly immobilized on the surface and the layer covers the titanium oxide surface well, as confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The Ti-GNP was used to investigate the effectiveness of this system both in vitro and in vivo. The in vitro results showed that the Ti-GNP significantly enhances the osteogenic differentiation with increased mRNA expression of osteogenic differentiation specific genes in human adipose-derived stem cells (ADSCs). Furthermore, the in vivo results showed that Ti-GNP had a significant influence on the osseous interface formation. Through these in vitro and vivo tests, we found that Ti-GNP can be useful as osseo-integration inducing dental implants for formation of an osseous interface and maintenance of nascent bone formation. PMID:26874978

  13. Direct thiol-ene photocoating of polyorganosiloxane microparticles.

    PubMed

    Kuttner, Christian; Maier, Petra C; Kunert, Carmen; Schlaad, Helmut; Fery, Andreas

    2013-12-31

    This work presents the modification of polyorganosiloxane microparticles by surface-initiated thiol-ene photochemistry. By this photocoating, we prepared different core/shell particles with a polymeric shell within narrow size distributions (PDI = 0.041-0.12). As core particle, we used highly monodisperse spherical polyorganosiloxane particles prepared from (3-mercaptopropyl)trimethoxysilane (MPTMS) with a radius of 0.49 μm. We utilize the high surface coverage of mercaptopropyl functions to generate surface-localized radicals upon irradiation with UVA-light without additional photoinitiator. The continuous generation of radicals was followed by a dye degradation experiment (UV/vis spectroscopy). Surface-localized radicals were used as copolymer anchoring sites ("grafting-onto" deposition of different PB-b-PS diblock copolymers) and polymerization initiators ("grafting-from" polymerization of PS). Photocoated particles were characterized for their morphology (SEM, TEM), size, and size distribution (DLS). For PS-coated particles, the polymer content (up to 24% in 24 h) was controlled by the polymerization time upon UVA exposure. The coating thickness was evaluated by thermogravimetric analysis (TGA) using a simple analytical core/shell model. Raman spectroscopy was applied to directly follow the time-dependent consumption of thiols by photoinitiation. PMID:24320891

  14. Titanium dental implants surface-immobilized with gold nanoparticles as osteoinductive agents for rapid osseointegration.

    PubMed

    Heo, Dong Nyoung; Ko, Wan-Kyu; Lee, Hak Rae; Lee, Sang Jin; Lee, Donghyun; Um, Soong Ho; Lee, Jung Haeng; Woo, Yi-Hyung; Zhang, Lijie Grace; Lee, Deok-Won; Kwon, Il Keun

    2016-05-01

    Gold nanoparticles (GNPs) are quite attractive materials for use as osteogenic agents due to their potential effects on the stimulation of osteoblast differentiation. In this study, an osseo-integrated titanium (Ti) implant surface coated with GNPs was used for promotion of bone regeneration. We prepared a silanized Ti surface by chemical treatment of (3-Mercaptopropyl) trimethoxysilane (MPTMS) and immobilized the GNP layer (Ti-GNP) on their surfaces via Au-S bonding. The GNP layer is uniformly immobilized on the surface and the layer covers the titanium oxide surface well, as confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The Ti-GNP was used to investigate the effectiveness of this system both in vitro and in vivo. The in vitro results showed that the Ti-GNP significantly enhances the osteogenic differentiation with increased mRNA expression of osteogenic differentiation specific genes in human adipose-derived stem cells (ADSCs). Furthermore, the in vivo results showed that Ti-GNP had a significant influence on the osseous interface formation. Through these in vitro and vivo tests, we found that Ti-GNP can be useful as osseo-integration inducing dental implants for formation of an osseous interface and maintenance of nascent bone formation.

  15. Nano-scaled hydroxyapatite/polymer composite I. Coating of sintered hydroxyapatite particles on poly(gamma-methacryloxypropyl trimethoxysilane)grafted silk fibroin fibers through chemical bonding.

    PubMed

    Furuzono, T; Kishida, A; Tanaka, J

    2004-01-01

    The inorganic-organic composite consisting of nano-scaled hydroxyapatite (HAp) and silk fibroin (SF) fibers was prepared through covalent linkage to develop a novel biomaterial for a soft-tissue-compatible material. The preparation of the composite was conducted through the three-step procedure consisting of chemical modification using 2-methacryloxyethyl isocyanate (MOI) monomer to introduce vinyl groups on SF, poly(gamma-methacryloxypropyl trimethoxysilane) (MPTS) graft-polymerization on SF, and coupling process between the surface of polyMPTS-grafted SF and HAp nano-particles. The amount of the graft-polymerization of polyMPTS through vinyl groups was well controlled by the reaction time. The nano-crystals were subsequently coated on the grafted fibers by heating at 120 degrees C for 2 h in a vacuum. The crystalline structure of the SF substrate did not change in the procedure. In the SEM observation of the composite surface, it was found that the bonded nano-crystals were separated and partially aggregated with several crystals attached on the SF fiber surface. The HAp particles adhered more strongly on the SF surface with separation or aggregation of several crystals than on the surface of the original SF after ultrasonic treatment.

  16. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    PubMed

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers.

  17. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    PubMed

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers. PMID:26652418

  18. Direct formation of S-nitroso silica nanoparticles from a single silica source.

    PubMed

    Chou, Hung-Chang; Chiu, Shih-Jiuan; Liu, Ying-Ling; Hu, Teh-Min

    2014-01-28

    Nitric oxide (NO) is a ubiquitous molecule in the body. Because of its multiple pathophysiologic roles, the potential for treating various diseases by the exogenous administration of NO has been under intensive investigation. However, the unstable, radical nature of NO poses a major challenge to the effective delivery of NO. Previously, silica nanoparticles synthesized by the traditional method have been developed into NO-carrying systems. In the present study, for the first time NO-carrying silica nanoparticles were prepared from a single silica precursor using a simple nanoprecipitation method. (3-Mercaptopropyl)-trimethoxysilane (MPTMS) was used as the sole silane source, which was subjected to acid-catalyzed S-nitrosation and condensation reactions in a one-pot organic phase. S-Nitroso silica nanoparticles (SNO-SiNPs) were then produced by injecting a smaller quantity of the organic phase into a larger amount of water without surfactants. Various preparation parameters were tested to obtain optimized conditions. Moreover, a phase diagram demonstrating the ouzo effect was constructed. The prepared SNO-SiNPs were spherical particles with a tunable size in the range of 100-400 nm. The nanoparticles in aqueous dispersions exhibited high colloid stability, possibly resulting from highly negatively charged surfaces. The result of solid-state (29)Si NMR shows the predominance of T(2) and T(3) silicon structures, suggesting that nanoparticles were formed from polycondensed silica species. In conclusion, NO-loaded silica nanoparticles have been directly prepared from a single silane precursor using a surfactant-free, low-energy, one-step nanoprecipitation approach. The method precludes the need for the initial formation of bare particles and subsequent functionalization steps. PMID:24410024

  19. An exploratory study of the effects of the dielectric-barrier-discharge surface pre-treatment on the self-assembly processes of a (3-Aminopropyl) trimethoxysilane on glass substrates

    NASA Astrophysics Data System (ADS)

    Cui, Nai-Yi; Liu, Chaozong; Brown, Norman M. D.; Meenan, Brian J.

    2007-06-01

    X-ray photoelectron spectrometry (XPS), Fourier transform infrared spectrometry (FTIR), secondary-ion-mass spectrometry (SIMS) and contact angle measurement have been used in study of the enhancement effect of substrate pre-treatment by dielectric-barrier-discharge (DBD) for the self-assembly of a (3-Aminopropyl) trimethoxysilane (APTS) on glass substrates. In results, the concentration of the APTS molecules self-assembled on the surfaces of both the acetone-washed and the DBD-treated substrates were more than three times of that on the as-supplied substrate. Meanwhile, the self-assembly (SA) layers grown on the DBD-treated substrates have the best quality compared to those grown on the substrates pre-treated in other ways in terms of the silane-substrate bonding and the order of arrangement of the silane molecules.

  20. Comparing Surfaces and Engineered Interfaces using Self-Assembled Monolayers (SAMs) and Injected SAMs Silanes

    SciTech Connect

    Morris, Mark J.; Simmons, Kevin L.

    2003-11-01

    The objective of this study was to show a comparison between property changes by formation of a self-assembled monolayer on the surface of PPG synthetic precipitated silica, which is a technique developed at PNNL, and by adding the SAMs silane chemical directly into the mixing bowl. These coatings have the potential to greatly increase the bond strength and enhance other properties between the particle and the rubber matrix of a rubber compound. Tensile testing measured peak stress and elongation at break. The increase in tensile strength shows how well the polymer-filler interfacial adhesion is doing. The study used five different SAM systems with a sulfur cured styrene butadiene rubber (SBR) tire rubber formulation. The three propylsilanes were propyl triethoxysilane, allyl triethoxysilane and 3-mercaptopropyl triethoxysilane. Five combinations of silanes were used in this study. The application of the silanes were 100% propyl triethoxy silane (100% Alkyl); a 10/90 mixture of allyl and propyl triethoxy silanes (10% vinyl/90% alkyl); a 50/50 mixture of the allyl and propyl (50% vinyl/50% alkyl); a 10/90mixture of 3-mercaptopropyl trimethoxysilane and propyl trimethoxysilane (10% mercaptan/90% alkyl) and lastly a 50/50 3-mercaptopropyl and propylsilanes (50% mercaptan/alkyl). The data not only shows improvement with SAMs, the peak stress data (ultimate strength) shows that the by changing the amount of silane content can change the physical properties

  1. Continuous ultrathin silver films deposited on SiO2 and SiNx using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hafezian, Soroush; Maloney, Kate; Lefebvre, Josianne; Martinu, Ludvik; Kéna-Cohen, Stéphane

    2016-09-01

    In this letter, we study the deposition of ultrathin silver films on silicon oxide and nitride surfaces functionalized with self-assembled monolayers of (3-mercaptopropyl)-trimethoxysilane. First, we compare both solution and vapour-phase functionalization techniques and find the greatest improvement in electrical and optical properties using deposition from solution. Using X-ray photoelectron spectroscopy, we demonstrate that the formation of silver-sulfur covalent bonds is at the root of the improved wetting confirmed by ellipsometry, sheet resistance measurement, and atomic force microscopy. Second, we show that this technique can be extended to functionalize silicon nitride. Finally, we demonstrate a simple, but efficient, low-emissivity optical filter.

  2. Novel titration method for surface-functionalised silica

    NASA Astrophysics Data System (ADS)

    Hofen, Kai; Weber, Siegfried; Chan, Chiu Ping Candace; Majewski, Peter

    2011-01-01

    This paper describes three inexpensive and fast analytical methods to characterise grafted particle surfaces. The reaction of silica with (3-aminopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane and N-(phosphonomethyl)iminodiacetic acid hydrate, respectively, leads to NH2-, SO3H- or COOH-functionalised silica, which were characterised by X-ray photoelectron spectrometry and titration in nonaqueous media as well as with two titration methods in a water-based environment. In the work presented, factors influencing the titrations are pointed out and solutions are presented to overcome these limiting factors are shown.

  3. Solvent optimization for niacinamide adsorption on organo-functionalized SBA-15 mesoporous silica

    NASA Astrophysics Data System (ADS)

    Moritz, Michał

    2013-10-01

    This work describes the application of organo-modified SBA-15 siliceous materials as the carrier for niacinamide. The surface functionalization of SBA-15 by a grafting strategy with triethoxyphenylsilane, triethoxy(4-methoxyphenyl)silane, triethoxymethylsilane and (3-mercaptopropyl)trimethoxysilane as modifying agents has been successfully achieved. The adsorption process was performed in acetonitrile, methanol, 2-propanol, 1-pentanol and ethyl acetate. The obtained results indicated a promote niacinamide adsorption on sulfopropyl-modified (119 mg/g) and non-modified (78 mg/g) SBA-15 from ethyl acetate. The pure and derivatized SBA-15 products have been characterized by elemental analysis, thermogravimetry, nitrogen adsorption and diffuse reflectance UV spectroscopy. After niacinamide adsorption the textural parameters of mesoporous carriers such as BET surface area, pore volume and microporosity were reduced. The mesoporous matrices loaded with niacinamide exhibited prolonged-release kinetics of this vitamin, especially from sulfopropyl-modified SBA-15 carrier.

  4. Composition controlled synthesis of PCL-PEG Janus nanoparticles: magnetite nanoparticles prepared from one-pot photo-click reaction.

    PubMed

    Khoee, S; Bagheri, Y; Hashemi, A

    2015-03-01

    The aim of this study is to investigate the effect of polymer nature on the morphology of synthesized nanoparticles. Super paramagnetic iron oxide nanoparticles (SPIONs) were prepared by co-precipitation method and then reacted with (3-mercaptopropyl) trimethoxysilane to obtain thiol-decorated SPIONs. Acrylated poly(caprolactone) and methoxy poly(ethylene glycol) were prepared, and then "thiol-ene click" reaction was performed under UV irradiation to attach two types of polymers on the surface of magnetite nanoparticles via the "photo-click" reaction method. Computational modelling was used for the prediction of the self-assembly of polymers on the surface of SPIONs, which determines the morphology of polymer coated nanoparticles.

  5. Detection of polycyclic aromatic hydrocarbon (PAH) compounds in artificial sea-water using surface-enhanced Raman scattering (SERS).

    PubMed

    Péron, Olivier; Rinnert, Emmanuel; Lehaitre, Michel; Crassous, Philippe; Compère, Chantal

    2009-07-15

    This paper reports an accurate synthesis of surface-enhanced Raman scattering (SERS) active substrates, based on gold colloidal monolayer, suitable for in situ environmental analysis. Quartz substrates were functionalized by silanization with (3-mercaptopropyl)trimethoxysilane (MPMS) or (3-aminopropyl)trimethoxysilane (APTMS) and they subsequently reacted with colloidal suspension of gold metal nanoparticles: respectively, the functional groups SH and NH(2) bound gold nanoparticles. Gold nanoparticles were prepared by the chemical reduction of HAuCl(4) using sodium tricitrate and immobilized onto silanized quartz substrates. Active substrate surface morphology was characterized with scanning electron microscopy (SEM) measurements and gold nanoparticles presented a diameter in the range 40-100 nm. Colloidal hydrophobic films, allowing nonpolar molecule pre-concentration, were obtained. The surfaces exhibit strong enhancement of Raman scattering from molecules adsorbed on the films. Spectra were recorded for two PAHs, naphthalene and pyrene, in artificial sea-water (ASW) with limits of detection (LODs) of 10 ppb for both on MPMS silanized substrates. PMID:19559865

  6. Gold nanoparticles supported on mesoporous silica: origin of high activity and role of Au NPs in selective oxidation of cyclohexane

    PubMed Central

    Wu, Pingping; Bai, Peng; Yan, Zifeng; Zhao, George X. S.

    2016-01-01

    Homogeneous immobilization of gold nanoparticles (Au NPs) on mesoporous silica has been achieved by using a one-pot synthesis method in the presence of organosilane mercapto-propyl-trimethoxysilane (MPTMS). The resultant Au NPs exhibited an excellent catalytic activity in the solvent-free selective oxidation of cyclohexane using molecular oxygen. By establishing the structure-performance relationship, the origin of the high activity of mesoporous supported Au catalyst was identified to be due to the presence of low-coordinated Au (0) sites with high dispersion. Au NPs were confirmed to play a critical role in the catalytic oxidation of cyclohexane by promoting the activation of O2 molecules and accelerating the formation of surface-active oxygen species. PMID:26729288

  7. Gold nanoparticles supported on mesoporous silica: origin of high activity and role of Au NPs in selective oxidation of cyclohexane

    NASA Astrophysics Data System (ADS)

    Wu, Pingping; Bai, Peng; Yan, Zifeng; Zhao, George X. S.

    2016-01-01

    Homogeneous immobilization of gold nanoparticles (Au NPs) on mesoporous silica has been achieved by using a one-pot synthesis method in the presence of organosilane mercapto-propyl-trimethoxysilane (MPTMS). The resultant Au NPs exhibited an excellent catalytic activity in the solvent-free selective oxidation of cyclohexane using molecular oxygen. By establishing the structure-performance relationship, the origin of the high activity of mesoporous supported Au catalyst was identified to be due to the presence of low-coordinated Au (0) sites with high dispersion. Au NPs were confirmed to play a critical role in the catalytic oxidation of cyclohexane by promoting the activation of O2 molecules and accelerating the formation of surface-active oxygen species.

  8. 3-mercaptopropyltrimethoxysilane as insulating coating and surface for protein immobilization for piezoelectric microcantilever sensors

    SciTech Connect

    Capobianco, Joseph A.; Shih, Wan Y.; Shih, W.-H.

    2007-04-15

    We have examined coating (PbMg{sub 1/3}Nb{sub 2/3}O{sub 3}){sub 0.63}-(PbTiO{sub 3}){sub 0.37} (PMN-PT)/tin and lead zirconate titanate (PZT)/glass piezoelectric microcantilever sensor (PEMS) with 3-mercaptopropyl-trimethoxysilane (MPS) by a simple solution method to electrically insulate the PEMS for in-water applications. In contrast to earlier methytrimethoxysilane insulation coating, the MPS coating also facilitated receptor immobilization on the sensor surface via bonding of its sulhydryl group to a bifunctional linker, sulfosuccinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate. We showed that a MPS coating of 21 nm in thickness is sufficient to electrically insulate and provide immobilization surface to the PEMS for in-liquid electrical self-excitation and self-sensing. The in-phosphate buffered saline solution resonance spectra were stable with Q values ranging from 41 to 55. The mass detection sensitivities were determined to be 5x10{sup -11} and 8x10{sup -12} g/Hz for the MPS-insulated PZT-glass and PMN-PT/tin PEMSs, respectively.

  9. 3-mercaptopropyltrimethoxysilane as insulating coating and surface for protein immobilization for piezoelectric microcantilever sensors.

    PubMed

    Capobianco, Joseph A; Shih, Wan Y; Shih, Wei-Heng

    2007-04-01

    We have examined coating (PbMg(13)Nb(23)O(3))(0.63)-(PbTiO(3))(0.37) (PMN-PT)/tin and lead zirconate titanate (PZT)/glass piezoelectric microcantilever sensor (PEMS) with 3-mercaptopropyl-trimethoxysilane (MPS) by a simple solution method to electrically insulate the PEMS for in-water applications. In contrast to earlier methytrimethoxysilane insulation coating, the MPS coating also facilitated receptor immobilization on the sensor surface via bonding of its sulhydryl group to a bifunctional linker, sulfosuccinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate. We showed that a MPS coating of 21 nm in thickness is sufficient to electrically insulate and provide immobilization surface to the PEMS for in-liquid electrical self-excitation and self-sensing. The in-phosphate buffered saline solution resonance spectra were stable with Q values ranging from 41 to 55. The mass detection sensitivities were determined to be 5x10(-11) and 8x10(-12) gHz for the MPS-insulated PZT-glass and PMN-PT/tin PEMSs, respectively.

  10. Preparation of a β-Cyclodextrin-Based Open-Tubular Capillary Electrochromatography Column and Application for Enantioseparations of Ten Basic Drugs.

    PubMed

    Fang, Linlin; Yu, Jia; Jiang, Zhen; Guo, Xingjie

    2016-01-01

    An open-tubular capillary electrochromatography column was prepared by chemically immobilized β-cyclodextrin modified gold nanoparticles onto new surface with the prederivatization of (3-mercaptopropyl)-trimethoxysilane. The synthesized nanoparticles and the prepared column were characterized by transmission electron microscopy, scanning electron microscopy, infrared spectroscopy and ultraviolet visible spectroscopy. When the column was employed as the chiral stationary phase, no enantioselectivity was observed for ten model basic drugs. So β-cyclodextrin was added to the background electrolyte as chiral additive to expect a possible synergistic effect occurring and resulting in a better separation. Fortunately, significant improvement in enantioselectivity was obtained for ten pairs of drug enantiomers. Then, the effects of β-cyclodextrin concentration and background electrolyte pH on the chiral separation were investigated. With the developed separation mode, all the enantiomers (except for venlafaxine) were baseline separated in resolutions of 4.49, 1.68, 1.88, 1.57, 2.52, 2.33, 3.24, 1.63 and 3.90 for zopiclone, chlorphenamine maleate, brompheniramine maleate, dioxopromethazine hydrochloride, carvedilol, homatropine hydrobromide, homatropine methylbromide, venlafaxine, sibutramine hydrochloride and terbutaline sulfate, respectively. Further, the possible separation mechanism involved was discussed. PMID:26771454

  11. A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples.

    PubMed

    Song, Yonghai; Chen, Jingyi; Sun, Min; Gong, Coucong; Shen, Yuan; Song, Yonggui; Wang, Li

    2016-03-01

    A simple electrochemical biosensor for quantitative determination of carbamate pesticide was developed based on a sensing interface of citrate-capped gold nanoparticles (AuNPs)/(3-mercaptopropyl)-trimethoxysilane (MPS)/gold electrode (Au). The biosensor was fabricated by firstly assembling three-dimensional (3D) MPS networks on Au electrode and subsequently assembling citrate-capped AuNPs on 3D MPS network via AuS bond. The interface of AuNPs/MPS/Au was negatively charged originating from the citrate coated on AuNPs that would repulse the negatively charged ferricyanide ([Fe(CN)6](3-/4-)) to produce a negative response. In the presence of acetylcholinesterase (AChE) and acetylthiocholine (ATCl), the AChE catalyzes the hydrolysis of ATCl into positively charged thiocholine which would replace the citrate on AuNPs through the strong AuS bond and convert the negative charged surface to be positively charged. The resulted positively charged AuNPs/MPS/Au then attracted the [Fe(CN)6](3-/4-) to produce a positive response. Based on the inhibition of carbamate pesticides on the activity of AChE, the pesticide could be quantitatively determined at a very low potential. The linear range was from 0.003 to 2.00 μM. The sensing platform was also proved to be suitable for carbamate pesticides detection in practical sample.

  12. Synthesis of a quantum nanocrystal-gold nanoshell complex for near-infrared generated fluorescence and photothermal decay of luminescence.

    PubMed

    Lin, Adam Y; Young, Joseph K; Nixon, Ariel V; Drezek, Rebekah A

    2014-09-21

    Multifunction nanoparticle complexes have previously been developed to aid physicians in both diagnosis and treatment of cancerous tissue. Here, we designed a nanoparticle complex structure that consists of a plasmonically active hollow gold nanoshell core surrounded by photoluminescent quantum nanocrystals (QNs) in the form of PbS encapsulated by a silica layer. There are three main design variables including HGN synthesis and optical tuning, formation of the silica layer on the hollow gold nanoshell surface, and fabrication and photoluminescence tuning of PbS quantum nanocrystals. The hollow gold nanoshells were deliberately designed to function in the optical regimes that maximize tissue transmissivity (800 nm) and minimize tissue absorption (1100 nm). Secondly, several chemical ligands were tested such as (3-mercaptopropyl)trimethoxysilane and mercaptoundecanoic acid for controlled growth of the silica layer. Last, PbS QNs were synthesized and optimized with various capping agents, where the nanocrystals excited at the same wavelength were used to activate the photothermal properties of the hollow gold nanoshells. Upon irradiation of the complex with a lower power 800 nm laser, the nanocrystals luminesce at 1100 nm. At ablative temperatures the intrinsic luminescent properties of the QNs are altered and the luminescent output is significantly reduced (>70%). While this paper focuses on synthesis and optimization of the QN-HGN complex, in the future we believe that this novel particle complex design may have the potential to serve as a triple theranostic agent, which will aid satellite tumor localization, photothermal treatment, and ablative confirmation. PMID:25096858

  13. Effective and selective bisphenol A synthesis on a layered silicate with spatially arranged sulfonic acid.

    PubMed

    Ide, Yusuke; Kagawa, Noriko; Itakura, Masaya; Imae, Ichiro; Sadakane, Masahiro; Sano, Tsuneji

    2012-04-01

    The silylated derivatives of a layered alkali silicate, magadiite, modified with propylsulfonic or arylsulfonic acid were synthesized and used as catalysts for an acid-catalyzed condensation of phenol with acetone. The propylsulfonated magadiites with a different amount of the attached silyl group were synthesized by the silylation of the dodecylammonium-exchanged magadiite with the tuned amount of 3-(mercaptopropyl)trimethoxysilane and the subsequent oxidation of the attached thiol to sulfonic acid. The arylsulfonated magadiite was synthesized by the silylation of the dodecylammonium-exchanged magadiite with 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane and the subsequent hydrolysis of the attached sulfonyl chloride to sulfonic acid. The X-ray diffraction (XRD) patterns and elemental mappings of the products, and the photoluminescent spectra of the Eu(3+)-exchanged products suggested that propylsulfonic or arylsulfonic acid was homogeneously distributed in the interlayer space. When all the sulfonated materials were used as an acid catalyst for condensation between phenol and acetone, p,p' bisphenol A selectively formed over the o,p' isomer, and higher yield and selectivity were attained on the catalysts with larger amount of the attached sulfonic acid. When the interlayer space of the propylsulfonated magadiite was expanded by the co-attachment of octadecylsilyl group, lower selectivity was obtained. The arylsulfonated magadiite showed considerably higher p,p' bisphenol A yield than the propylsulfonated magadiites.

  14. Facile "one-pot" synthesis of poly(methacrylic acid)-based hybrid monolith via thiol-ene click reaction for hydrophilic interaction chromatography.

    PubMed

    Lv, Xumei; Tan, Wangming; Chen, Ye; Chen, Yingzhuang; Ma, Ming; Chen, Bo; Yao, Shouzhuo

    2016-07-01

    A novel sol-gel "one-pot" approach in tandem with a radical-mediated thiol-ene reaction for the synthesis of a methacrylic acid-based hybrid monolith was developed. The polymerization monomers, tetramethoxysilane (TMOS) and 3-mercaptopropyl trimethoxysilane (MPTS), were hydrolyzed in high-concentration methacrylic acid solution that also served as a hydrophilic functional monomer. The resulting solution was then mixed with initiator (2, 2'-azobis (2-methylpropionamide) dihydrochloride) and porogen (urea, polyethylene glycol 20,000) in a capillary column and polymerized in water bath. The column had a uniform porous structure and a good permeability. The evaluation of the monolith was performed by separation of small molecules including nucleosides, phenols, amides, bases and Triton X-100. The calibration curves for uridine, inosine, adenosine and cytidine were determined. All the calibration curves exhibited good linear regressions (R(2)≥0.995) within the test ranges of 0.5-40μg/mL for four nucleosides. Additionaliy, atypical hydrophilic mechanism was proved by elution order from low to high according to polarity retention time increased with increases in the content of the organic solvent in the mobile phase. Further studies indicated that hydrogen bond and electrostatic interactions existed between the polar analytes and the stationary phase. This was the mechanism of retention. The excellent separation of the BSA digest showed good hydrophility of the column and indicated the potential in separation of complex biological samples.

  15. Diamond nanoparticles as a way to improve electron transfer in sol-gel L-lactate biosensing platforms.

    PubMed

    Briones, M; Casero, E; Vázquez, L; Pariente, F; Lorenzo, E; Petit-Domínguez, M D

    2016-02-18

    In the present work, we have included for the first time diamond nanoparticles (DNPs) in a sol-gel matrix derived from (3-mercaptopropyl)-trimethoxysilane (MPTS) in order to improve electron transfer in a lactate oxidase (LOx) based electrochemical biosensing platform. Firstly, an exhaustive AFM study, including topographical, surface potential (KFM) and capacitance gradient (CG) measurements, of each step involved in the biosensing platform development was performed. The platform is based on gold electrodes (Au) modified with the sol-gel matrix (Au/MPTS) in which diamond nanoparticles (Au/MPTS/DNPs) and lactate oxidase (Au/MPTS/DNPs/LOx) have been included. For the sake of comparison, we have also characterized a gold electrode directly modified with DNPs (Au/DNPs). Secondly, the electrochemical behavior of a redox mediator (hydroxymethyl-ferrocene, HMF) was evaluated at the platforms mentioned above. The response of Au/MPTS/DNPs/LOx towards lactate was obtained. A linear concentration range from 0.053 mM to 1.6 mM, a sensitivity of 2.6 μA mM(-1) and a detection limit of 16 μM were obtained. These analytical properties are comparable to other biosensors, presenting also as advantages that DNPs are inexpensive, environment-friendly and easy-handled nanomaterials. Finally, the developed biosensor was applied for lactate determination in wine samples.

  16. Facile "one-pot" synthesis of poly(methacrylic acid)-based hybrid monolith via thiol-ene click reaction for hydrophilic interaction chromatography.

    PubMed

    Lv, Xumei; Tan, Wangming; Chen, Ye; Chen, Yingzhuang; Ma, Ming; Chen, Bo; Yao, Shouzhuo

    2016-07-01

    A novel sol-gel "one-pot" approach in tandem with a radical-mediated thiol-ene reaction for the synthesis of a methacrylic acid-based hybrid monolith was developed. The polymerization monomers, tetramethoxysilane (TMOS) and 3-mercaptopropyl trimethoxysilane (MPTS), were hydrolyzed in high-concentration methacrylic acid solution that also served as a hydrophilic functional monomer. The resulting solution was then mixed with initiator (2, 2'-azobis (2-methylpropionamide) dihydrochloride) and porogen (urea, polyethylene glycol 20,000) in a capillary column and polymerized in water bath. The column had a uniform porous structure and a good permeability. The evaluation of the monolith was performed by separation of small molecules including nucleosides, phenols, amides, bases and Triton X-100. The calibration curves for uridine, inosine, adenosine and cytidine were determined. All the calibration curves exhibited good linear regressions (R(2)≥0.995) within the test ranges of 0.5-40μg/mL for four nucleosides. Additionaliy, atypical hydrophilic mechanism was proved by elution order from low to high according to polarity retention time increased with increases in the content of the organic solvent in the mobile phase. Further studies indicated that hydrogen bond and electrostatic interactions existed between the polar analytes and the stationary phase. This was the mechanism of retention. The excellent separation of the BSA digest showed good hydrophility of the column and indicated the potential in separation of complex biological samples. PMID:27264742

  17. A novel optical DNA biosensor for detection of trace amounts of mercuric ions using gold nanoparticles introduced onto modified glass surface

    NASA Astrophysics Data System (ADS)

    Mashhadizadeh, Mohammad Hossein; Talemi, Rasoul Pourtaghavi

    2014-11-01

    In this work we report a DNA spectrophotometric biosensor for detection of Hg2+ ions in which a pair of oligonucleotides with four thymine-thymine (T-T) mismatched bases was immobilized onto modified glass surface. Firstly, glass surface modified with 3-(mercaptopropyl) trimethoxysilane (MSPT) and gold nano-particles respectively and then one oligonucleotide (P1) modified with hexanthiol at 5-terminal was immobilized on gold nano-particles via self-assembly and inserted in methylene blue. Methylene blue can intercalate on single strand DNA (ss-DNA) and its absorption peak can measure spectrophotometrically. Then the other oligonucleotide was able to hybridize with P1 by forming thymine-Hg2+-thymine (T-Hg2+-T) complexes in the presence of Hg2+, and absorption signal of methylene blue reduced upon Hg2+ increasing concentration because inaccessibility of guanine base in DNA duplex. However, when Hg2+ was absent, the two oligonucleotides could not hybridize due to the T-T mismatched bases, and P2 could not be fixed on the modified glass surface and any change in absorption peak of methylene blue takes place. The UV-Vis spectrum showed a linear correlation between the absorption peak of methylene blue and the concentration of Hg2+ over the range from 10 nM to 10 μM (R2 = 0.9985) with a detection limit of 6 nM. This spectrophotometric biosensor could be widely used for selective detection of Hg2+.

  18. Synthesis and characterization of the NiFe2O4@TEOS-TPS@Ag nanocomposite and investigation of its antibacterial activity

    NASA Astrophysics Data System (ADS)

    Allafchian, Ali R.; Jalali, S. A. H.; Amiri, R.; Shahabadi, Sh.

    2016-11-01

    In this study, the NiFe2O4 was embedded in (3-mercaptopropyl) trimethoxysilane (TPS) and tetraethyl orthosilicate (TEOS) using the sol-gel method. These compounds were used as the support of Ag nanoparticles (Ag NPs). The NiFe2O4@TEOS-TPS@Ag nanocomposites were obtained with the development of bonding between the silver atoms of Ag NPs and the sulfur atoms of TPS molecule. Field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were used for the characterization of the Ag nanocomposites. Also, the magnetic properties of these nanocomposites were studied by using a vibrating sample magnetometer (VSM) technique. The disk diffusion, minimum inhibition concentration (MIC) and minimum bactericidal concentrations (MBC) tests were used for the investigation of the antibacterial effect of this nanocomposite against bacterial strains. The synthesized nanocomposite presented high reusability and good antibacterial activity against gram-positive and gram-negative bacteria. Remarkably, this nanocomposite could be easily removed from the disinfected media by magnetic decantation.

  19. Synthesis of a quantum nanocrystal-gold nanoshell complex for near-infrared generated fluorescence and photothermal decay of luminescence.

    PubMed

    Lin, Adam Y; Young, Joseph K; Nixon, Ariel V; Drezek, Rebekah A

    2014-09-21

    Multifunction nanoparticle complexes have previously been developed to aid physicians in both diagnosis and treatment of cancerous tissue. Here, we designed a nanoparticle complex structure that consists of a plasmonically active hollow gold nanoshell core surrounded by photoluminescent quantum nanocrystals (QNs) in the form of PbS encapsulated by a silica layer. There are three main design variables including HGN synthesis and optical tuning, formation of the silica layer on the hollow gold nanoshell surface, and fabrication and photoluminescence tuning of PbS quantum nanocrystals. The hollow gold nanoshells were deliberately designed to function in the optical regimes that maximize tissue transmissivity (800 nm) and minimize tissue absorption (1100 nm). Secondly, several chemical ligands were tested such as (3-mercaptopropyl)trimethoxysilane and mercaptoundecanoic acid for controlled growth of the silica layer. Last, PbS QNs were synthesized and optimized with various capping agents, where the nanocrystals excited at the same wavelength were used to activate the photothermal properties of the hollow gold nanoshells. Upon irradiation of the complex with a lower power 800 nm laser, the nanocrystals luminesce at 1100 nm. At ablative temperatures the intrinsic luminescent properties of the QNs are altered and the luminescent output is significantly reduced (>70%). While this paper focuses on synthesis and optimization of the QN-HGN complex, in the future we believe that this novel particle complex design may have the potential to serve as a triple theranostic agent, which will aid satellite tumor localization, photothermal treatment, and ablative confirmation.

  20. Application of electrochemical impedance spectroscopy for monitoring allergen-antibody reactions using gold nanoparticle-based biomolecular immobilization method.

    PubMed

    Huang, Haizhen; Liu, Zhigang; Yang, Xiurong

    2006-09-15

    Gold nanoparticles were used to enhance the immobilization amount and retain the immunoactivity of recombinant dust mite allergen Der f2 immobilized on a glassy carbon electrode (GCE). The interaction between allergen and antibody was studied by electrochemical impedance spectroscopy (EIS). Self-assembled Au colloid layer (ø=16nm) deposited on (3-mercaptopropyl)trimethoxysilane (MPTS)-modified GCE offered a basis to control the immobilization of allergen Der f2. The impedance measurements were based on the charge transfer kinetics of the [Fe(CN)(6)](3-/4-) redox pair, compared with bare GCE, the immobilization of allergen Der f2 and the allergen-antibody interaction that occurred on the electrode surface altered the interfacial electron transfer resistance and thereby slowed down the charge transfer kinetics by reducing the active area of the electrode or by preventing the redox species in electrolyte solution from approaching the electrode. The interactions of allergen with various concentrations of monoclonal antibody were also monitored through the change of impedance response. The results showed that the electron transfer resistance increased with increasing concentrations of monoclonal antibody. PMID:16836968

  1. Adsorption enhancement of elemental mercury onto sulphur-functionalized silica gel adsorbents.

    PubMed

    Johari, Khairiraihanna; Saman, Norasikin; Mat, Hanapi

    2014-01-01

    In this study, elemental mercury (EM) adsorbents were synthesized using tetraethyl orthosilicate (TEOS) and 3-mercaptopropyl trimethoxysilane as silica precursors. The synthesized silica gel (SG)-TEOS was further functionalized through impregnation with elemental sulphur and carbon disulphide (CS2). The SG adsorbents were then characterized by using scanning electron microscope, Fourier transform infra-red spectrophotometer, nitrogen adsorption/desorption, and energy-dispersive X-ray diffractometer. The EM adsorption of the SG adsorbents was determined using fabricated fixed-bed adsorber. The EM adsorption results showed that the sulphur-functionalized SG adsorbents had a greater Hgo breakthrough adsorption capacity, confirming that the presence of sulphur in silica matrices can improve Hgo adsorption performance due to their high affinity towards mercury. The highest Hgo adsorption capacity was observed for SG-TEOS(CS2) (82.62 microg/g), which was approximately 2.9 times higher than SG-TEOS (28.47 microg/g). The rate of Hgo adsorption was observed higher for sulphur-impregnated adsorbents, and decreased with the increase in the bed temperatures.

  2. Laccase biosensors based on different enzyme immobilization strategies for phenolic compounds determination.

    PubMed

    Casero, E; Petit-Domínguez, M D; Vázquez, L; Ramírez-Asperilla, I; Parra-Alfambra, A M; Pariente, F; Lorenzo, E

    2013-10-15

    Different enzyme immobilization approaches of Trametes versicolor laccase (TvL) onto gold surfaces and their influence on the performance of the final bioanalytical platforms are described. The laccase immobilization methods include: (i) direct adsorption onto gold electrodes (TvL/Au), (ii) covalent attachment to a gold surface modified with a bifunctional reagent, 3,3'-Dithiodipropionic acid di (N-succinimidyl ester) (DTSP), and (iii) integration of the enzyme into a sol-gel 3D polymeric network derived from (3-mercaptopropyl)-trimethoxysilane (MPTS) previously formed onto a gold surface (TvL/MPTS/Au). The characterization and applicability of these biosensors are described. Characterization is performed in aqueous acetate buffer solutions using atomic force microscopy (AFM), providing valuable information concerning morphological data at the nanoscale level. The response of the three biosensing platforms developed, TvL/Au, TvL/DTSP/Au and TvL/MPTS/Au, is evaluated in the presence of hydroquinone (HQ), used as a phenolic enzymatic substrate. All systems exhibit a clear electrocatalytic activity and HQ can be amperometrically determined at -0.10 V versus Ag/AgCl. However, the performance of biosensors - evaluated in terms of sensitivity, detection limit, linear response range, reproducibility and stability - depends clearly on the enzyme immobilization strategy, which allows establishing its influence on the enzyme catalytic activity.

  3. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    SciTech Connect

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  4. HSQ double patterning process for 12 nm resolution x-ray zone plates

    SciTech Connect

    Chao, Weilun; Kim, Jihoon; Rekawa, Senajith; Fischer, Peter; Anderson, Erik H.

    2009-06-16

    Soft x-ray zone plate microscopy is a powerful nano-analytic technique used for a wide variety of scientific and technological studies. Pushing its spatial resolution to 10 nm and below is highly desired and feasible due to the short wavelength of soft x-rays. Instruments using Fresnel zone plate lenses achieve a spatial resolution approximately equal to the smallest, outer most zone width. We developed a double patterning zone plate fabrication process based on a high-resolution resist, hydrogen silsesquioxane (HSQ), to bypass the limitations of conventional single exposure fabrication to pattern density, such as finite beam size, scattering in resist and modest intrinsic resist contrast. To fabricate HSQ structures with zone widths in the order of 10 nm on gold plating base, a surface conditioning process with (3-mercaptopropyl) trimethoxysilane, 3-MPT, is used, which forms a homogeneous hydroxylation surface on gold surface and provides good anchoring for the desired HSQ structures. Using the new HSQ double patterning process, coupled with an internally developed, sub-pixel alignment algorithm, we have successfully fabricated in-house gold zone plates of 12 nm outer zones. Promising results for 10 nm zone plates have also been obtained. With the 12 nm zone plates, we have achieved a resolution of 12 nm using the full-field soft x-ray microscope, XM-1.

  5. Hydrogen-bonding-driven self-assembly of PEGylated organosilica nanoparticles with poly(acrylic acid) in aqueous solutions and in layer-by-layer deposition at solid surfaces.

    PubMed

    Irmukhametova, Galiya S; Fraser, Brian J; Keddie, Joseph L; Mun, Grigoriy A; Khutoryanskiy, Vitaliy V

    2012-01-10

    PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed.

  6. Synthesis of Quantum Nanocrystal-Gold Nanoshell Complex for Near Infrared Generated Fluorescence and Photothermal Decay of Luminescence

    PubMed Central

    Lin, Adam Y.; Young, Joseph K.; Nixon, Ariel V.; Drezek, Rebekah A.

    2015-01-01

    Multifunction nanoparticle complexes have previously been developed to aid physicians in both diagnosis and treatment of cancerous tissue. Here, we designed a nanoparticle complex structure that consists of a plasmonically active hollow gold nanoshell core surrounded by photoluminescent quantum nanocrystals (QNs) in the form of PbS encapsulated by a silica layer. There are three main design variables including HGN synthesis and optical tuning, formation of the silica layer on the hollow gold nanoshell surface, and fabrication and photoluminescence tuning of PbS quantum nanocrystals. The hollow gold nanoshells were deliberately designed to function in the optical regimes that maximize tissue transmissivity (800 nm) and minimize tissue absorption (1100 nm). Secondly, several chemical ligands were tested such as (3-mercaptopropyl) trimethoxysilane and mercaptoundecanoic acid for controlled growth of the silica layer. Last, PbS QNs were synthesized and optimized with various capping agents, where the nanocrystals were excited at the same wavelength used to activate the photothermal properties of the hollow gold nanoshells. Upon irradiation of the complex with a lower power 800 nm laser, the nanocrystals luminesce at 1100 nm. At ablative temperatures the intrinsic luminescent properties of the QNs is altered and the luminescent output significantly reduced (>70%). While this paper focuses on synthesis and optimization of the QN-HGN complex, in the future we believe that this novel particle complex design may have the potential to serve as a triple theranostic agent, which will aid satellite tumor localization, photothermal treatment, and ablative confirmation. PMID:25096858

  7. Preparation of a β-Cyclodextrin-Based Open-Tubular Capillary Electrochromatography Column and Application for Enantioseparations of Ten Basic Drugs

    PubMed Central

    Fang, Linlin; Yu, Jia; Jiang, Zhen; Guo, Xingjie

    2016-01-01

    An open-tubular capillary electrochromatography column was prepared by chemically immobilized β-cyclodextrin modified gold nanoparticles onto new surface with the prederivatization of (3-mercaptopropyl)-trimethoxysilane. The synthesized nanoparticles and the prepared column were characterized by transmission electron microscopy, scanning electron microscopy, infrared spectroscopy and ultraviolet visible spectroscopy. When the column was employed as the chiral stationary phase, no enantioselectivity was observed for ten model basic drugs. So β-cyclodextrin was added to the background electrolyte as chiral additive to expect a possible synergistic effect occurring and resulting in a better separation. Fortunately, significant improvement in enantioselectivity was obtained for ten pairs of drug enantiomers. Then, the effects of β-cyclodextrin concentration and background electrolyte pH on the chiral separation were investigated. With the developed separation mode, all the enantiomers (except for venlafaxine) were baseline separated in resolutions of 4.49, 1.68, 1.88, 1.57, 2.52, 2.33, 3.24, 1.63 and 3.90 for zopiclone, chlorphenamine maleate, brompheniramine maleate, dioxopromethazine hydrochloride, carvedilol, homatropine hydrobromide, homatropine methylbromide, venlafaxine, sibutramine hydrochloride and terbutaline sulfate, respectively. Further, the possible separation mechanism involved was discussed. PMID:26771454

  8. Synthesis of a quantum nanocrystal-gold nanoshell complex for near-infrared generated fluorescence and photothermal decay of luminescence

    NASA Astrophysics Data System (ADS)

    Lin, Adam Y.; Young, Joseph K.; Nixon, Ariel V.; Drezek, Rebekah A.

    2014-08-01

    Multifunction nanoparticle complexes have previously been developed to aid physicians in both diagnosis and treatment of cancerous tissue. Here, we designed a nanoparticle complex structure that consists of a plasmonically active hollow gold nanoshell core surrounded by photoluminescent quantum nanocrystals (QNs) in the form of PbS encapsulated by a silica layer. There are three main design variables including HGN synthesis and optical tuning, formation of the silica layer on the hollow gold nanoshell surface, and fabrication and photoluminescence tuning of PbS quantum nanocrystals. The hollow gold nanoshells were deliberately designed to function in the optical regimes that maximize tissue transmissivity (800 nm) and minimize tissue absorption (1100 nm). Secondly, several chemical ligands were tested such as (3-mercaptopropyl)trimethoxysilane and mercaptoundecanoic acid for controlled growth of the silica layer. Last, PbS QNs were synthesized and optimized with various capping agents, where the nanocrystals excited at the same wavelength were used to activate the photothermal properties of the hollow gold nanoshells. Upon irradiation of the complex with a lower power 800 nm laser, the nanocrystals luminesce at 1100 nm. At ablative temperatures the intrinsic luminescent properties of the QNs are altered and the luminescent output is significantly reduced (>70%). While this paper focuses on synthesis and optimization of the QN-HGN complex, in the future we believe that this novel particle complex design may have the potential to serve as a triple theranostic agent, which will aid satellite tumor localization, photothermal treatment, and ablative confirmation.Multifunction nanoparticle complexes have previously been developed to aid physicians in both diagnosis and treatment of cancerous tissue. Here, we designed a nanoparticle complex structure that consists of a plasmonically active hollow gold nanoshell core surrounded by photoluminescent quantum nanocrystals (QNs

  9. Self-assembly and photoluminescence evolution of hydrophilic and hydrophobic quantum dots in sol–gel processes

    SciTech Connect

    Yang, Ping; Matras-Postolek, Katarzyna; Song, Xueling; Zheng, Yan; Liu, Yumeng; Ding, Kun; Nie, Shijie

    2015-10-15

    Graphical abstract: Highly luminescent quantum dots (QDs) with tunable photoluminescence (PL) wavelength were assembled into various morphologies including chain, hollow spheres, fibers, and ring structures through sol–gel processes. The PL properties during assembly as investigated. - Highlights: • Highly luminescent quantum dots (QDs) were synthesized from several ligands. • The evolution of PL in self-assembly via sol–gel processes was investigated. • CdTe QDs were assembled into a chain by controlling hydrolysis and condensation reactions. • Hollow spheres, fibers, and ring structures were created via CdSe/ZnS QDs in sol–gel processes. - Abstract: Highly luminescent quantum dots (QDs) with tunable photoluminescence (PL) wavelength were synthesized from several ligands to investigate the PL evolution in QD self-assembly via sol–gel processes. After ligand exchange, CdTe QDs were assembled into a chain by controlling the hydrolysis and condensation reaction of 3-mercaptopropyl-trimethoxysilane. The chain was then coated with a SiO{sub 2} shell from tetraethyl orthosilicate (TEOS). Hollow spheres, fibers, and ring structures were created from CdSe/ZnS QDs via various sol–gel processes. CdTe QDs revealed red-shifted and narrowed PL spectrum after assembly compared with their initial one. In contrast, the red-shift of PL spectra of CdSe/ZnS QDs is small. By optimizing experimental conditions, SiO{sub 2} spheres with multiple CdSe/ZnS QDs were fabricated using TEOS and MPS. The QDs in these SiO{sub 2} spheres retained their initial PL properties. This result is useful for application because of their high stability and high PL efficiency of 33%.

  10. An electrochemical aptasensor for thrombin detection based on direct electrochemistry of glucose oxidase using a functionalized graphene hybrid for amplification.

    PubMed

    Bai, Lijuan; Yan, Bin; Chai, Yaqin; Yuan, Ruo; Yuan, Yali; Xie, Shunbi; Jiang, Liping; He, Ying

    2013-11-01

    In this work, we reported a new label-free electrochemical aptasensor for highly sensitive detection of thrombin using direct electron transfer of glucose oxidase (GOD) as a redox probe and a gold nanoparticle-polyaniline-graphene (Au-PANI-Gra) hybrid for amplification. The Au-PANI-Gra hybrid with large surface area provided a biocompatible sensing platform for the immobilization of GOD. GOD was encapsulated into the three-dimensional netlike (3-mercaptopropyl)trimethoxysilane (MPTS) to form the MPTS-GOD biocomposite, which not only retained the native functions and properties, but also exhibited tunable porosity, high thermal stability, and chemical inertness. With abundant thiol tail groups on MPTS, MPTS-GOD was able to chemisorb onto the surface of the Au-PANI-Gra modified electrode through the strong affinity of the Au-S bond. The electrochemical signal originated from GOD, avoiding the addition or labeling of other redox mediators. After immobilizing the thiolated thrombin binding aptamer through gold nanoparticles (AuNPs), GOD as a blocking reagent was employed to block the remaining active sites of the AuNPs and avoid the nonspecific adsorption. The proposed method avoided the labeling process of redox probes and increased the amount of electroactive GOD. The concentration of thrombin was monitored based on the decrease of current response through cyclic voltammetry (CV) in 0.1 M PBS (pH 7.4). With the excellent direct electron transfer of double layer GOD membranes, the resulting aptasensor exhibited high sensitivity for detection of thrombin with a wide linear range from 1.0 × 10(-12) to 3.0 × 10(-8) M. The proposed aptasensor also showed good stability, satisfactory reproducibility and high specificity, which provided a promising strategy for electrochemical aptamer-based detection of other biomolecules.

  11. Highly sensitive determination of hydroxylamine using fused gold nanoparticles immobilized on sol-gel film modified gold electrode.

    PubMed

    Kannan, P; John, S Abraham

    2010-03-24

    We are reporting the highly sensitive determination of hydroxylamine (HA) using 2-mercapto-4-methyl-5-thiazoleacetic acid (TAA) capped fused spherical gold nanoparticles (AuNPs) modified Au electrode. The fused TAA-AuNPs were immobilized on (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film, which was pre-assembled on Au electrode. The immobilization of fused TAA-AuNPs on MPTS sol-gel film was confirmed by UV-vis absorption spectroscopy and atomic force microscopy (AFM). The AFM image showed that the AuNPs retained the fused spherical morphology after immobilized on sol-gel film. The fused TAA-AuNPs on MPTS modified Au electrode were used for the determination of HA in phosphate buffer (PB) solution (pH=7.2). When compared to bare Au electrode, the fused AuNPs modified electrode not only shifted the oxidation potential of HA towards less positive potential but also enhanced its oxidation peak current. Further, the oxidation of HA was highly stable at fused AuNPs modified electrode. Using amperometric method, determination of 17.5 nM HA was achieved for the first time. Further, the current response of HA increases linearly while increasing its concentration from 17.5 nM to 22 mM and a detection limit was found to be 0.39 nM (S/N=3). The present modified electrode was also successfully used for the determination of 17.5 nM HA in the presence of 200-fold excess of common interferents such as urea, NO(2)(-), NH(4)(+), oxalate, Mn(2+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+) and Cu(2+). The practical application of the present modified electrode was demonstrated by measuring the concentration of HA in ground water samples.

  12. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    PubMed

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation. PMID:27574979

  13. Surface-engineered growth of AgIn₅S₈ crystals.

    PubMed

    Lai, Chia-Hung; Chiang, Ching-Yeh; Lin, Po-Chang; Yang, Kai-Yu; Hua, Chi Chung; Lee, Tai-Chou

    2013-05-01

    The growth of semiconductor crystals and thin films plays an essential role in industry and academic research. Considering the environmental damage caused by energy consumption during their fabrication, a simpler and cheaper method is desired. In fact, preparing semiconductor materials at lower temperatures using solution chemistry has potential in this research field. We found that solution chemistry, the physical and chemical properties of the substrate surface, and the phase diagram of the multicomponent compound semiconductor have a decisive influence on the crystal structure of the material. In this study, we used self-assembled monolayers (SAMs) to modify the silicon/glass substrate surface and effectively control the density of the functional groups and surface energy of the substrates. We first employed various solutions to grow octadecyltrichlorosilane (OTS), 3-mercaptopropyl-trimethoxysilane (MPS), and mixed OTS-MPS SAMs. The surface energy can be adjusted between 24.9 and 50.8 erg/cm(2). Using metal sulfide precursors in appropriate concentrations, AgIn5S8 crystals can be grown on the modified substrates without any post-thermal treatment. We can easily adjust the nucleation in order to vary the density of AgIn5S8 crystals. Our current process can achieve AgIn5S8 crystals of a maximum of 1 μm in diameter and a minimum crystal density of approximately 0.038/μm(2). One proof-of-concept experiment demonstrated that the material prepared from this low temperature process showed positive photocatalytic activity. This method for growing crystals can be applied to the green fabrication of optoelectronic materials.

  14. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    PubMed

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

  15. Biotinylation of ZnO nanoparticles and thin films: a two-step surface functionalization study.

    PubMed

    SelegArd, Linnéa; Khranovskyy, Volodymyr; Söderlind, Fredrik; Vahlberg, Cecilia; Ahrén, Maria; Käll, Per-Olov; Yakimova, Rositza; Uvdal, Kajsa

    2010-07-01

    This study reports ZnO nanoparticles and thin film surface modification using a two-step functionalization strategy. A small silane molecule was used to build up a stabilizing layer and for conjugation of biotin (vitamin B7), as a specific tag. Biotin was chosen because it is a well-studied bioactive molecule with high affinity for avidin. ZnO nanoparticles were synthesized by electrochemical deposition under oxidizing condition, and ZnO films were prepared by plasma-enhanced metal-organic chemical vapor deposition. Both ZnO nanoparticles and ZnO thin films were surface modified by forming a (3-mercaptopropyl)trimethoxysilane (MPTS) layer followed by attachment of a biotin derivate. Iodoacetyl-PEG2-biotin molecule was coupled to the thiol unit in MPTS through a substitution reaction. Powder X-ray diffraction, transmission electron microscopy, X-ray photoemission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure spectroscopy were used to investigate the as-synthesized and functionalized ZnO materials. The measurements showed highly crystalline materials in both cases with a ZnO nanoparticle diameter of about 5 nm and a grain size of about 45 nm for the as-grown ZnO thin films. The surface modification process resulted in coupling of silanes and biotin to both the ZnO nanoparticles and ZnO thin films. The two-step functionalization strategy has a high potential for specific targeting in bioimaging probes and for recognition studies in biosensing applications.

  16. Microdroplet-Based Potentiometric Redox Measurements on Gold Nanoporous Electrodes.

    PubMed

    Freeman, Christopher J; Farghaly, Ahmed A; Choudhary, Hajira; Chavis, Amy E; Brady, Kyle T; Reiner, Joseph E; Collinson, Maryanne M

    2016-04-01

    Potentiometric redox measurements were made in subnanoliter droplets of solutions using an optically transparent nanoporous gold electrode strategically mounted on the stage of an inverted microscope. Nanoporous gold was prepared via dealloying gold leaf with concentrated nitric acid and was chemisorbed to a standard microscope coverslip with (3-mercaptopropyl)trimethoxysilane. The gold surface was further modified with 1-hexanethiol to optimize hydrophobicity of the surface to allow for redox measurements to be made in nanoscopic volumes. Time traces of the open-circuit potential (OCP) were used to construct Nernst plots to evaluate the applicability of the droplet-based potentiometric redox measurement system. Two poised one-electron transfer systems (potassium ferricyanide/ferrocyanide and ferrous/ferric ammonium sulfate) yielded Nernstian slopes of -58.5 and -60.3 mV, respectively, with regression coefficients greater than 0.99. The y-intercepts of the two agreed well to the formal potential of the two standard oxidation-reduction potential (ORP) calibrants, ZoBell's and Light's solution. The benzoquinone and hydroquinone redox couple was examined as a representative two-electron redox system; a Nernst slope of -30.8 mV was obtained. Additionally, two unpoised systems (potassium ferricyanide and ascorbic acid) were studied to evaluate the system under conditions where only one form of the redox couple is present in appreciable concentrations. Again, slopes near the Nernstian values of -59 and -29 mV, respectively, were obtained. All experiments were carried out using solution volumes between 280 and 1400 pL with injection volumes between 8 and 100 pL. The miniscule volumes allowed for extremely rapid mixing (<305 ms) as well. The small volumes and rapid mixing along with the high accuracy and sensitivity of these measurements lend support to the use of this approach in applications where time is a factor and only small volumes are available for testing. PMID

  17. Efficient epoxidation over cyanocobalamine containing SBA-15 organic-inorganic nanohybrids

    NASA Astrophysics Data System (ADS)

    Karimi, Z.; Mahjoub, A. R.

    2010-05-01

    SBA-15 mesoporous silica is synthesized using triblock copolymer P123 surfactant and chemically modified by aminopropyl, thiol, ammonium and sulfonic acid functional groups. Functionalization is performed via post synthesize method using 3-aminopropyltriethoxysilane (APTES) or 3-mercatopropyl trimethoxysilane (MPTMS) precursor. The as synthesized mesoporous systems are applied for immobilization of cyanocobalamine. Functionalization effectively improves sorption properties of the supports, while different functional groups exert different effects. The organic-inorganic mesoporous materials are characterized via X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy (TEM), FT-IR and inductively coupled plasma-optical emission (ICP). The newly synthesized systems exhibit high catalytic activity for heterogeneous epoxidation of cyclooctene in presence of hydrogen peroxide. Reaction conditions are optimized, effect of functional groups on performance of the catalysts is taken into consideration and reusability of the designed heterogeneous systems is studied. Systems with chemically modified supports are shown to be more efficient and stable catalysts however; chemical nature of functional groups plays a crucial role.

  18. Mercapto-based coupling agent for improved thermophotovoltaic device back surface reflector adhesion and reflectance

    DOEpatents

    Wernsman, Bernard; Fiedor, Joseph N.; Irr, Lawrence G.; Palmisiano, Marc N.

    2016-10-04

    A back surface reflector (BSR) is described. The BSR includes a reflecting layer, a substrate and an adhesion layer between the reflecting layer and the substrate. The adhesion layer includes 3-mercaptopropyl (trimethoxy) silane (a.k.a. Merc).

  19. Synthesis and characterization of aqueous quantum dots for biomedical applications

    NASA Astrophysics Data System (ADS)

    Li, Hui

    Quantum Dots (QDs) are semiconductor nanocrystals (1˜20 nm) exhibiting distinctive photoluminescence (PL) properties due to the quantum confinement effect. Having many advantages over organic dyes, such as broad excitation and resistance to photobleaching, QDs are widely used in bioapplications as one of most exciting nanobiotechnologies. To date, most commercial QDs are synthesized through the traditional organometallic method and contain toxic elements, such as cadmium, lead, mercury, arsenic, etc. The overall goal of this thesis study is to develop an aqueous synthesis method to produce nontoxic quantum dots with strong emission and good stability, suitable for biomedical imaging applications. Firstly, an aqueous, simple, environmentally friendly synthesis method was developed. With cadmium sulfide (CdS) QDs as an example system, various processing parameters and capping molecules were examined to improve the synthesis and optimize the PL properties. The obtained water soluble QDs exhibited ultra small size (˜5 nm), strong PL and good stability. Thereafter, using the aqueous method, the zinc sulfide (ZnS) QDs were synthesized with different capping molecules, i.e., 3-mercaptopropionic acid (MPA) and 3-(mercaptopropyl)trimethoxysilane (MPS). Especially, via a newly developed capping molecule replacement method, the present ZnS QDs exhibited bright blue emission with a quantum yield of 75% and more than 60 days lifetime in the ambient conditions. Two cytotoxicity tests with human endothelial cells verified the nontoxicity of the ZnS QDs by cell counting with Trypan blue staining and fluorescence assay with Alamar Blue. Taking advantage of the versatile surface chemistry, several strategies were explored to conjugate the water soluble QDs with biomolecules, i.e., antibody and streptavidin. Accordingly, the imaging of Salmonella t. cells and biotinylated microbeads has been successfully demonstrated. In addition, polyethylenimine (PEI)-QDs complex was formed and

  20. The regulation of sepiolite surface free energy and its impact on the thermal insulation property of coating.

    PubMed

    Chen, Cong; Liang, Jinsheng; Wang, Fei; Tang, Qingguo; Chen, Yalei

    2014-05-01

    Surface modification is used to regulate surface free energy of sepiolite with 3-glycidoxypropyltrimethoxysilanes (3-GPTMS), 3-methacryloxypropyltrimethoxysilanes (3-MAPTMS) and 3-mercaptopropyltrimethoxysilane (3-MPTMS). Through characterization by Fourier transform infrared spectroscopy, surface free energy, zeta potential and sedimentation measurements and infrared emissivity, it is found that the surface free energy of 3-MPTMS modified sepiolite decreases to 31.72 mJ/m2 and the percentage of polar component increases to 89.75%, thus leading to that the infrared emissivity of 3-MPTMS modified sepiolite increase to be higher than 0.8 and the dispersion of sepiolite has been improved. The excellent thermal insulation property of coating is prepared with 10% additive amount of 3-MPTMS modified sepiolite and the temperature difference between upper and lower box of modified sepiolite coatings is 10 degrees C which is higher than the untreated sepiolite.

  1. Antibacterial cotton fibers treated with silver nanoparticles and quaternary ammonium salts.

    PubMed

    Kang, Chan Kyu; Kim, Sam Soo; Kim, Soojung; Lee, Jintae; Lee, Jin-Hyung; Roh, Changhyun; Lee, Jaewoong

    2016-10-20

    Cotton fibers were treated chemically with glycidyltrimethylammonium chloride (GTAC), a quaternary ammonium salt, and coated with silver nanoparticles/3-mercaptopropyltrimethoxysilane (3-MPTMS) to increase the antibacterial efficacy. The coating process was accomplished by soaking the cotton fibers into a GTAC solution followed by a dry-cure method, and silver colloid/3-MPTMS solution was then applied at 43°C for 90min. The properties of the cotton fibers were analyzed by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. SEM showed a rough surface when the cotton fibers were treated with GTAC/3-MPTMS/silver nanoparticles due to the increasing surface attachment. The existence of silver and 3-MPTMS on the cotton fibers was confirmed by XPS. The cotton fibers treated with both GTAC and silver nanoparticles showed synergistic antibacterial properties against P. aeruginosa. PMID:27474649

  2. Development of uniform density control with self-assembled colloidal gold nanoparticles on a modified silicon substrate.

    PubMed

    Kang, ChanKyu; Ashurst, Robert W; Shim, Jae-Jin; Huh, Yun Suk; Roh, Changhyun

    2014-10-01

    Here, we present a simple method for controlling the density of Au nanoparticles (Au NPs) on a modified silicon substrate, by destabilizing the colloidal Au NPs with 3-mercaptopropyltrimethoxylsilane (3-MPTMS) for microelectromechanical-system-based applications to reduce tribological issues. A silicon surface was pretreated with a 3-MPTMS solution, immediately after which thiolated Au NPs were added to it, resulting in their uniform deposition on the silicon substrate. Without any material property change of the colloidal Au NPs, we observed the formation of large clusters Au NPs on the modified silicon surface. Analysis by scanning electron microscopy with energy dispersive X-ray spectroscopy indicated that the addition of 3-MPTMS resulted in an alternation of the chemical characteristics of the solution. Atomic force microscopy imaging supported the notion that silicon surface modification is the most important factor on tribological properties of materials along with ligand-modified Au NPs. The density of Au NPs on a silicon surface was significantly dependent on several factors, including the concentration of colloidal Au NPs, deposition time, and concentration of 3-MPTMS solution, while temperature range which was used throughout experiment was determined to have no significant effect. A relatively high density of Au NPs forms on the silicon surface as the concentrations of Au NPs and 3-MPTMS are increased. In addition, the maximum deposition of Au NPs on silicon wafer was observed at 3 h, while the effects of temperature variation were minimal.

  3. Chemical functionalization of diatom silica microparticles for adsorption of gold (III) ions.

    PubMed

    Yu, Yang; Addai-Mensah, Jonas; Losic, Dusan

    2011-12-01

    Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions. PMID:22408909

  4. Preparation of nanoporous carbons via a grafting method for the application to electrochemical double layer capacitors.

    PubMed

    Kim, Wooyoung; Kang, Mi Yeong; Kim, Nam Dong; Joo, Ji Bong; Yi, Jongheop

    2011-01-01

    Nanoporous carbon materials with a controlled pore size and surface area were prepared using grafting method. The use of 3-mercaptopropyltrimethoxysilane (MPTMS) as a grafting material played an important role in producing a porous structure by linking the silica to the polymer, with the subsequent formation of a silica-polymer composite. Importantly, the use of an organic solvent, compared to an aqueous solvent, has a positive effect in forming uniform and well-developed carbon structures, due to the high degree of dispersion with well-mixing of the carbon and silica precursors. The amounts of MPTMS and carbon precursor used determined the pore size and surface area of resulting carbon materials. The optimum ratio of MPTMS and carbon precursor for achieving a high surface area in excess of 2000 m2/g was determined. The use of a large amount of carbon precursor resulted in carbons with a relatively small surface area and an increase in MPTMS content led to an increase in the microporous structures. The capacitance value of the porous carbon prepared using the optimum ratio was determined to be 150 F/g.

  5. The effect of electron irradiation on the structure and the optical properties of silver particulate films deposited on modified thermoplastic polymer substrates

    NASA Astrophysics Data System (ADS)

    Kakkrannaya, A. Rakesha; Rao, K. Mohan; Tolpadi, Amita; Sanjeev, Ganesh; Pattabi, Manjunatha

    2016-03-01

    The silver (Ag) particulate films are prepared by the vacuum evaporation onto polystyrene (PS) substrates modified with 3-mercaptopropyltrimethoxysilane (MPTMS), pre-irradiated with the 8-MeV electron beam, held at a temperature 453 K. The effect of organosilane and electron irradiation dose on the Ag particulate structure is studied through optical spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) with selected area electron diffraction (SAED) pattern, atomic-force microscopy (AFM), and X-ray diffraction (XRD). The flat spectrum observed for the lower irradiation doses may be due to the formation of the clusters of different sizes and shapes. The band shift toward the higher wavelength is attributed to the increased aggregation leading to the formation of the larger-sized nanoclusters. A long tail extending to the higher wavelength region is also observed due to aggregation process. The FESEM studies indicate the formation of the silver nanoclusters. The decrease in the particle size with the increase in irradiation dose as seen through TEM studies is interpreted on the basis of polymer-metal particle interaction caused by the free radicals formed due to the electron irradiation of the MPTMS-modified PS substrates. The SAED pattern shows the crystalline nature of the silver particles formed on the pure PS and the MPTMS-modified PS substrates irradiated with the electron beam. The AFM studies show an increase in the average surface roughness of the silver films with the electron irradiation dose and the MPTMS concentration. XRD indicated the polycrystalline nature of silver film on the pre-irradiated PS substrates and formation of nanocrystallites of silver with preferred orientation on the MPTMS-modified PS substrates pre-irradiated with electron beam.

  6. A new, simple approach to confer permanent antimicrobial properties to hydroxylated surfaces by surface functionalization.

    PubMed

    Bouloussa, Othman; Rondelez, Francis; Semetey, Vincent

    2008-02-28

    A new, simple method to obtain ultrathin polycationic monolayers on hydroxylated surfaces is described which uses a bifunctional copolymer comprising a reactive part (trimethoxysilane) and positive charges (quaternary ammonium salts) to confer antimicrobial properties.

  7. The significant adhesion enhancement of Ag-polytetrafluoroethylene antibacterial coatings by using of molecular bridge

    NASA Astrophysics Data System (ADS)

    Guo, Ruijie; Yin, Guangda; Sha, Xiaojuan; Zhao, Qi; Wei, Liqiao; Wang, Huifang

    2015-06-01

    Weak adhesion between the metal-based antibacterial coatings and polymer substrates limits their clinical applications; surface modification is an effective way to solve this intrinsic problem. In this study, UV irradiation was employed to activate the inert silicon rubber substrates, and the grafting of coupling agent (3-mercaptopropyl) trimethoxy silane into the UV-irradiated substrates generated reactive surface containing sbnd SH groups. During electroless plating S which has lone pair electrons anchored Ag+ and produced antibacterial coatings with improved adhesion. The grafting of (3-mercaptopropyl) trimethoxy silane into silicon rubber was verified by X-ray photoelectron spectroscopy (XPS). The adhesion was tested by American Society of Testing Materials (ASTM D 3359-02). Surface elements content and distribution were observed and analyzed by X-ray energy disperse spectroscopy (EDS). The antibacterial performance was characterized by inhibition halo test and shake flash method. The results showed that the as-prepared composite Ag-polytetrafluoroethylene coatings possessed remarkably enhanced adhesion and superior antibacterial activity.

  8. 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

  9. A precise and efficient detection of Beta-Cyfluthrin via fluorescent molecularly imprinted polymers with ally fluorescein as functional monomer in agricultural products.

    PubMed

    Qiu, Hao; Gao, Lin; Wang, Jixiang; Pan, Jianming; Yan, Yongsheng; Zhang, Xifeng

    2017-02-15

    In this study, an effective and precise fluorescent molecularly imprinted polymers (FMIPs) for the determination of Beta-Cyfluthrin (BC) was synthesized via precipitation polymerization with SiO2 as the carrier, BC as the target molecule, ally fluorescein as the functional monomer, trimethylolpropane trimethacrylate (TRIM) as the crosslinker. Moreover, the characteristic of material has been measured by FTIR, TEM, SEM, TGA, LSCM and fluorescence spectrophotometer. Average diameter and shell thickness of as-synthesized microspheres were 300nm and 50nm, respectively. An excellent linear relationship of SiO2-MPTMS@FMIPs with a correlation coefficient of 0.9919 could be gained covering a wide concentration range of 10.11-80nM described by the Stern-Volmer equation. The limit of detection (LOD) was evaluated with the equation LOD=3σ/S and was found to be 10.11nM. The study demonstrated that SiO2-MPTMS@FMIPs could improve the determination for BC and illustrated the good prospects of SiO2-MPTMS@FMIPs for BC detection in agricultural products.

  10. A precise and efficient detection of Beta-Cyfluthrin via fluorescent molecularly imprinted polymers with ally fluorescein as functional monomer in agricultural products.

    PubMed

    Qiu, Hao; Gao, Lin; Wang, Jixiang; Pan, Jianming; Yan, Yongsheng; Zhang, Xifeng

    2017-02-15

    In this study, an effective and precise fluorescent molecularly imprinted polymers (FMIPs) for the determination of Beta-Cyfluthrin (BC) was synthesized via precipitation polymerization with SiO2 as the carrier, BC as the target molecule, ally fluorescein as the functional monomer, trimethylolpropane trimethacrylate (TRIM) as the crosslinker. Moreover, the characteristic of material has been measured by FTIR, TEM, SEM, TGA, LSCM and fluorescence spectrophotometer. Average diameter and shell thickness of as-synthesized microspheres were 300nm and 50nm, respectively. An excellent linear relationship of SiO2-MPTMS@FMIPs with a correlation coefficient of 0.9919 could be gained covering a wide concentration range of 10.11-80nM described by the Stern-Volmer equation. The limit of detection (LOD) was evaluated with the equation LOD=3σ/S and was found to be 10.11nM. The study demonstrated that SiO2-MPTMS@FMIPs could improve the determination for BC and illustrated the good prospects of SiO2-MPTMS@FMIPs for BC detection in agricultural products. PMID:27664679

  11. The influence of silanisation on the mechanical and degradation behaviour of PLGA/HA composites.

    PubMed

    Naik, Ashutosh; Best, Serena M; Cameron, Ruth E

    2015-03-01

    This study investigates the influence of silanisation on the mechanical and degradation behaviour of PLGA/HA composites. Three different silanes (mercaptopropyl trimethoxy silane (MPTMS), aminopropyl trimethoxy silane (APTMS) and aminopropyltriethoxy silane (APTES)) were applied to HA substrates in order to study the effect of head group (which binds to the polymer) and tail group (which binds to the surface hydroxyl groups in HA). A composite of hydroxyapatite (HA) and poly(d,l lactide-co-glycolide (50:50)) (PLGA) was investigated. The influence of concentration, the reaction time, drying temperature and substrate surface on silanisation was examined. TGA was used to detect the degree of silanisation. HA with MPTMS (1wt.% MPTMS with reaction time of 1h) was used as filler in PLGA-30wt.% HA composites for an in-vitro degradation study carried out in PBS. In addition, the mechanical properties of the composites were studied. Silanisation affects the properties of the composite by improving the bonding at the interface and hence it was found to influence the plastic mechanical properties rather than the elastic mechanical properties or the degradation profile of the composite.

  12. Silicon Oxycarbide/Carbon Nanohybrids with Tiny Silicon Oxycarbide Particles Embedded in Free Carbon Matrix Based on Photoactive Dental Methacrylates.

    PubMed

    Wang, Meimei; Xia, Yonggao; Wang, Xiaoyan; Xiao, Ying; Liu, Rui; Wu, Qiang; Qiu, Bao; Metwalli, Ezzeldin; Xia, Senlin; Yao, Yuan; Chen, Guoxin; Liu, Yan; Liu, Zhaoping; Meng, Jian-Qiang; Yang, Zhaohui; Sun, Ling-Dong; Yan, Chun-Hua; Müller-Buschbaum, Peter; Pan, Jing; Cheng, Ya-Jun

    2016-06-01

    A new facile scalable method has been developed to synthesize silicon oxycarbide (SiOC)/carbon nanohybrids using difunctional dental methacrylate monomers as solvent and carbon source and the silane coupling agent as the precursor for SiOC. The content (from 100% to 40% by mass) and structure (ratio of disordered carbon over ordered carbon) of the free carbon matrix have been systematically tuned by varying the mass ratio of methacryloxypropyltrimethoxysilane (MPTMS) over the total mass of the resin monomers from 0.0 to 6.0. Compared to the bare carbon anode, the introduction of MPTMS significantly improves the electrochemical performance as a lithium-ion battery anode. The initial and cycled discharge/charge capacities of the SiOC/C nanohybrid anodes reach maximum with the MPTMS ratio of 0.50, which displays very good rate performance as well. Detailed structures and electrochemical performance as lithium-ion battery anodes have been systematically investigated. The structure-property correlation and corresponding mechanism have been discussed. PMID:27186647

  13. SBA-15 mesoporous silica coated with macrocyclic calix[4]arene derivatives: solid extraction phases for heavy transition metal ions.

    PubMed

    Su, Bao-Lian; Ma, Xu-Chu; Xu, Fen; Chen, Li-Hua; Fu, Zheng-Yi; Moniotte, Nicolas; Ben Maamar, Sami; Lamartine, Roger; Vocanson, Francis

    2011-08-01

    A layer of macrocyclic calix[4]arene derivatives has been grafted on the internal surface of the mesochannels of the ordered mesoporous SBA-15 to develop highly efficient trap for heavy transition metal (HTM) ions. To ensure the successful anchoring of calix[4]arene derivatives on the surface of SBA-15, two different types of calix[4]arene derivatives, one with one trimethoxysilane functional group and another with two trimethoxysilane functional groups have been explored. XRD, N(2) adsorption and TEM results provide strong evidence that the mesoporous structure of the supporting materials retain their long range ordering throughout the grafting process. Solid-state NMR, TG and FT-IR spectroscopy indicate that both types of calix[4]arene derivatives can be well-anchored on the surface of the wall of SBA-15. Calix[4]arene derivative with only one trimethoxysilane functional group showed high grafting efficiency compared to that with two trimethoxysilane functional groups due to the intramolecular and intermolecular polycondensation between two trimethoxysilane functional groups. The HTM ions extraction capacity in aqueous solution of macrocycle functionalized SBA-15 nanohybrides for a series of HTM ions has been studied. The obtained materials demonstrated very high HTM ions extraction capacity up to 96% for Pb(2+) in aqueous solution.

  14. Preparation and evaluation of novel chiral stationary phases based on quinine derivatives comprising crown ether moieties.

    PubMed

    Wang, Dongqiang; Zhao, Jianchao; Wu, Haixia; Wu, Haibo; Cai, Jianfeng; Ke, Yanxiong; Liang, Xinmiao

    2015-01-01

    The C9-position of quinine was modified by meta- or para-substituted benzo-18-crown-6, and immobilized on 3-mercaptopropyl-modified silica gel through the radical thiol-ene addition reaction. These two chiral stationary phases were evaluated by chiral acids, amino acids, and chiral primary amines. The crown ether moiety on the quinine anion exchanger provided a ligand-exchange site for primary amino groups, which played an important role in the retention and enantioselectivity for chiral compounds containing primary amine groups. These two stationary phases showed good selectivity for some amino acids. The complex interaction between crown ether and protonated primary amino group was investigated by the addition of inorganic salts such as LiCl, NH4Cl, NaCl, and KCl to the mobile phase. The resolution results showed that the simultaneous interactions between two function moieties (quinine and crown ether) and amino acids were important for the chiral separation.

  15. Highly Luminescent Heterostructured Copper-Doped Zinc Sulfide Nanocrystals for Application in Cancer Cell Labeling.

    PubMed

    Ang, Huixiang; Bosman, Michel; Thamankar, Ramesh; Zulkifli, Muhammad Faizal B; Yen, Swee Kuan; Hariharan, Anushya; Sudhaharan, Thankiah; Selvan, Subramanian Tamil

    2016-08-18

    The structural characteristics of the seed-mediated synthesis of heterostructured CuS-ZnS nanocrystals (NCs) and Cu-doped ZnS (ZnS:Cu) NCs synthesized by two different protocols are compared and analyzed. At high Cu dopant concentrations, segregated subclusters of ZnS and CuS are observed. The photoluminescence quantum yield of ZnS:Cu NCs is about 50-80 %; a value much higher than that of ZnS NCs (6 %). Finally, these NCs are coated with a thin silica shell by using (3-mercaptopropyl)triethoxysilane in a reverse microemulsion to make them water soluble. Cytotoxicity experiments show that these silica-coated NCs have greatly reduced toxicity on both cancerous HeLa and noncancerous Chinese hamster ovary cells. The labeling of cancerous HeLa cells is also demonstrated. PMID:27146419

  16. Behaviour of dental pulp stem cells on different types of innovative mesoporous and nanoporous silicon scaffolds with different functionalizations of the surfaces.

    PubMed

    Marrelli, M; Falisi, G; Apicella, A; Apicella, D; Amantea, M; Cielo, A; Bonanome, L; Palmieri, F; Santacroce, L; Giannini, S; Di Fabrizio, E; Rastelli, C; Gargari, M; Cuda, G; Paduano, F; Tatullo, M

    2015-01-01

    Dental pulp stem cells (DPSCs) are stem cells found in the dental pulp. The ability of DPSCs to differentiate towards odontoblastic and osteoblastic phenotype was reported first in the literature, then in the following years, numerous studies on odontogenesis were carried out, starting from mesenchymal stem cells isolated from tissues of dental and oral origin. The aim of this research was to evaluate the behaviour of DPSCs grown on silicon nanoporous and mesoporous matrices and differentiated towards the osteogenic phenotype, but also to investigate the use of DPSCs in pilot studies focused on the biological compatibility of innovative dental biomaterials. Twenty-eight silicon samples were created with standardized procedures. These scaffolds were divided into samples made of silicon bulk, nanoporous silicon, mesoporous silicon, nanoporous silicon functionalized with (3-Aminopropyl) Trimethoxysilane (APTMS) and methanol (MeOH), nanoporous silicon functionalized with (3-Aminopropyl) Trimethoxysilane (APTMS)/toluene, mesoporous silicon functionalized with (3-Aminopropyl) Trimethoxysilane (APTMS) and methanol (MeOH) andmesoporous silicon functionalized with (3-Aminopropyl) Trimethoxysilane (APTMS)/toluene. DPSC proliferation on the tested silicon scaffolds was analyzed at 3 and 5 days. The assay showed that DPSCs proliferated better on mesoporous scaffolds functionalized with APTMS/toluene compared to a silicon one. These results show that the functionalization of silicon scaffold with APTMS/toluene supports the growth of DPSCs and could be used for future applications in tissue engineering.

  17. Alternative mounting media for preservation of some protozoa.

    PubMed

    Criado-Fornelio, A; Heredero-Bermejo, I; Pérez-Serrano, J

    2014-10-01

    Protozoa resistant stages are disintegrated when mounted in toluene-based media. To overcome such problem, three toluene-free mountants were tested on preserve Acanthamoeba spp and gregarines. Two commercial glues based on cyanoacrylate or trimethoxysilane were suitable for preserving both cysts and trophozoites. Hoyer's medium showed good results for mounting gregarine oocysts.

  18. Surface self-segregation, wettability, and adsorption behavior of core-shell and pentablock fluorosilicone acrylate copolymers.

    PubMed

    Liang, Junyan; He, Ling; Dong, Xia; Zhou, Tie

    2012-03-01

    The surfaces of films cast from core-shell fluorosilicone acrylate copolymer (BA/MMA/DFHM and BA/MMA/DFHM/MPTMS/D(4)) latexes and linear pentablock fluorosilicone acrylate copolymer (PDMS-b-(PMMA-b-PDFHM)(2)) solutions are intensively investigated and compared by XPS, DCA, AFM, and QCM-D measurements. It is found that the molecular structures and in-solution aggregate structures of these well-defined copolymers have a dramatic influence on the surface structure formation, surface wetting, and adsorption behavior. The PDMS-b-(PMMA-b-PDFHM)(2) film cast from chloroform solution with high concentration of low-density unimers is able to perform as strong surface self-segregation of fluorine-containing groups as core-shell copolymer latex films. The BA/MMA/DFHM/MPTMS/D(4) in the core-shell latex particles exhibits the less pronounced surface self-segregation of silicon-containing groups than PDMS-b-(PMMA-b-PDFHM)(2) due to the occurrence of cross-linking reactions between polysiloxane chains. Indeed, such reactions induce the formation of silica network within the film material, which immobilizes tightly the fluorinated groups on the film surface and thus endows the film with higher surface structural stability for water compared to PDMS-b-(PMMA-b-PDFHM)(2) film with similar surface fluorine concentration and even higher silicon concentration. Still, the PDMS-b-(PMMA-b-PDFHM)(2) film definitely demonstrates higher advancing and receding contact angles for water than BA/MMA/DFHM/MPTMS/D(4) latex film in the case of synergism between surface enrichment of fluorine and silicon.

  19. Factors affecting the preparation and properties of electrodeposited silica thin films functionalized with amine or thiol groups.

    PubMed

    Sibottier, Emilie; Sayen, Stéphanie; Gaboriaud, Fabien; Walcarius, Alain

    2006-09-26

    Well-adherent sol-gel-derived silica films functionalized with amine or thiol groups have been electrogenerated on gold electrodes and both the deposition process and the film properties have been studied by various physicochemical techniques. Electrodeposition was achieved by combining the formation of a self-assembled "nanoglue" on the electrode surface, the sol-gel process, and the electrochemical manipulation of pH to catalyze polycondensation of the precursors. Gold electrodes pretreated with mercaptopropyltrimethoxysilane (MPTMS) were immersed in sol solutions containing the selected precursors (tetraethoxysilane, TEOS, in mixture with (3-aminopropyl)triethoxysilane, APTES, or MPTMS) where they underwent a cathodic electrolysis to generate the hydroxyl ions that are necessary to catalyze the formation of the organosilica films on the electrode surface. Special attention was given to analyze the effects of deposition time and applied potential and to compare APTES and MPTMS films. Characterization was made using quartz crystal microbalance, scanning electron microscopy, cyclic voltammetry, and atomic force microscopy (including in situ monitoring). The electrodeposition process was found to occur at two growing rates: a first slow stage giving rise to rather homogeneous, yet rough, films with thickness in the sub-mum range (increasing continuously when increasing the deposition time), which was followed by a faster gelification step resulting in much thicker (>1 microm) and rougher macroporous deposits. These two successive situations were observed independently on the applied potential except that more cathodic values led to narrower sub-microm ranges (as expected from the larger amounts of the electrogenerated hydroxyl catalyst). Thiol-functionalized silica films were deposited more rapidly than the amine ones and, for both of them, permeability to redox probe was found to decrease when increasing the film thickness because of higher resistance to mass

  20. Effect of surface chemical composition on the surface potential and iso-electric point of silicon substrates modified with self-assembled monolayers.

    PubMed

    Kuo, Che-Hung; Chang, Hsun-Yun; Liu, Chi-Ping; Lee, Szu-Hsian; You, Yun-Wen; Shyue, Jing-Jong

    2011-03-01

    Self-assembled monolayer (SAM)-modified nano-materials are a new technology to deliver drug molecules. While the majority of these depend on covalently immobilizing molecules on the surface, it is proposed that electrostatic interactions may be used to deliver drugs. By tuning the surface potential of solid substrates with SAMs, drug molecules could be either absorbed on or desorbed from substrates through the difference in electrostatic interactions around the selected iso-electric point (IEP). In this work, the surface of silicon substrates was tailored with various ratios of 3-aminopropyltrimethoxysilane (APTMS) and 3-mercaptopropyltrimethoxysilane (MPTMS), which form amine- and thiol-bearing SAMs, respectively. The ratio of the functional groups on the silicon surface was quantified by X-ray photoelectron spectrometry (XPS); in general, the deposition kinetics of APTMS were found to be faster than those of MPTMS. Furthermore, for solutions with high MPTMS concentrations, the relative deposition rate of APTMS increased dramatically due to the acid-base reaction in the solution and subsequent electrostatic interactions between the molecules and the substrate. The zeta potential in aqueous electrolytes was determined with an electro-kinetic analyzer. By depositing SAMs of binary functional groups in varied ratios, the surface potential and IEP of silicon substrates could be fine-tuned. For <50% amine concentration in SAMs, the IEP changed linearly with the chemical composition from <2 to 7.18. For higher amine concentrations, the IEP slowly increased with concentration to 7.94 because the formation of hydrogen-bonding suppressed the subsequent protonation of amines.

  1. Fiber Surface Modification Technology for Fiber-Optic Localized Surface Plasmon Resonance Biosensors

    PubMed Central

    Zhang, Qiang; Xue, Chenyang; Yuan, Yanling; Lee, Junyang; Sun, Dong; Xiong, Jijun

    2012-01-01

    Considerable studies have been performed on the development of optical fiber sensors modified by gold nanoparticles based on the localized surface plasmon resonance (LSPR) technique. The current paper presents a new approach in fiber surface modification technology for biosensors. Star-shaped gold nanoparticles obtained through the seed-mediated solution growth method were found to self-assemble on the surface of tapered optical fibers via amino- and mercapto-silane coupling agents. Transmitted power spectra of 3-aminopropyltrimethoxy silane (APTMS)-modified fiber were obtained, which can verify that the silane coupling agent surface modification method is successful. Transmission spectra are characterized in different concentrations of ethanol and gentian violet solutions to validate the sensitivity of the modified fiber. Assembly using star-shaped gold nanoparticles and amino/mercapto silane coupling agent are analyzed and compared. The transmission spectra of the gold nanoparticles show that the nanoparticles are sensitive to the dielectric properties of the surrounding medium. After the fibers are treated in t-dodecylmercaptan to obtain their transmission spectra, APTMS-modified fiber becomes less sensitive to different media, except that modified by 3-mercaptopropyltrimethoxy silane (MPTMS). Experimental results of the transmission spectra show that the surface modified by the gold nanoparticles using MPTMS is firmer compared to that obtained using APTMS. PMID:22736974

  2. Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups.

    PubMed

    Tsai, Hui-Hsu Gavin; Chiu, Po-Jui; Jheng, Guang-Liang; Ting, Chun-Chiang; Pan, Yu-Chi; Kao, Hsien-Ming

    2011-07-01

    Well-ordered cubic mesoporous silicas SBA-1 functionalized with sulfonic acid groups have been synthesized through in situ oxidation of mercaptopropyl groups with H(2)O(2) via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strong acidic conditions. Various synthesis parameters such as the amounts of H(2)O(2) and MPTMS on the structural ordering of the resultant materials were systematically investigated. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), multinuclear solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, (29)Si{(1)H} 2D HETCOR (heteronuclear correlation) NMR spectroscopy, thermogravimetric analysis (TGA), and nitrogen sorption measurements. By using (13)C CPMAS NMR technique, the status of the incorporated thiol groups and their transformation to sulfonic acid groups can be monitored and, as an extension, to define the optimum conditions to be used for the oxidation reaction to be quantitative. In particular, (29)Si{(1)H} 2D HETCOR NMR revealed that the protons in sulfonic acid groups are in close proximity to the silanol Q(3) species, but not close enough to form a hydrogen bond.

  3. [Preparation of organic-inorganic hybrid boronate affinity monolith via thiol-ene click reaction for specific capture of glycoproteins].

    PubMed

    Yang, Fan; Mao, Jie; He, Xiwen; Chen, Langxing; Zhang, Yukui

    2013-06-01

    A novel strategy for the preparation of the organic-inorganic hybrid boronate affinity monolith was developed via the "thiol-ene" click reaction. A thiol group-modified silica monolith was first synthesized via the sol-gel process by the in situ co-condensation with tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) as precursors. Then 3-acrylamidophenylboronic acid (AAPBA) was covalently immobilized on the hybrid monolith via the "thiol-ene" click reaction to form AAPBA-silica hybrid affinity monolith. The reaction conditions for the preparation of AAPBA-silica hybrid affinity monolith were optimized, including the ratio of TMOS to MPTMS, the contents of poly(ethylene glycol) (PEG) and methanol. The morphology and mechanical stability of the boronate affinity monolith were characterized and evaluated by scanning electron microscopy and Fourier-transform infrared spectroscopy. The obtained boronate affinity hybrid monolith exhibited excellent specificity toward the nucleosides containing cis-diols under neutral conditions. It was further applied to the specific capture of the glycoproteins ovalbumin and horseradish peroxidase. The method is novel and reliable, which has a great potential for the preparation of different kinds of the boronate affinity monoliths.

  4. Silica-coated magnetic nanoparticles modified with γ-mercaptopropyltrimethoxysilane for fast and selective solid phase extraction of trace amounts of Cd, Cu, Hg, and Pb in environmental and biological samples prior to their determination by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Huang, Chaozhang; Hu, Bin

    2008-03-01

    We report here the synthesis of a new sorbent comprising silica-coated magnetic nanoparticles (SCMNPs) modified with γ-mercaptopropyltrimethoxysilane (γ-MPTMS) for solid phase extraction of trace amounts of Cd, Cu, Hg, and Pb from biological and environmental samples. The prepared nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, and static adsorption-desorption experiments. These magnetic nanoparticles carrying the target metals could be easily separated from the aqueous solution simply by applying an external magnetic field; no filtration or centrifugation was necessary. Using this novel magnetic material, we have developed an efficient and cost-effective two-step method for detecting trace amounts of Cd, Cu, Hg, and Pb in environmental and biological samples. The first step of the method is a separation/preconcentration step, in which metals are adsorbed onto γ-MPTMS-SCMNPs. In the second step, inductively coupled plasma mass spectrometry is used to study the adsorbed metals. The effects of pH, sample volume, eluent, and interfering ions have been investigated. Under the optimized conditions, the limits of detection for Cd, Cu, Hg, and Pb were as low as 24, 92, 107, and 56 pg L - 1 , respectively. Relative standard deviations (RSDs, C = 2 ng L - 1 , n = 7) were 6.7%, 9.6%, 8.3%, and 3.7%, respectively.The proposed method has been validated using three certified reference materials, and it has been applied successfully in the determination of trace metals in biological and environmental samples.

  5. Role of palladium in the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within ORMOSIL networks.

    PubMed

    Pandey, P C; Upadhyay, B C

    2005-07-14

    We report herein the effect of palladium on the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within an organically modified sol-gel glass network (ORMOSIL). It has been found that amount of palladium and its geometrical distribution significantly alter the redox electrochemistry of FcMCA. The geometrical distribution of palladium has been controlled by two methods: (i) palladium is allowed to link within nanostructured network of the ORMOSIL which was subsequently availed from the reactivity of palladium chloride and trimethoxysilane; (ii) palladium powder is encapsulated together FcMCA thus allowing the presence of palladium within the nanoporous domain. The content of palladium is varied by controlling the reaction dynamics of palladium chloride and trimethoxysilane interaction. For this we initially allowed to trigger hydrolysis, condensation and poly-condensation of trimethoxysilane and dimethyldiethoxysilane in acidic medium and subsequently partially dried ORMOSIL film was allowed to interact with palladium chloride. Even with partially dried ORMOSIL derived from trimethoxysilane and dimethyldiethoxysilane undergoes rapid interaction with palladium chloride and the transparent color of ORMOSIL changed to a black colour due to the formation of palladium silicon linkage. The palladium-silicon linkage has been identified by NMR, UV-VIS and transmission electron spectroscopy. The electrochemistry of FcMCA encapsulated within such an ORMOSIL matrix has been studied. Excellent redox electrochemistry of ferrocene monocarboxylic acid having peak potential separation tending to 0 for a multilayered electrode was investigated. The palladium content has been found to affect the redox electrochemistry of ferrocene as well as electrocatalytic efficiency of new ORMOSIL material. The electroanalysis of NADH is reported. The modified electrode is very sensitive to NADH with lowest detection limit of < 1 microM.

  6. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    PubMed

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules.

  7. Novel chiral stationary phases based on peptoid combining a quinine/quinidine moiety through a C9-position carbamate group.

    PubMed

    Wu, Haibo; Wang, Dongqiang; Song, Guangjun; Ke, Yanxiong; Liang, Xinmiao

    2014-04-01

    By connecting a quinine or quinidine moiety to the peptoid chain through the C9-position carbamate group, we synthesized two new chiral selectors. After immobilizing them onto 3-mercaptopropyl-modified silica gel, two novel chiral stationary phases were prepared. With neutral, acid, and basic chiral compounds as analytes, we evaluated these two stationary phases and compared their chromatographic performance with chiral columns based on quinine tert-butyl carbamate and the previous peptoid. From the resolution of neutral and basic analytes under normal-phase mode, it was found that the new stationary phases exhibited much better enantioselectivity than the quinine tert-butyl carbamate column; the peptoid moiety played an important role in enantiorecognition, which controlled the elution orders of enantiomers; the assisting role of the cinchona alkaloid moieties was observed in some separations. Under acid polar organic phase mode, it was proved that cinchona alkaloid moieties introduced excellent enantiorecognitions for chiral acid compounds; in some separations, the peptoid moiety affected enantioseparations as well. Overall, chiral moieties with specific enantioselectivity were demonstrated to improve the performance of peptoid chiral stationary phase efficiently.

  8. Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

    PubMed

    Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2014-02-21

    In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange.

  9. Functionalization of multiwalled carbon nanotubes for the solid-phase extraction of silver, cadmium, palladium, zinc, manganese and copper by flame atomic absorption spectrometry.

    PubMed

    Ghaedi, Mehrorang; Montazerozohori, M; Nazari, E; Nejabat, R

    2013-07-01

    In the present work, multiwalled carbon nanotube (MWCNT) chemically modified with (3-mercaptopropyl) silanetriolate is efficiently used for the solid-phase extraction of Cu(2+), Ag(+), Cd(2+), Pb(2+), Zn(2+) and Mn(2+) ions prior to their flame atomic absorption spectrometric determination. The influences of the various analytical parameters, including pH, amounts of solid phase, sample volume and eluent conditions and so on, on the recoveries of target analytes were investigated and optimized by one at a time optimization method. The influences of alkaline, alkaline earth and some transition metals on the adsorption and elution of the analytes were also examined. The detection limits for all understudied metal ions were between 1.4 and 2.8 ng mL(-1) (3Sb, n = 10). The evaluation of the thermodynamic parameters such as enthalpy (positive value), Gibbs free energy (negative value) in addition to high value of entropy shows the endothermic and spontaneous nature of sorption process. Following the optimization of variables, the adsorption process follows the intraparticle kinetic model with R (2) of 0.98 and the Langmuir isotherm with high correlation coefficient (R (2) > 0.95). The procedure was applied for the analytes determination in the food samples with satisfactory results (recoveries >95% and relative standard deviation's (RSD) lower than 4%).

  10. Site-specific immobilization and micrometer and nanometer scale photopatterning of yellow fluorescent protein on glass surfaces.

    PubMed

    Reynolds, Nicholas P; Tucker, Jaimey D; Davison, Paul A; Timney, John A; Hunter, C Neil; Leggett, Graham J

    2009-01-28

    A simple method is described for the site-specific attachment of yellow fluorescent protein (YFP) to glass surfaces on length scales ranging from tens of micrometers to ca. 200 nm. 3-Mercaptopropyl(triethoxy silane) is adsorbed onto a glass substrate and subsequently derivatized using a maleimide-functionalized oligomer of ethylene glycol. The resulting protein-resistant surface is patterned by exposure to UV light, causing photochemical degradation of the oligo(ethylene glycol) units to yield aldehyde groups in exposed regions. These are covalently bound to N-(5-amino-1-carboxypentyl)iminoacetic acid, yielding a nitrilotriacetic acid (NTA)-functionalized surface, which following complexation with Ni(2+), is coupled to His-tagged YFP. Using scanning near-field photolithography, in which a UV laser coupled to a scanning near-field optical microscope is utilized as the light source for photolithography, it is possible to fabricate lines of protein smaller than 200 nm, in which the biomolecules remain strongly optically active, facilitating the acquisition of diffraction-limited fluorescence images by confocal microscopy.

  11. Ultra-trace electrochemical impedance determination of bovine serum albumin by a two dimensional silica network citrate-capped gold nanoparticles modified gold electrode.

    PubMed

    Yari, Abdollah; Saeidikhah, Marzieh

    2015-11-01

    In this work, a gold electrode (GE) was modified by coating with two dimensional silica network/citrate capped gold nanoparticles-poly(diallyldimethylammonium chloride) (GE-TDSN-CGNP-PDDA) for ultra-sensitive determination of Bovine Serum Albumin (BSA). After covalently binding of a silica network (in two-dimensional form) on the surface of a gold electrode, via twice in situ hydrolysis of 3-mercaptopropyl-tri-ethoxysilane, citrate capped gold nanoparticles (CGNP) were chemically adsorbed on the silica cage. Subsequently, PDDA was bonded to CGNP via electrostatic interaction of positively charged polymer and negatively charged stabilizer of CGNP. Analytical properties of GE-TDSN-CGNP-PDDA were studied by Electrochemical Impedance Spectroscopy (EIS). The detection limit for measured BSA was found to be 8.4×10(-13) mol L(-1) and the measuring linear concentration range of the proposed sensor was 9.9×10(-12)-1.6×10(-10) mol L(-1) of BSA. In addition, GE-TDSN-CGNP-PDDA exhibited good stability with high selectivity and was applied for determination of BSA in some samples with satisfactory results.

  12. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly

    PubMed Central

    Li, Zihui; Sai, Hiroaki; Warren, Scott C.; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M.; Wiesner, Ulrich

    2010-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules. PMID:21103025

  13. Synthesis, characterization and catalytic activity of ordered macroporous silicas functionalized with organosulfur groups

    SciTech Connect

    Wu Quanzhou Liao Jufang; Yin Qiang; Li Yuguang

    2008-05-06

    Hybrid three-dimensionally ordered macroporous (3DOM) SiO{sub 2}-SO{sub 3}H materials with different S/Si ratio have been prepared by colloidal crystal templating method. The process involved preparation of 3DOM SiO{sub 2}-SH materials by co-condensation of (3-mercaptopropyl)triethoxysilane and tetraethoxysilane via sol-gel transformation, and following oxidation of -SH group to -SO{sub 3}H group by H{sub 2}O{sub 2}. Materials were characterized by scanning electron microscopy (SEM), Fourier transform infra-red spectrometer (FTIR), thermogravimetric analysis (TGA), and nitrogen adsorption measurement. SEM observation shows that the macropores are highly ordered with a typical 'surface-templated' structure. The surface area of 3DOM SiO{sub 2}-SH material is 25.1 m{sup 2}/g and SiO{sub 2}-SO{sub 3}H material is 18.6 m{sup 2}/g. Catalytic activity test shows that 3DOM SiO{sub 2}-SO{sub 3}H materials possess a high activity for the esterification of acetic acid and n-butanol, and the activity is increased with the amount of sulfur in the materials. This study provided significant results for developing new application of 3DOM materials.

  14. Adsorption and recovery of alkylphenol polyethoxylates from synthetic wastewater using hexagonal mesoporous silicate.

    PubMed

    Punyapalakul, P; Takizawa, S

    2006-01-01

    A large amount of alkylphenol polyethoxylate (APnEOs), one of endocrine disrupters, is disposed of directly to biological wastewater treatment plants. But microbial oxidation processes cannot completely degrade these molecules to nontoxic forms. Adsorption and recovery efficiency of APnEOs was investigated using four different types of Hexagonal Mesoporous Silicate (HMSs) and powdered activated carbon (PAC). HMSs were synthesized by surfactant-templating methods, and two of them were subsequently grafted with surface functional groups. The two types of organic functional groups grafted on the surface were n-octyldimethyl- and 3-mercaptopropyl- groups. Titanium substituted HMS was also made in the same way as HMS. Adsorption of APnEOs on synthesized HMSs was higher than that on PAC. Larger pore sizes of HMS and Ti-HMS enhanced accessibility of APnEOs to active surface sites in mesopores, which realized higher adsorption capacities and L-shape (Langmuir) adsorption isotherms. Adsorption capacities of APnEOs are influenced by water solubility of APnEOs. APnEOs adsorbed on HMSs can be completely recovered by a mixture of alcohol and water at 5:5 ratio, which is more effective than the recovery from PAC. PMID:16749450

  15. The effects of zeolite molecular sieve based surface treatments on the properties of wool fabrics

    NASA Astrophysics Data System (ADS)

    Carran, Richard S.; Ghosh, Arun; Dyer, Jolon M.

    2013-12-01

    Wool is a natural composite fiber, with keratin and keratin-associated proteins as the key molecular components. The outermost surface of wool fibers comprises a hydrophobic lipid layer that can lead to unsatisfactory processing and properties of fabric products. In this study, molecular sieve 5A, a Na+ and Ca2+ exchanged type A zeolite with a 1:1 Si:Al ratio was integrated onto the surface of wool using 3-mercaptopropyl trimethoxy silane. The resultant surface morphology, hydrophilicity and mechanical performance of the treated wool fabrics were then evaluated. Notably, the surface hydrophilicity of wool was observed to increase dramatically. When wool was treated with a dispersion of 2 wt% acetic acid, 2.5 wt% zeolite and 0.3 wt% or more silane, the water contact angle was observed to decrease from an average value of 148° to 0° over a period of approximately 30 s. Scanning electron microscopic imaging indicated good coverage of the wool surface with zeolite particles, with infrared spectroscopic evaluation indicating strong bonding of the dealuminated zeolite to wool keratins. This application of zeolite showed no adverse effects on the tensile and other mechanical properties of the fabric. This study indicates that zeolite-based treatment is a potentially efficient approach to increasing the surface hydrophilicity and modifying other key surface properties of wool and wool fabrics.

  16. Functional layer-by-layer design of xerogel-based first-generation amperometric glucose biosensors.

    PubMed

    Poulos, Nicholas G; Hall, Jackson R; Leopold, Michael C

    2015-02-01

    Xerogel-based first-generation amperometric glucose biosensors, constructed through specific layer-by-layer assembly of films featuring glucose oxidase doped xerogel, a diffusion-limiting xerogel layer, and capped with both electropolymerized polyphenol and blended polyurethane semipermeable membranes, are presented. The specific combination of xerogels formed from specific silane precursors, including propyl-trimethoxysilane, isobutyl-trimethoxysilane, octyl-trimethoxysilane, and hydroxymethyl-triethoxysilane, exhibit impressive dynamic and linear ranges of detection (e.g., ≥24-28 mM glucose) and low response times, as well as significant discrimination against common interferent species such as acetaminophen, ascorbic acid, sodium nitrite, oxalic acid, and uric acid as determined by selectivity coefficients. Additionally, systematic electrochemical and contact angle studies of different xerogel silane precursors, varying in structure, chain length, and/or functional group, reveal that sensor performance is more dependent on the tunable porosity/permeability of the layered interfaces rather than the hydrophobic character or functional groups within the films. While the sensing performance largely exceeds that of existing electrochemical glucose sensing schemes in the literature, the presented layered approach establishes the specific functionality of each layer working in concert with each other and suggests that the strategy may be readily adaptable to other clinically relevant targets and is amenable to miniaturization for eventual in situ or in vivo sensing. PMID:25562760

  17. Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

    PubMed

    Ko, Young Gun; Shin, Seung Su; Choi, Ung Su

    2011-09-15

    CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket". PMID:21708387

  18. Enhanced Durability of Antisticking Layers by Recoating a Silica Surface with Fluorinated Alkylsilane Derivatives by Chemical Vapor Surface Modification

    NASA Astrophysics Data System (ADS)

    Kohno, Akihiro; Sakai, Nobuji; Matsui, Shinji; Nakagawa, Masaru

    2010-06-01

    Adsorbed monolayers from (3,3,3-trifluoropropyl)trimethoxysilane (FAS3), (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (FAS13), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (FAS17), and (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane (FAS17-Cl) were formed by chemical vapor surface modification (CVSM) on silica lens surfaces cleaned by exposure to vacuum ultraviolet (VUV) light at 172 nm. Changes in monolayer-modified lens surfaces concomitant with repeating a cycle of curing to induce the radical polymerization of a UV-curable resin and detaching the UV-cured resin were monitored by contact angle measurement with water and atomic force microscopy to investigate the property of the adsorbed monolayers as antisticking layers in UV nanoimprint lithography. A decrease of the contact angle for water with increasing the number of repeated cycles was mainly responsible for the removal of surface impurities in the form of nanoparticles on detaching the cured resin repeatedly. It was found that recoating the silica lens surface with monolayers from FAS13, FAS17, and FAS17-Cl after cleaning by VUV-light exposure resulted in the suppression of the decrease in the contact angle. These results indicate that the durability of an antisticking layer in UV nanoimprint lithography is markedly improved by the recoating.

  19. Covalently bonded sulfonic acid magnetic graphene oxide: Fe3O4@GO-Pr-SO3H as a powerful hybrid catalyst for synthesis of indazolophthalazinetriones.

    PubMed

    Doustkhah, Esmail; Rostamnia, Sadegh

    2016-09-15

    Multistep synthesis of covalently sulfonated magnetic graphene oxide was achieved by starting from Hummer's method to produce graphene oxide (GO) from chemical oxidation of graphite. Then, GO nanosheets were applied to support Fe3O4 nanoparticles (Fe3O4@GO) using co-precipitation method in the presence of GO sheets. This strategy led to formation of uniform particles of Fe3O4 on the surface of GO sheets. Then, it was sulfonated (Fe3O4@GO-Pr-SO3H) through modification with 3-mercaptopropyltrimethoxysilane (MPTMS) and subsequent oxidation with hydrogen peroxide (H2O2). In comparison, the covalently bonded propyl sulfonic acid groups were more prevailing rather to sulfonic acids of GO itself. The proposed catalyst was more active and recyclable at least for 11 runs.

  20. Preparation of polystyrene/SiO2 microsphere via Pickering emulsion polymerization: Synergistic effect of SiO2 concentrations and initiator sorts

    NASA Astrophysics Data System (ADS)

    Zhou, Haiou; Shi, Tiejun; Zhou, Xun

    2013-02-01

    In this paper, polystyrene (PS)/SiO2 microspheres were successfully prepared via Pickering emulsion polymerization stabilized solely by ethacryloxypropyltrimethoxysilane (MPTMS) modified SiO2 nanoparticles. The formation mechanisms of PS/SiO2 microspheres with different morphology were investigated under various Pickering emulsion polymerization conditions. The results showed that SiO2 concentrations and initiator sorts would synergistically impact on the morphology of products corresponding to distinct formation mechanisms. When SiO2 concentrations was low and water-solute initiator potassium persulfate (KPS) was used, aqueous nucleation was dominant, which was deduced to the formation of dispersive microspheres sparsely anchored by SiO2 particles. When SiO2 concentrations was increased and oil-solute initiator azobisisobutyronitrile (AIBN) was applied, nucleation in oil phase prevailed which lead to the formation of microspheres densely packed by SiO2 particles.

  1. Covalently bonded sulfonic acid magnetic graphene oxide: Fe3O4@GO-Pr-SO3H as a powerful hybrid catalyst for synthesis of indazolophthalazinetriones.

    PubMed

    Doustkhah, Esmail; Rostamnia, Sadegh

    2016-09-15

    Multistep synthesis of covalently sulfonated magnetic graphene oxide was achieved by starting from Hummer's method to produce graphene oxide (GO) from chemical oxidation of graphite. Then, GO nanosheets were applied to support Fe3O4 nanoparticles (Fe3O4@GO) using co-precipitation method in the presence of GO sheets. This strategy led to formation of uniform particles of Fe3O4 on the surface of GO sheets. Then, it was sulfonated (Fe3O4@GO-Pr-SO3H) through modification with 3-mercaptopropyltrimethoxysilane (MPTMS) and subsequent oxidation with hydrogen peroxide (H2O2). In comparison, the covalently bonded propyl sulfonic acid groups were more prevailing rather to sulfonic acids of GO itself. The proposed catalyst was more active and recyclable at least for 11 runs. PMID:27309948

  2. Silica Ouzo Effect: Amphiphilic Drugs Facilitate Nanoprecipitation of Polycondensed Mercaptosilanes.

    PubMed

    Chiu, Shih-Jiuan; Lin, Chien-Yu; Chou, Hung-Chang; Hu, Teh-Min

    2016-01-12

    Amphiphilic drugs are therapeutic agents whose molecular structures contain both hydrophobic and hydrophilic portions. Here we report a systematic study on how amphiphilic drugs can assist in silica nanoprecipitation. 3-Mercaptopropyltrimethoxysilane (MPTMS) was used as the sole silica material and 12 amphiphilic drugs spanning a wide spectrum of therapeutic categories were included. MPTMS polycondensation was conducted in a DMSO-based organic phase. After a sufficient time, particle formation was induced by injecting a small amount of the organic phase into a water solution containing various amphiphiles. The results show that all amphiphilic drugs studied exerted concentration-dependent facilitating effect on nanoparticle formation. Under certain preparation conditions, the particle solution showed physical stability over a long period and the formed particles could be as small as 100 nm. By systematically varying drug concentrations and injection volumes, the ability of each amphiphile to promote nanoprecipitation can be quantified and compared, based on two novel indices: the area under the critical volume-concentration curve (AUC) and the critical stabilization concentration (CSC). We demonstrate that both ability indices significantly correlated with the drug's log P and critical micelle concentrations (CMC). Furthermore, we have optimized the aging and particle purification condition and extensively characterized our system through comprehensive TEM and zeta-potential measurements, as well as determinations for drug entrapment and release. In conclusion, we have established a quantitative structure-activity relationship for amphiphilic small-molecular drugs in their ability to interact with poly(mercaptopropyl)silsesquioxane species and form nanoparticles via solvent shifting. We speculate that both hydrophobic and electrostatic interactions play important roles in the formation and stabilization of nanoparticles. PMID:26673354

  3. Coating of magnetite with mercapto modified rice hull ash silica in a one-pot process.

    PubMed

    Nuryono, Nuryono; Mutia Rosiati, Nur; Rusdiarso, Bambang; Sakti, Satya Candra Wibawa; Tanaka, Shunitz

    2014-01-01

    In this research, mercapto-silica coated magnetite (Fe3O4-SiO2-SH) has been prepared in aqueous solution through a simple approach so called a one-pot process. The Fe3O4-SiO2-SH was prepared in nitrogen condition by mixing magnetite, 3-mercaptopropyltrimethoxysilane (MPTMS), and sodium silicate (Na2SiO3) solution extracted from rice hull ash, and adjusting the pH of 7.0 using hydrochloric acid. The residue was washed with deionized water, dried at 150°C and separated with an external magnetic field. In that work, the volume of MPTMS and Na2SiO3 was varied and the total amount of Si represented as silica was kept constant. Characters of the material including the functional group presence, the structure, the porosity, the morphology and stability toward various solvents were identified and evaluated. Results of characterization indicated that mercapto-silica has been coated magnetite particle with a simple one-pot process. Coating mercapto-silica on magnetite increases particle size, surface area, and chemical stability. Additionally, Fe3O4-SiO2-SH also shows high stability toward various organic solvents. The magnetic property of magnetite does not change after coating and the addition of nonmagnetic material still gives high value of maximum saturation magnetization. The presence of mercapto groups effective for interaction with heavy metal ions, the high chemical stability without removing the magnetic property promises the prospective application of Fe3O4-SiO2-SH in the future such as for separation and removal of heavy metal ions from aquatic environments.

  4. Silica Ouzo Effect: Amphiphilic Drugs Facilitate Nanoprecipitation of Polycondensed Mercaptosilanes.

    PubMed

    Chiu, Shih-Jiuan; Lin, Chien-Yu; Chou, Hung-Chang; Hu, Teh-Min

    2016-01-12

    Amphiphilic drugs are therapeutic agents whose molecular structures contain both hydrophobic and hydrophilic portions. Here we report a systematic study on how amphiphilic drugs can assist in silica nanoprecipitation. 3-Mercaptopropyltrimethoxysilane (MPTMS) was used as the sole silica material and 12 amphiphilic drugs spanning a wide spectrum of therapeutic categories were included. MPTMS polycondensation was conducted in a DMSO-based organic phase. After a sufficient time, particle formation was induced by injecting a small amount of the organic phase into a water solution containing various amphiphiles. The results show that all amphiphilic drugs studied exerted concentration-dependent facilitating effect on nanoparticle formation. Under certain preparation conditions, the particle solution showed physical stability over a long period and the formed particles could be as small as 100 nm. By systematically varying drug concentrations and injection volumes, the ability of each amphiphile to promote nanoprecipitation can be quantified and compared, based on two novel indices: the area under the critical volume-concentration curve (AUC) and the critical stabilization concentration (CSC). We demonstrate that both ability indices significantly correlated with the drug's log P and critical micelle concentrations (CMC). Furthermore, we have optimized the aging and particle purification condition and extensively characterized our system through comprehensive TEM and zeta-potential measurements, as well as determinations for drug entrapment and release. In conclusion, we have established a quantitative structure-activity relationship for amphiphilic small-molecular drugs in their ability to interact with poly(mercaptopropyl)silsesquioxane species and form nanoparticles via solvent shifting. We speculate that both hydrophobic and electrostatic interactions play important roles in the formation and stabilization of nanoparticles.

  5. Novel material concepts of transducers for chemical and biosensors.

    PubMed

    Yakimova, R; Steinhoff, G; Petoral, R M; Vahlberg, C; Khranovskyy, V; Yazdi, G R; Uvdal, K; Lloyd Spetz, A

    2007-06-15

    The objectives of this work are to contribute to the knowledge about physical and chemical properties of WBG semiconductors, such as ZnO and GaN towards development of advanced bio- and chemical sensors. For the semiconductors, growth techniques typically yielding single crystal material are applied. Thin epitaxial quality films of ZnO and GaN are fabricated on SiC or sapphire substrates. An emphasis is given to ZnO due to the interesting combination of the semiconductor and oxide properties. Surface bio-functionalization of ZnO is performed by APTES, MPA or MP-TMS molecules. We have compared some of the results to (hydroxylated) GaN surfaces functionalized by MP-TMS. The covalent attachment of the self-assembled biomolecular layers has been proven by XPS analysis. For complementary electrical characterization impedance spectroscopy measurements were performed. The results are intended to serve the realization of bioelectronic transducer devices based on SiC or GaN transistors with a ZnO gate layer. To take advantage of the catalytic properties of ZnO, initial prototypes of chemical sensors for gas sensing are processed on ZnO deposited either on SiC or on sapphire and they are further tested for the response to reducing or oxidizing gas ambient. The sensor devices show sensitivity to oxygen in the surface resistivity mode while a Pt Schottky contact ZnO/SiC device responds to reducing gases. These results are compared to published results on Pt/GaN Schottky diodes. PMID:17289367

  6. Monolayer-protected nanoparticle doped xerogels as functional components of amperometric glucose biosensors.

    PubMed

    Freeman, Michael H; Hall, Jackson R; Leopold, Michael C

    2013-04-16

    First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during amperometry. MPC-doped xerogels yield significant enhancement of several sensor attributes compared to analogous films without nanoparticles: doubling of the linear range, sensitivity enhancement by an order of magnitude, and 4-fold faster response times accompany long-term stability and resistance to common interfering agents that are competitive with current glucose biosensing literature. Ligand chain length and the MPC/silane ratio studies suggest the MPC-induced enhancements are critically related to structure-function relationships, particularly those affecting interparticle electronic communication where the MPC network behaves as a three-dimensional extension of the working electrode into the xerogel film, reducing the system's dependence on diffusion and maximizing efficiency of the sensing mechanism. The integration of MPCs as a functional component of amperometric biosensor schemes has implications for future development of biosensors targeting clinically relevant species.

  7. In situ speciation of dissolved inorganic antimony in surface waters and sediment porewaters: development of a thiol-based diffusive gradients in thin films technique for Sb(III).

    PubMed

    Bennett, William W; Arsic, Maja; Welsh, David T; Teasdale, Peter R

    2016-08-10

    Antimony is a priority environmental contaminant typically present as either the trivalent (Sb(III)) or the pentavalent (Sb(V)) oxidation state in aquatic systems. Both the toxicity and mobility of antimony are affected by its speciation, and thus the accurate measurement of antimony speciation is essential for investigating the behaviour of this contaminant in aquatic systems. Here we present a diffusive gradients in thin films (DGT) technique, which utilises a binding layer containing a thiol-based adsorbent (3-mercaptopropyl functionalised silica gel), for the selective measurement of Sb(III) in surface waters and sediment porewaters. We also evaluated the Metsorb DGT technique, which has been previously reported to accurately measure Sb(V), for its ability to accumulate Sb(III) and thus allow the measurement of total inorganic antimony. Both the mercapto-silica and Metsorb DGT techniques showed a high affinity for Sb(III), with uptake efficiencies >97%. Elution efficiencies of 86.9 ± 2.6% and 88.1 ± 1.2% were obtained for mercapto-silica and Metsorb, respectively, with 1 mol L(-1) H2O2 in 1 mol L(-1) NaOH. The accumulation of Sb(III) by these DGT techniques was linear with time (R(2) > 0.99) and unaffected by pH (4.07-8.05), ionic strength (0.001-1.0 mol L(-1) NaCl), bicarbonate (1-15 mmol L(-1)), and an artificial seawater matrix (pH 8.34; salinity 34.8). Finally, the mercapto-silica DGT technique was applied to measure porewater concentrations of Sb(III) and As(III) in a contaminated freshwater sediment at high resolution. PMID:27192548

  8. Evaluation of performance of three different hybrid mesoporous solids based on silica for preconcentration purposes in analytical chemistry: From the study of sorption features to the determination of elements of group IB.

    PubMed

    Kim, Manuela Leticia; Tudino, Mabel Beatríz

    2010-08-15

    Several studies involving the physicochemical interaction of three silica based hybrid mesoporous materials with metal ions of the group IB have been performed in order to employ them for preconcentration purposes in the determination of traces of Cu(II), Ag(I) and Au(III). The three solids were obtained from mesoporous silica functionalized with 3-aminopropyl (APS), 3-mercaptopropyl (MPS) and N-[2-aminoethyl]-3-aminopropyl (NN) groups, respectively. Adsorption capacities for Au, Cu and Ag were calculated using Langmuir's isotherm model and then, the optimal values for the retention of each element onto each one of the solids were found. Physicochemical data obtained under thermodynamic equilibrium and under kinetic conditions - imposed by flow through experiments - allowed the design of simple analytical methodologies where the solids were employed as fillings of microcolumns held in continuous systems coupled on-line to an atomic absorption spectrometry. In order to control the interaction between the filling and the analyte at short times (flow through conditions) and thus, its effect on the analytical signal and the presence of interferences, the initial adsorption velocities were calculated using the pseudo second order model. All these experiments allowed the comparison of the solids in terms of their analytical behaviour at the moment of facing the determination of the three elements. Under optimized conditions mainly given by the features of the filling, the analytical methodologies developed in this work showed excellent performances with limits of detection of 0.14, 0.02 and 0.025 microg L(-1) and RSD % values of 3.4, 2.7 and 3.1 for Au, Cu and Ag, respectively. A full discussion of the main findings on the interaction metal ions/fillings will be provided. The analytical results for the determination of the three metals will be also presented.

  9. In situ high-resolution evaluation of labile arsenic and mercury in sediment of a large shallow lake.

    PubMed

    Wang, Chao; Yao, Yu; Wang, Peifang; Hou, Jun; Qian, Jin; Yuan, Ye; Fan, Xiulei

    2016-01-15

    The precise evaluation of arsenic (As) and mercury (Hg) bioavailability in sediment is crucial to controlling As and Hg contamination, but traditional ex situ measurements hamper comprehensive analysis of labile As and Hg in sediment. In this study, we characterized in situ labile As and Hg in sediment of Lake Hongze using the zirconium (Zr) oxide diffusive gradients in thin films (DGT) technique and 3-mercaptopropyl functionalized silica gel DGT, respectively. The concentrations of DGT-labile As and Hg in the sediment profiles were found to exhibit considerable variation, ranging from 0.15 to 4.15 μg L(-1) for As and from 0.04 to 1.35 μg L(-1) for Hg. As and Hg flux values, calculated based on the concentration gradients measured from the DGT profiles for both the overlying water and sediment close to the sediment-water interface, were used to determine the contamination status of As and Hg. Flux values of As and Hg were between -0.066 and 0.067 ng cm(-2)d(-1) and between -0.0187 and 0.0181 ng cm(-2)d(-1), respectively. The GNU's Not Unix R (GNU R) programming language was used to identify outliers of As and Hg at various depths at the sampling sites. The results indicate that the sites with the most outliers were all located in the regions that were seriously affected by contaminants from the Huai River. The DGT-labile As and Hg concentrations in the 0-30 mm layer were found to be significantly correlated with concentrations of labile As and Hg, total dissolved As and Hg, and total As and Hg in the overlying water, as indicated by ex situ measurements. Results show that DGT is a reliable and high-resolution technique that can be used for in situ monitoring of the labile fractions of As and Hg in sediment in fresh water bodies. PMID:26398454

  10. In situ high-resolution evaluation of labile arsenic and mercury in sediment of a large shallow lake.

    PubMed

    Wang, Chao; Yao, Yu; Wang, Peifang; Hou, Jun; Qian, Jin; Yuan, Ye; Fan, Xiulei

    2016-01-15

    The precise evaluation of arsenic (As) and mercury (Hg) bioavailability in sediment is crucial to controlling As and Hg contamination, but traditional ex situ measurements hamper comprehensive analysis of labile As and Hg in sediment. In this study, we characterized in situ labile As and Hg in sediment of Lake Hongze using the zirconium (Zr) oxide diffusive gradients in thin films (DGT) technique and 3-mercaptopropyl functionalized silica gel DGT, respectively. The concentrations of DGT-labile As and Hg in the sediment profiles were found to exhibit considerable variation, ranging from 0.15 to 4.15 μg L(-1) for As and from 0.04 to 1.35 μg L(-1) for Hg. As and Hg flux values, calculated based on the concentration gradients measured from the DGT profiles for both the overlying water and sediment close to the sediment-water interface, were used to determine the contamination status of As and Hg. Flux values of As and Hg were between -0.066 and 0.067 ng cm(-2)d(-1) and between -0.0187 and 0.0181 ng cm(-2)d(-1), respectively. The GNU's Not Unix R (GNU R) programming language was used to identify outliers of As and Hg at various depths at the sampling sites. The results indicate that the sites with the most outliers were all located in the regions that were seriously affected by contaminants from the Huai River. The DGT-labile As and Hg concentrations in the 0-30 mm layer were found to be significantly correlated with concentrations of labile As and Hg, total dissolved As and Hg, and total As and Hg in the overlying water, as indicated by ex situ measurements. Results show that DGT is a reliable and high-resolution technique that can be used for in situ monitoring of the labile fractions of As and Hg in sediment in fresh water bodies.

  11. Functionalized mesoporous materials for adsorption and release of different drug molecules: A comparative study

    SciTech Connect

    Wang Gang; Otuonye, Amy N.; Blair, Elizabeth A.; Denton, Kelley; Tao Zhimin; Asefa, Tewodros

    2009-07-15

    The adsorption capacity and release properties of mesoporous materials for drug molecules can be improved by functionalizing their surfaces with judiciously chosen organic groups. Functionalized ordered mesoporous materials containing various types of organic groups via a co-condensation synthetic method from 15% organosilane and by post-grafting organosilanes onto a pre-made mesoporous silica were synthesized. Comparative studies of their adsorption and release properties for various model drug molecules were then conducted. Functional groups including 3-aminopropyl, 3-mercaptopropyl, vinyl, and secondary amine groups were used to functionalize the mesoporous materials while rhodamine 6G and ibuprofen were utilized to investigate the materials' relative adsorption and release properties. The self-assembly of the mesoporous materials was carried out in the presence of cetyltrimethylammonium bromide (CTAB) surfactant, which produced MCM-41 type materials with pore diameters of {approx}2.7-3.3 nm and moderate to high surface areas up to {approx}1000 m{sup 2}/g. The different functional groups introduced into the materials dictated their adsorption capacity and release properties. While mercaptopropyl and vinyl functionalized samples showed high adsorption capacity for rhodamine 6G, amine functionalized samples exhibited higher adsorption capacity for ibuprofen. While the diffusional release of ibuprofen was fitted on the Fickian diffusion model, the release of rhodamine 6G followed Super Case-II transport model. - Graphical abstract: The adsorption capacity and release properties of mesoporous materials for various drug molecules are tuned by functionalizing the surfaces of the materials with judiciously chosen organic groups. This work reports comparative studies of the adsorption and release properties of functionalized ordered mesoporous materials containing different hydrophobic and hydrophilic groups that are synthesized via a co-condensation and post

  12. Bio-polymer coatings on neural probe surfaces: Influence of the initial sample composition

    NASA Astrophysics Data System (ADS)

    Chow, Winnie W. Y.; Herwik, Stanislav; Ruther, Patrick; Göthelid, Emmanuelle; Oscarsson, Sven

    2012-08-01

    This paper presents the results of the study of hyaluronic acid (HyA) coating on two structural materials, silicon oxide (dielectric) surface and platinum (Pt) surface used for fabrication of probes developed for neurological investigations in the framework of the EU-project NeuroProbes. The silicon-based neural probes consist of multiple Pt electrodes on the probe shafts for neural recording applications. HyA coatings were proposed to apply on the probe surfaces to enhance the biocompatibility [1]. This study aims at understanding the influence of the initial composition of the probe surface on the structure and morphology of HyA coating. HyA was chemically functionalized by SS-pyridin using (N-Succinimidyl 3-[2-pyridyldithio]-propionate) (SPDP) and was immobilized on the surfaces via a covalent bond. The dielectric and Pt surfaces were derivatized by use of (3-mercaptopropyl) methyldimethoxysilane (MPMDMS). The silanol groups in MPMDMS bind to the dielectric surface, leaving the thiol groups at the uppermost surface and the thiol groups then bind covalently to the functionalized HyA. On the Pt surface, it is the thiol group which binds on the Pt surface. The coated surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). A well-defined HyA layer was observed on both dielectric and Pt surfaces. The coating of two molecular weights (340 kDa and 1.3 MDa) of HyA was examined. The influence of the silanized layer on the HyA coating was also investigated.

  13. Adhesion and growth of human bone marrow mesenchymal stem cells on precise-geometry 3D organic-inorganic composite scaffolds for bone repair.

    PubMed

    Chatzinikolaidou, Maria; Rekstyte, Sima; Danilevicius, Paulius; Pontikoglou, Charalampos; Papadaki, Helen; Farsari, Maria; Vamvakaki, Maria

    2015-03-01

    Engineering biomaterial scaffolds that promote attachment and growth of mesenchymal stem cells in three dimensions is a crucial parameter for successful bone tissue engineering. Towards this direction, a lot of research effort has focused recently into the development of three-dimensional porous scaffolds, aiming to elicit positive cellular behavior. However, the fabrication of three-dimensional tissue scaffolds with a precise geometry and complex micro- and nano-features, supporting cell in-growth remains a challenge. In this study we report on a positive cellular response of human bone marrow-derived (BM) mesenchymal stem cells (MSCs) onto hybrid material scaffolds consisting of methacryloxypropyl trimethoxysilane, zirconium propoxide, and 2-(dimethylamino)ethyl methacrylate (DMAEMA). First, we use Direct fs Laser Writing, a 3D scaffolding technology to fabricate the complex structures. Subsequently, we investigate the morphology, viability and proliferation of BM-MSCs onto the hybrid scaffolds and examine the cellular response from different donors. Finally, we explore the effect of the materials' chemical composition on cell proliferation, employing three different material surfaces: (i) a hybrid consisting of methacryloxypropyl trimethoxysilane, zirconium propoxide and 50mol% DMAEMA, (ii) a hybrid material comprising methacryloxypropyl trimethoxysilane and zirconium propoxide, and (iii) a purely organic polyDMAEMA. Our results show a strong adhesion of BM-MSCs onto the hybrid material containing 50% DMAEMA from the first 2h after seeding, and up to several days, and a proliferation increase after 14 and 21days, similar to the polystyrene control, independent of cell donor. These findings support the potential use of our proposed cell-material combination in bone tissue engineering.

  14. Organic memory device with polyaniline nanoparticles embedded as charging elements

    NASA Astrophysics Data System (ADS)

    Kim, Yo-Han; Kim, Minkeun; Oh, Sewook; Jung, Hunsang; Kim, Yejin; Yoon, Tae-Sik; Kim, Yong-Sang; Ho Lee, Hyun

    2012-04-01

    Polyaniline nanoparticles (PANI NPs) were synthesized and fabricated as charging elements for organic memory devices. The PANI NPs charging layer was self-assembled by epoxy-amine bonds between 3-glycidylpropyl trimethoxysilane functionalized dielectrics and PANI NPs. A memory window of 5.8 V (ΔVFB) represented by capacitance-voltage hysteresis was obtained for metal-pentacene-insulator-silicon capacitor. In addition, program/erase operations controlled by gate bias (-/+90 V) were demonstrated in the PANI NPs embedded pentacene thin film transistor device with polyvinylalcohol dielectric on flexible polyimide substrate. These results can be extended to development of fully organic-based electronic device.

  15. DICOR surface treatments for enhanced bonding.

    PubMed

    Bailey, L F; Bennett, R J

    1988-06-01

    Treatments for preparing castable ceramic surfaces for enhanced bonding to specially formulated resin-based cements were examined. An ammonium bifluoride etch combined with gamma-methacryloxypropyl-trimethoxysilane produced shear bond strengths higher than when an ammonium bifluoride treatment was used alone. The method of curing the silane was highly significant in the contribution to the cement/substrate bond strength, with the heat-cure producing the highest values. Long-term water storage tests indicated that the cement bond with etch plus silane-treated castable ceramic surfaces (whether heat or chemically cured silane was used) demonstrated no significant decrease in strength after a one-year period.

  16. Electron paramagnetic resonance as an effective method for a characterization of functionalized iron oxide

    NASA Astrophysics Data System (ADS)

    Dobosz, Bernadeta; Krzyminiewski, Ryszard; Schroeder, Grzegorz; Kurczewska, Joanna

    2014-05-01

    Iron(II, III) oxide magnetic nanoparticles (NPs) have been coated with (3-Chloropropyl) trimethoxysilane and subsequently functionalized with 4-Amino-2,2,6,6-tetramethylpiperidine-N-oxyl and Amoxicillin. Finally, the functionalized iron oxide NPs have been coated with natural polymer, chitosan, in order to prevent NPs agglomeration in aqueous environment. The product was characterized by Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). It was studied by the electron paramagnetic resonance method and the parameters describing the magnetic properties of the investigated nanoparticles, such as g-factor and line width, were calculated.

  17. Gas adsorption surface analysis of silane-coated fused amorphous silica

    SciTech Connect

    Horn, A.F.

    1996-12-31

    Certain types of high frequency electrical circuit substrates consist of copper foil clad PTFE (poly(tetrafluoroethylene)) composite dielectric material that is highly filled (>50 vol.%) with various ceramic powders. The ceramic powders are chosen primarily to modify the dielectric constant of the composite, but also function to reduce the composite`s coefficient of thermal expansion (CTE). The ceramic powders are frequently treated with organosilane coupling agents to reduce the composite water absorption. To be effective, the coupling agents must not significantly degrade at the high processing temperature of PTFE (>350{degrees}C). Phenyl-trimethoxysilane (PTMS) or silane mixtures containing a high fraction of PTMS are often used.

  18. A new procedure for handling impervious biological specimens.

    PubMed

    Lindley, V A

    1992-06-01

    A new application of techniques for preparing impervious biological specimens for light microscopy (LM) and transmission electron microscopy (TEM) has been developed. Microwave irradiation was used to facilitate fixation. A priming technique was used to increase the bonding of the outer surface of the specimens with the resin. Priming the waxy or cuticular surface with Z-6040 (gamma-glycidoxypropyl trimethoxysilane) solved the problem of specimen "pull out" from the resin. Insect specimens with various types of cuticles (waxy or chitinous) and seeds were successfully studied ultrastructurally using this technique.

  19. Ag-TiO2 nanoparticle codoped SiO2 films on ZrO2 barrier-coated glass substrates with antibacterial activity in ambient condition.

    PubMed

    Mukhopadhyay, Anindita; Basak, Sujit; Das, Jugal Kishore; Medda, Samar Kumar; Chattopadhyay, Krishnananda; De, Goutam

    2010-09-01

    Anatase TiO2 and Ag nanoparticles (NPs) codoped SiO2 films were prepared by the sol-gel method. Proportionate amounts of 3-(glycidoxypropyl)trimethoxysilane (GLYMO), tetraethylorthosilicate (TEOS) and 3-(methacryloxypropyl)trimethoxysilane (MEMO) derived inorganic-organic silica sol, commercially available dispersed anatase TiO2 NPs, and AgNO3 were used to prepare the sols. The films were prepared on ZrO2 (cubic) precoated soda-lime glass substrates by a single-dipping technique and heat-treated at 450 °C in air and H2/Ar atmosphere to obtain hard, relatively porous, and transparent coatings of thickness>600 nm. The ZrO2 barrier layer was previously applied on soda-lime glass to restrict the diffusion of Ag into the substrate. The Ag-TiO2 NPs incorporated SiO2 films were intense yellow in color and found to be fairly stable at ambient condition for several days under fluorescent light. These films show a considerable growth inhibition on contact with the gram negative bacteria E. coli.

  20. Synthesis of waterborne polyurethane containing alkoxysilane side groups and the properties of the hybrid coating films

    NASA Astrophysics Data System (ADS)

    Li, Qi; Guo, Longhai; Qiu, Teng; Xiao, Weidong; Du, Dianxing; Li, Xiaoyu

    2016-07-01

    A series of waterborne polyurethane (WPU) containing alkoxysilane side groups were synthesized by using the dihydroxy functionalized alkoxysilane. The diol with trimethoxysilane groups at the side chains was synthesized via Michael addition between 3-(methacryloxypropyl)trimethoxysilane (MAPTS) and diethanolamine (DEA). The silane diol was applied as the chain extender for the NCO-endcapped prepolymer of isophorone diisocyanate, polycarbonate diol, 2,2-bis(hydroxymethyl) butyric acid and 1,4-butanediol. The products with the silane content varied from 1.2 to 16.5 wt% were dispersed in water after neutralization. The effect of the silane diol on the particle size and morphology of the WPU dispersion was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. X-ray photoelectron spectroscopy (XPS) characterization was carried out on the coating film of the WPU, revealing that the long flexible side chain is favorable for the silane components to emigrate toward the film surface and crosslink during the film formation process. As a result, both the surface contact angle to water and water adsorption of the WPU coating films increased with the silane content. Furthermore, the mechanical properties including the modulus and tensile strength of the films were also improved by the incorporation of silane diol.

  1. Synthesis and electron microscopy of inorganic and hybrid organic-inorganic mesoporous and macroporous materials

    NASA Astrophysics Data System (ADS)

    Blanford, Christopher Francis

    This work describes the creation and analysis of ordered porous inorganic and organic-inorganic hybrid materials with an emphasis on the qualitative and quantitative characterization by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Two major systems were studied: MCM-41-type mesoporous molecular sieves and three-dimensionally ordered macroporous (3DOM) materials. The microanalysis of mesoporous samples is discussed first. Samples of unmodified siliceous MCM-41, MCM-41 with grafted titanium dioxide species, and MCM-41 with incorporated 3-mercaptopropyl groups were examined in the TEM at three accelerating voltages. The beam stability of all the samples increased with increasing accelerating voltage. The particles were significantly more resistant to beam damage with the surfactant template in place, when the samples were synthesized above room temperature, and when the silicate precursor was hydrolyzed in acid. The samples with organic and inorganic groups were more stable than siliceous analogs. The discussion of 3DOM materials begins with their synthesis and characterization: 3DOM materials were created from colloidal crystals of uniform, sub-micrometer diameter polystyrene and poly(methyl methacrylate) spheres. Metal alkoxides, solutions of metal salts, and mixed salt-alkoxide precursors were employed to create 3DOM metal oxides, silicates with incorporated organic groups and polyoxometalate clusters, metals, and metal alloys. SEM and TEM were used extensively to characterize the morphology, crystallinity, grain size, and phase of the 3DOM products. The formation of 3DOM nickel oxide was studied by heating a nickel oxalate-colloidal crystal composite in an environmental SEM. The growth of the grains in 3DOM cobalt metal and 3DOM iron oxide were observed by high-temperature TEM. The arrangement of the pores in 3DOM materials was studied by analyzing diffractograms of TEM images of single particles tilted into different orientations

  2. Selective adsorption of nonionic surfactant on hexagonal mesoporous silicates (HMSs) in the presence of ionic dyes.

    PubMed

    Punyapalakul, Patiparn; Takizawa, Satoshi

    2006-10-01

    Selective adsorption of alkylphenol polyethoxylates (APnEOs) from synthetic textile wastewater was investigated using hexagonal mesoporous silicates (HMSs). HMSs are synthetic silicate that have uniform mesopores, large surface areas and uniform surface functional groups. Five different types of HMSs were synthesized by surfactant-templating methods, and three of them were grafted with organic surface functional groups, i.e., n-octyldimethyl-, 3-aminopropyltriethoxy-, and 3-mercaptopropyl-groups. Titanium-substituted HMS was also made in the same way as HMS. Adsorption capacities and selectivities of these HMSs for APnEOs were investigated in batch adsorption experiments either in single-solute APnEO solutions or in mixed solutions with ionic dyes. Triton X-100 was used as a model APnEO and either Basic Yellow 1 or Acid Blue 45 was used as cationic or anionic dyes, respectively. All the HMSs except 3-aminopropyltriethoxy-grafted HMS had higher adsorption capacities of Triton X-100 than powdered activated carbon. HMS and Ti-HMS had the highest BET surface areas and mesopore volumes measured by the nitrogen adsorption method, and thereby the highest adsorption capacities for Triton X-100. Surface charge was the most important attractive force between HMSs and dyes. FT-IR spectra proved that hydrophilic HMSs adsorbed both Basic Yellow 1 and Acid Blue 45 by hydrogen bonding. Acid-base titration experiments revealed that all the HMSs except 3-aminopropyltriethoxy-grafted HMS were negatively charged at neutral pH, whereas PAC and 3-aminopropyltriethoxy-grafted HMS were positively charged. Due to negative surface charge, the anionic dye (Acid Blue 45) was not adsorbed on the four HMSs, which proves high selectivities of these HMSs for Triton X-100 over Acid Blue 45. On the contrary, a small amount of cationic dye (Basic Yellow 1) was adsorbed on all HMSs, but 3-aminopropyltriethoxy-grafted HMS showed the lowest adsorption capacity for Basic Yellow 1 due to positive

  3. Room temperature trapping of stibine and bismuthine onto quartz substrates coated with nanostructured palladium for total reflection X-ray fluorescence analysis

    NASA Astrophysics Data System (ADS)

    Romero, Vanesa; Costas-Mora, Isabel; Lavilla, Isela; Bendicho, Carlos

    2015-05-01

    In this work, a novel method for determining Sb and Bi based on the trapping of their covalent hydrides onto quartz reflectors coated with immobilized palladium nanoparticles (Pd NPs) followed by total reflection X-ray fluorescence (TXRF) analysis is proposed. Pd NPs were synthesized by chemical reduction of the metal precursor using a mixture of water:ethanol as mild reducing agent. Silanization using 3-mercaptopropyltrimethoxysilane (MPTMS) was performed for the immobilization of Pd NPs onto the quartz substrates. Volatile hydrides (stibine and bismuthine) generated by means of a continuous flow system were flushed onto the immobilized Pd NPs and retained by catalytic decomposition. As a result of the high catalytic activity of the nanostructured film, trapping can be performed at ambient temperature with good efficiency. Limits of detection (LODs) were 2.3 and 0.70 μg L- 1 for Sb and Bi, respectively. Enrichment factors of 534 and 192 were obtained for Sb and Bi, respectively. The new method was applied for the analysis of several matrices (milk, soil, sediment, cutaneous powder). Recoveries were in the range of 98.4-101% for both elements with a relative standard deviation of 2.5% (N = 5).

  4. Facile preparation of organic-silica hybrid monolith for capillary hydrophilic liquid chromatography based on "thiol-ene" click chemistry.

    PubMed

    Chen, Ming-Luan; Zhang, Jun; Zhang, Zheng; Yuan, Bi-Feng; Yu, Qiong-Wei; Feng, Yu-Qi

    2013-04-01

    In this work, a one-step approach to facile preparation of organic-inorganic hybrid monoliths was successfully developed. After vinyl-end organic monomers and azobisisobutyronitrile (AIBN) were mixed with hydrolyzed tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS), the homogeneous mixture was introduced into a fused-silica capillary for simultaneous polycondensation and "thiol-ene" click reaction to form the organic-silica hybrid monoliths. By employing this strategy, two types of organic-silica hybrid monoliths with positively charged quaternary ammonium and amide groups were prepared, respectively. The functional groups were successfully introduced onto the monoliths during the sol-gel process with "thiol-ene" click reaction, which was demonstrated by ζ-potential assessment, energy dispersive X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) spectroscopy. The porous structure of the prepared monolithic columns was examined by scanning electron microscopy (SEM), nitrogen adsorption-desorption measurement, and mercury intrusion porosimetry. These results indicate the prepared organic-silica hybrid monoliths possess homogeneous column bed, large specific surface area, good mechanical stability, and excellent permeability. The prepared monolithic columns were then applied for anion-exchange/hydrophilic interaction liquid chromatography. Different types of analytes, including benzoic acids, inorganic ions, nucleosides, and nucleotides, were well separated with high column efficiency around 80,000-130,000 plates/m. Taken together, we present a facile and universal strategy to prepare organic-silica hybrid monoliths with a variety of organic monomers using one-step approach.

  5. Preparation of organic-inorganic hybrid silica monolith with octyl and sulfonic acid groups for capillary electrochromatograhpy and application in determination of theophylline and caffeine in beverage.

    PubMed

    Chen, Ming-Luan; Zheng, Ming-Ming; Feng, Yu-Qi

    2010-05-21

    An organic-inorganic hybrid silica monolithic column with octyl and sulfonic acid groups has been prepared by sol-gel technique for capillary electrochromatograhpy. The structure of hybrid monolith was optimized by changing the composition of tetraethoxysilane (TEOS), octyltriethoxysilane (C(8)-TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) in the mixture of precursors. Then, the obtained hybrid monolith was oxidized using hydrogen peroxide (30%, w/w) to yield sulfonic acid groups. The sulfonic acid group, which served as strong cation-exchanger, dominated the charge on the surface of the capillary column and generated stable electroosmotic flow (EOF) in a wide range of pH. The monolithic column was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and elemental analysis (EA), and the performance of column was evaluated in detail by separating different kinds of compounds with column efficiency up to 155,000 plates/m for thiourea. In addition, this monolithic column was also applied in the analysis of theophylline (TP) and caffeine (CA) in beverages. The detection limits were 0.39 and 0.48 microg/mL for theophylline and caffeine, respectively. The method reproducibility was tested by evaluating the intra- and inter-day precisions, and relative standard deviations of less than 3.9 and 8.4%, respectively, were obtained. Recoveries of compounds from spiked beverage samples ranged from 87.2 to 105.2%.

  6. Organized thiol functional groups in mesoporous core shell colloids

    SciTech Connect

    Marchena, Martin H.; Granada, Mara; Bordoni, Andrea V.; Joselevich, Maria; Troiani, Horacio; Williams, Federico J.; Wolosiuk, Alejandro

    2012-03-15

    The co-condensation in situ of tetraethoxysilane (TEOS) and mercaptopropyltrimethoxysilane (MPTMS) using cetyltrimethylammonium bromide (CTAB) as a template results in the synthesis of multilayered mesoporous structured SiO{sub 2} colloids with 'onion-like' chemical environments. Thiol groups were anchored to an inner selected SiO{sub 2} porous layer in a bilayered core shell particle producing different chemical regions inside the colloidal layered structure. X-Ray Photoelectron Spectroscopy (XPS) shows a preferential anchoring of the -SH groups in the double layer shell system, while porosimetry and simple chemical modifications confirm that pores are accessible. We can envision the synthesis of interesting colloidal objects with defined chemical environments with highly controlled properties. - Graphical abstract: Mesoporous core shell SiO{sub 2} colloids with organized thiol groups. Highlights: Black-Right-Pointing-Pointer Double shell mesoporous silica colloids templated with CTAB. Black-Right-Pointing-Pointer Sequential deposition of mesoporous SiO{sub 2} layers with different chemistries. Black-Right-Pointing-Pointer XPS shows the selective functionalization of mesoporous layers with thiol groups.

  7. Application of novel Polypyrrole/thiol-functionalized zeolite Beta/MCM-41 type mesoporous silica nanocomposite for adsorption of Hg2+ from aqueous solution and industrial wastewater: Kinetic, isotherm and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Javadian, Hamedreza; Taghavi, Mehdi

    2014-01-01

    Hierarchical zeolite consists of both microporous and unordered mesoporous structures. A composite of Polypyrrole/thiol-functionalized Beta/MCM-41 (PPy/SH-Beta/MCM-41) was prepared, characterized by FE-SEM, FT-IR, XRD, TGA and BET analysis and applied in the investigation of its adsorption characteristics for the removal of Hg2+ ions from aqueous solutions. Thiol-functionalized Beta/MCM-41 (SH-Beta/MCM-41) was prepared by 3-mercaptopropyltrimethoxysilane (MPTMS) in the presence of aerosil-200 as a silica source by two-step hydrothermal crystallization procedure. Batch mode experiments were conducted and three kinetic models were used to describe the adsorption process. The experimental data fitted very well with the Pseudo-second-order kinetic model. The calculated thermodynamic parameters (ΔH, ΔS and ΔG) revealed that the adsorption of Hg2+ onto PPy/SH-Beta/MCM-41 is an endothermic and spontaneous process. It was found that temperature has a positive effect on the removal efficiency and that PPy/SH-Beta/MCM-41 is potentially able to remove Hg2+ ions from aqueous solutions at even high concentrations (400 mg L-1). The recovery of Hg2+ from the PPy/SH-Beta/MCM-41 adsorbent was found to be more than 90% using 0.5 M H2SO4, and the ability of the absorbent to be reused for removal of Hg2+ was investigated.

  8. Preparation of polystyrene brush film by radical chain-transfer polymerization and micromechanical properties

    NASA Astrophysics Data System (ADS)

    Zhao, Jing; Chen, Miao; An, Yanqing; Liu, Jianxi; Yan, Fengyuan

    2008-12-01

    A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS).

  9. Functionalized nanoporous silicas for the immobilization of penicillin acylase

    NASA Astrophysics Data System (ADS)

    Maria Chong, A. S.; Zhao, X. S.

    2004-10-01

    Nanoporous silica materials with uniform pore size and ordered structure have drawn growing interest of researchers since 1990s. A large-pore nanoporous material, SBA-15, was functionalized with organosilanes by co-condensation method in the presence of nonionic triblock copolymer P123 as a template under acidic conditions. The functionalization was demonstrated by using five organosilanes, namely 3-aminopropyltriethoxysilane (APTES), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltriethoxysilane (VTES), and 4-(triethoxysilyl)butyronitrile (TSBN), which modified the surface properties of the silica materials, enabling the materials to be a promising support for immobilization of biological molecules. The functionalized SBA-15 materials exhibited long-range ordering of two-dimensional hexagonal pore arrays of size ranging from 66 to 90 Å as demonstrated by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and physical adsorption techniques. A variety of organosilane density in the range of 0.5-2.6 mmol/g was achieved as revealed by elemental analysis and solid-state nuclear magnetic resonance (NMR) techniques. The functionalized materials displayed improved properties for immobilization of penicillin acylase (PA) in comparison with pure-silica SBA-15. Such improvement is believed to be due to the enhanced surface hydrophobicity and electrostatic interactions of the functional groups with the enzyme.

  10. Facile preparation of organic-silica hybrid monolith for capillary hydrophilic liquid chromatography based on "thiol-ene" click chemistry.

    PubMed

    Chen, Ming-Luan; Zhang, Jun; Zhang, Zheng; Yuan, Bi-Feng; Yu, Qiong-Wei; Feng, Yu-Qi

    2013-04-01

    In this work, a one-step approach to facile preparation of organic-inorganic hybrid monoliths was successfully developed. After vinyl-end organic monomers and azobisisobutyronitrile (AIBN) were mixed with hydrolyzed tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS), the homogeneous mixture was introduced into a fused-silica capillary for simultaneous polycondensation and "thiol-ene" click reaction to form the organic-silica hybrid monoliths. By employing this strategy, two types of organic-silica hybrid monoliths with positively charged quaternary ammonium and amide groups were prepared, respectively. The functional groups were successfully introduced onto the monoliths during the sol-gel process with "thiol-ene" click reaction, which was demonstrated by ζ-potential assessment, energy dispersive X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) spectroscopy. The porous structure of the prepared monolithic columns was examined by scanning electron microscopy (SEM), nitrogen adsorption-desorption measurement, and mercury intrusion porosimetry. These results indicate the prepared organic-silica hybrid monoliths possess homogeneous column bed, large specific surface area, good mechanical stability, and excellent permeability. The prepared monolithic columns were then applied for anion-exchange/hydrophilic interaction liquid chromatography. Different types of analytes, including benzoic acids, inorganic ions, nucleosides, and nucleotides, were well separated with high column efficiency around 80,000-130,000 plates/m. Taken together, we present a facile and universal strategy to prepare organic-silica hybrid monoliths with a variety of organic monomers using one-step approach. PMID:23434082

  11. Synthesis and characterization of silane coated magnetic nanoparticles/glycidylmethacrylate-grafted-maleated cyclodextrin composite hydrogel as a drug carrier for the controlled delivery of 5-fluorouracil.

    PubMed

    Anirudhan, Thayyath S; Divya, Peethambaran L; Nima, Jayachandran

    2015-10-01

    A novel drug delivery system (DDS), 3-methacryloxypropyl trimethoxy silane coated magnetic nanoparticles polymerized with glycidylmethacrylate-grafted-maleated cyclodextrin (MPTMS-MNP-poly-(GMA-g-MACD)) was prepared in the presence of ethyleneglycoldimethacrylate as cross-linker and a,a'-azobisisobutyronitrile as initiator and characterized by means of SEM, FT-IR, XRD, DLS, VSM and TEM. The encapsulation efficiency (EE) and drug loading efficiency (DLE) of the DDS were tested using various formulations of DDS. The DDS showed activity against gram positive and negative bacteria. The cytotoxicity studies were also performed using MCF-7 (human breast carcinoma) cells and found that the drug carrier is biocompatible and it shows sustained and controlled release of drug to the targeted site. The drug release mechanism was found to obey non-Fickian diffusion (n=0.709) method where polymer relaxation and drug diffusion played important roles in drug release. In this DDS, advantages of core magnetic nanoparticles and host-guest interactions of β-CD were combined for the controlled delivery of 5-Fluorouracil (5-FU) to maintain the therapeutic index of the drug.

  12. Electrostatic powder spraying process for the fabrication of stable superhydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Gu, Guotuan; Tian, Yuping; Li, Zhantie; Lu, Dongfang

    2011-03-01

    Nano-sized Al2O3 particles were modified by heptadecafluorodecyl trimethoxysilane and 2,3-epoxy propoxy propyl trimethoxysilicane to make it both hydrophobic and reactive. The reactive nano-particles were mixed with polyester resin containing curing agents and electrostatic sprayed on stainless steel substrates to obtain stable superhydrophobic coatings after curing. The water contact angle (WCA) on the hybrid coating is influenced by the content of Al2O3 particles in the coating. As the Al2O3 concentration in the coating was increased from 0% to 8%, WCA increased from 68° to 165°. Surface topography of the coatings was examined using scanning electron microscopy (SEM). Nano-particles covered on the coating surface formed continuous film with greatly enhanced roughness, which was found to be responsible for the superhydrophobicity. The method is simple and cost effective and can be used for preparing self-cleaning superhydrophobic coating on large areas.

  13. Molecular design of one dimensional magnetic FeNi3 nanochains and their application in oil removal

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Kakoli; Gogoi, Monika; Deb, Pritam

    2016-05-01

    One dimensional magnetic nanochains (MNCs) of FeNi3 alloy is developed by reducing iron and nickel salts in ethylene glycol in a hydrothermal environment without the use of any external magnetic field or template. The as prepared nanochains, comprised of nanospheres of diameter 350 nm, exhibit an extraordinary length of around 2 µm. The he self assembly of the FeNi3 nanospheres is attributed to strong dipolar interaction. Hydrophilic to hydrophobic surface transformation achieved by using trimethoxysilane and stearic acid, also introduces oleophilicity to the MNCs. After surface modification, the hydrophobic and oleophilic MNCs shows quick and selective absorption of oils from water surface under the influence of magnetic field.

  14. Investigation of interaction between the Pt(II) ions and aminosilane-modified silica surface in heterogeneous system

    NASA Astrophysics Data System (ADS)

    Nowicki, Waldemar; Gąsowska, Anna; Kirszensztejn, Piotr

    2016-05-01

    UV-vis spectroscopy measurements confirmed the reaction in heterogeneous system between Pt(II) ions and ethylenediamine type ligand, n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, immobilized at the silica surface. The formation of complexes is a consequence of interaction between the amine groups from the ligand grafted onto SiO2 and ions of platinum. A potentiometric titration technique was to determine the stability constants of complexes of Pt(II) with immobilized insoluble ligand (SG-L), on the silica gel. The results show the formation of three surface complexes of the same type (PtHSG-L, Pt(HSG-L)2, PtSG-L) with SG-L ligand, in a wide range of pH for different Debye length. The concentration distribution of the complexes in a heterogeneous system is evaluated.

  15. Binding of terbium complex to polymerizable hybrid materials constructed from molecular assembly and its optical properties

    SciTech Connect

    Zhao Limin; Shao Xin; Yin Yibin; Li Wenzhi

    2009-06-03

    A new molecular precursor was synthesized by means of the amidation reaction of N-Phenylanthranilic acid with a cross-linking molecule (3-aminopropyl) trimethoxysilane, and characterized by nuclear magnetic resonance and infrared spectroscopy. Then, a chemically bonded rare-earth/inorganic polymeric hybrid material was constructed using the precursor as a bridge molecule that can both coordinate to rare-earth ions and form a Si-O network with tetraethoxysilane or polyvinyl alcohol after cohydrolysis and copolycondensation processes. Ultraviolet absorption and fluorescence spectra were applied to characterize the photophysical properties of the obtained hybrid material. The strong luminescence of Tb{sup 3+} substantiates optimum energy couple and effective intramolecular energy transfer between the triplet state energy of modified ligand bridge and emissive energy level of Tb{sup 3+}.

  16. Utilization of Metal Oxides and Chalcogenides Stabilized in Organic Solvents

    NASA Astrophysics Data System (ADS)

    Lampert, Lester; Flaig, Robby; Camacho, Jorge; Hamilton, James

    2011-03-01

    Metal oxides and metal chalcogenides are important materials for a variety of applications including photocatalysis for decomposition of water, conductive and optical coatings, catalysts, photovoltaics, pryoelectrics, self-cleaning surfaces, pigments, and high efficiency Li-insertion materials in batteries among many other applications. Fundamental discoveries of surprising solubility of insoluble materials such as single and multi-walled carbon nanotubes and graphene has lead us to discover that certain metal oxides and metal chalcogenides such as TiO2 are soluble in certain solvents. Due to the industrial importance of TiO2, discovering stable pure solvent systems demonstrates a possibility to avoid surface modification of TiO2 nanoparticles by use materials such as of (3-methacryloxypropyl)-trimethoxysilane and various other methods of artificial stabilization. We have created thin films of TiO2, transparent ultraviolet (UV) --absorptive polymers, and Li-ion battery anodes with graphene-TiO2 hybrid materials.

  17. Ultraviolet-oxidized mercaptan-terminated organosilane nanolayers as diffusion barriers at Cu-silica interfaces

    NASA Astrophysics Data System (ADS)

    Gandhi, D. D.; Tisch, U.; Singh, B.; Eizenberg, M.; Ramanath, G.

    2007-10-01

    We demonstrate the use of UV-exposed molecular nanolayers (MNLs) of 3-mercaptan-propyl-trimethoxysilane to inhibit copper-transport across Cu -SiO2 interfaces more efficiently than the pristine MNLs. Bias-thermal-annealing tests of Cu /MNL/SiO2/Si(001)/Al capacitors, with MNLs exposed to 254nm UV radiation, exhibit enhanced barrier properties to Cu diffusion, when compared with capacitors with MNLs not exposed to UV light. X-ray photoelectron spectroscopy reveals that UV exposure converts the mercaptan termini to sulfonates, which are more effective in inhibiting Cu diffusion. Our findings are of importance for tailoring the chemical and mechanical integrity of interfaces for use in applications such as nanodevice wiring and molecular electronics.

  18. In situ sol-gel composition of multicomponent hybrid precursor to hexagon-like Zn 2SiO 4:Tb 3+ microcrystalline phosphors with different silicate sources

    NASA Astrophysics Data System (ADS)

    Huang, Honghua; Yan, Bing

    2006-02-01

    Zn 2SiO 4 doped with Tb 3+ were in situ synthesized by a modified sol-gel technology with the assembly hybrid precursor employed four different silicate sources, i.e. 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM result shows that there exist some novel unexpected micromorphological structures of hexagon-like with the dimension of 0.5-1.0 μm. The photoluminescent properties of Zn 2SiO 4:Tb 3+ phosphors have been studied as a function of Tb 3+ doping concentration. Cross-relaxation process between identical Tb 3+ ions results in the quenching of the 5D 3 emission for high concentration sample.

  19. In situ sol-gel composition of multicomponent hybrid precursors to luminescent novel unexpected microrod of Y 2SiO 5:Eu 3+ employing different silicate sources

    NASA Astrophysics Data System (ADS)

    Huang, Honghua; Yan, Bing

    2004-12-01

    Y 2SiO 5 doped with Eu 3+ were in situ synthesized by a hybrid precursor assembly sol-gel technology employing four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM result shows that there exist some novel unexpected morphological microrod structures owing to using the crosslinking reagents other than TEOS as silicate source. The photoluminescent properties of Y 2SiO 5:Eu 3+ have been studied as a function of Eu 3+ doping concentration. A cross-relaxation process between identical Eu 3+ ions results in the quenching of the 5D 1 emission for high concentration sample.

  20. Covalent Modification of Organo-Functionalized Graphene Oxide and its Scope as Catalyst for One-Pot Pyrazolo-Pyranopyrimidine Derivatives.

    PubMed

    Rana, Surjyakanta; Maddila, Suresh; Yalagala, Kotaiah; Maddila, Suryanarayana; Jonnalagadda, Sreekantha B

    2015-12-01

    The surface of graphene oxide (GO) was modified using [3-(2-aminoethylamino)propyl]trimethoxysilane (diamine), which exhibited excellent catalytic activity for one-pot multicomponent reactions. The newly synthesized material was fully characterized by various instrumental techniques including Fourier-transfer infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The instrumental analysis confirmed the successful grafting of organic amine functional groups onto the graphene oxide surface. The diamine-functionalized GO proved to be an excellent catalyst for the synthesis of pyrazolo-pyranopyrimidine derivatives with 93 % yield and high selectivity. The catalytic activity almost remained unaltered up to three cycles. The newly synthesized pyrazolo-pyranopyrimidine derivatives have potential use as scaffolds in designing new pharmaceutical products. PMID:27308195

  1. Glucose microbiosensor based on alumina sol-gel matrix/electropolymerized composite membrane.

    PubMed

    Chen, Xiaohong; Hu, Yibai; Wilson, George S

    2002-12-01

    A procedure is described that provides co-immobilization of enzyme and bovine serum albumin (BSA) within an alumina sol-gel matrix and a polyphenol layer permselective for endogenous electroactive species. BSA has first been employed for the immobilization of glucose oxidase (GOx) on a Pt electrode in a sol-gel to produce a uniform, thin and compact film with enhanced enzyme activity. Electropolymerization of phenol was then employed to form an anti-interference and protective polyphenol film within the enzyme layer. In addition, a stability-reinforcing membrane derived from (3-aminopropyl)-trimethoxysilane was constructed by electrochemically-assisted crosslinking. This hybrid film outside the enzyme layer contributed both to the improved stability and to permselectivity. The resulting glucose sensor was characterized by a short response time (<10 s), high sensitivity (10.4 nA/mM mm(2)), low interference from endogenous electroactive species, and a working lifetime of at least 60 days. PMID:12392950

  2. Nanostructure and thermal properties of melt compounded PE/clay nanocomposites filled with an organosilylated montmorillonite

    SciTech Connect

    Scarfato, Paola; Incarnato, Loredana; Di Maio, Luciano; Dittrich, Bettina; Niebergall, Ute; Böhning, Martin; Schartel, Bernhard

    2015-12-17

    In this work we report on the functionalization of a natural sodium montmorillonite (MMT) with (3-glycidyloxypropyl)trimethoxysilane by a silylation procedure and on its use as nanofiller in melt compounding of polyethylene nanocomposites. The obtained organosilylated clay showed higher interlayer spacing than the original MMT and higher thermal stability with respect to most of commercial organoclays modified with alkylammonium salts. Its addition (at 5wt%) to two different polyethylene matrices (a low density polyethylene, LDPE, and a high density polyethylene, HDPE), processed in a pilot-scale twin-screw extruder, allowed to produce hybrids with nanoscale dispersion of the filler, as demonstrated by X-ray diffraction. Thermogravimetric and differential scanning thermal analyses point out that the obtained nanocomposites do not show noticeable changes in the thermal behavior of both LDPE and HDPE, even if a slight reduction in the overall bulk crystallinity was observed in presence of the nanofillers.

  3. Facile Synthesis of Silica-Encapsulated Gold Nanoflowers as Surface-Enhanced Raman Scattering Probes Using Silane-Mediated Sol-Gel Reaction.

    PubMed

    Yoo, Jihye; Park, Sang-Joon; Lee, Sang-Wha

    2016-06-01

    Flower-like gold nanoparticles, so called gold nanoflowers (AuNFs), were synthesized through the reduction of HAuC4 with ascorbic acid in the presence of chitosan polymers. Chitosan-mediated AuNFs exhibited the distinct SERS signals of 2-chlorothiophenol (CTP) due to the presence of many interstitial gaps (so called hot spots) on the surface. For the facile silica coating, the AuNFs were conjugated with terminal carboxylate groups of (3-glycidyloxypropyl)trimethoxysilane (GPTMS), consequently forming alkoxy-terminated AuNFs which could facilely participate in the sol-gel reaction for silica coating. The resulting core-shell particles, i.e., CTP-adsorbed AuNFs with silica coating, exhibited the distinct SERS signals of CTP embedded within silica layer, warranting the effectiveness of this chemical strategy for spectroscopic labeling of Raman probes. PMID:27427704

  4. A novel technique for preparing a mono-particle layer on a substrate through the epoxy-amino cross-linking

    NASA Astrophysics Data System (ADS)

    Onishi, Shogo; Ogawa, Kazufumi

    2006-12-01

    We present a novel technique for immobilizing nanoparticles on a substrate. This method contains two techniques, which are a preparing technique of self-assembled monomolecular layers (SAMs) terminated in an epoxy group or an amino group on surface of nanoparticles or a substrate and a reaction technique between the epoxy and amino groups. The epoxy terminated SAMs or the amino terminated SAMs were prepared on nanoparticle surfaces or a substrate surface by a chemical adsorption technique using 3-glycidoxypropyltrimethoxysilane or (3-aminopropyl) trimethoxysilane. The particles dispersed in an organic solvent were coated on the substrate, and then the epoxy and amino groups were reacted each other. Unreacted nanoparticles were removed by washing. As a result, the nanoparticles were immobilized to the substrate surface through covalent bonds of the epoxy-amine cross-linking. By using this method, a mono nanoparticle layer could be formed on the substrate.

  5. Preparation and characterization of biodegradable PLA/organosilylated clay nanocomposites

    NASA Astrophysics Data System (ADS)

    Olivieri, R.; Di Maio, L.; Scarfato, P.; Incarnato, L.

    2016-05-01

    In this work a new organosilylated clay was successfully synthesized by functionalization of a natural sodium montmorillonite (MMT) by (3-glycidyloxypropyl)trimethoxysilane (GOPTMS). This organosilylated clay was used as nanofiller for preparation, by solvent casting, of poly(lactic acid) nanocomposite systems. Similar systems, containing as nanofiller the commercial Cloisite 30B (i.e. a natural sodium montmorillonite organically modified with alkylammonium salt), were also prepared for comparison. All the obtained nanocomposite films were characterized using several techniques (XRD, permeability and mechanical tensile tests). Obtained results pointed out that nanocomposite system containing the organosilylated clay showed a better intercalation of the polymer chains into the clay layers and a higher improvement of the oxygen barrier properties, when compared to both the neat PLA film and the PLA film loaded with Cloisite 30B.

  6. Surface modification of nanoparticles for radiation curable acrylate clear coatings

    NASA Astrophysics Data System (ADS)

    Bauer, F.; Gläsel, H.-J.; Hartmann, E.; Bilz, E.; Mehnert, R.

    2003-08-01

    To obtain transparent, scratch and abrasion resistant coatings a high content of nanosized silica and alumina filler was embedded in radiation-curable acrylate formulations by acid catalyzed silylation using trialkoxysilanes. 29SiMAS NMR and MALDI-TOF mass spectrometry were employed to elucidate the structure of the surface-grafted methacryloxypropyl-, vinyl- and n-propyl-trimethoxysilane. In accordance with NMR findings, MALDI-TOF MS showed highly condensed oligomeric siloxanes of more than 20 monomeric silane units. A ladder-like structure of bound polysiloxanes is proposed rather than a simplified picture of tridentate silane bonding. Hence, silane coupling agents do not only modify the chemical nature of the filler surface but also strongly effect the rheological properties of the acrylate nanodispersions.

  7. Facile Synthesis of Silica-Encapsulated Gold Nanoflowers as Surface-Enhanced Raman Scattering Probes Using Silane-Mediated Sol-Gel Reaction.

    PubMed

    Yoo, Jihye; Park, Sang-Joon; Lee, Sang-Wha

    2016-06-01

    Flower-like gold nanoparticles, so called gold nanoflowers (AuNFs), were synthesized through the reduction of HAuC4 with ascorbic acid in the presence of chitosan polymers. Chitosan-mediated AuNFs exhibited the distinct SERS signals of 2-chlorothiophenol (CTP) due to the presence of many interstitial gaps (so called hot spots) on the surface. For the facile silica coating, the AuNFs were conjugated with terminal carboxylate groups of (3-glycidyloxypropyl)trimethoxysilane (GPTMS), consequently forming alkoxy-terminated AuNFs which could facilely participate in the sol-gel reaction for silica coating. The resulting core-shell particles, i.e., CTP-adsorbed AuNFs with silica coating, exhibited the distinct SERS signals of CTP embedded within silica layer, warranting the effectiveness of this chemical strategy for spectroscopic labeling of Raman probes.

  8. Preparation and study of complex self-assembled film as a super-thin barrier on silver

    NASA Astrophysics Data System (ADS)

    Yihong, Wang; Song, Wei; Jie, Zhou; Ning, Gu; Wesche, K. D.

    2006-09-01

    A self-assembled monolayers (SAMs) of (3-mercaptopropy) trimethoxysilane (3-MPT) chemisorbed on silver surface was chemically modified by 1-octadecanethiol (C 18H 37SH) (to form self-assembled mixed-monolayer (SAMM)) and the co-polymer of N-vinylcarbazole and methyl methacrylate ester to form complex self-assemblied film (CSAF). The combinative state of interface between SAMs (or SAMM) and co-polymer were characterized by dynamic mechanical thermal analysis (DMTA). The thickness of film on Ag was characterized by X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) measurements in 10% NaOH aqueous solution with the silver surface and covered with film indicated that 3-MPT SAMs modified with C 18H 37SH and then with co-polymer have higher capability against oxidation.

  9. Polyethyleneimine-modified superparamagnetic Fe3O4 nanoparticles: An efficient, reusable and water tolerance nanocatalyst

    NASA Astrophysics Data System (ADS)

    Khoobi, Mehdi; Delshad, Tayebeh Modiri; Vosooghi, Mohsen; Alipour, Masoumeh; Hamadi, Hosein; Alipour, Eskandar; Hamedani, Majid Pirali; Sadat ebrahimi, Seyed Esmaeil; Safaei, Zahra; Foroumadi, Alireza; Shafiee, Abbas

    2015-02-01

    A novel magnetically separable catalyst was prepared based on surface modification of Fe3O4 magnetic nanoparticle (MNPs) with polyethyleneimine (PEI) via covalent bonding. [3-(2,3-Epoxypropoxy)propyl]trimethoxysilane (EPO) was used as cross linker to bond PEI on the surface of MNPs with permanent stability in contrast to PEI coating via electrostatic interactions. The synthesized catalyst was characterized by Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The catalyst show high efficiency for one-pot synthesis of 2-amino-3-cyano-4H-pyran derivatives via multi-component reaction (MCR). This procedure offers the advantages of green reaction media, high yield, short reaction time, easy purification of the products and simple recovery and reuse of the catalyst by simple magnetic decantation without significant loss of catalytic activity.

  10. Nanostructure and thermal properties of melt compounded PE/clay nanocomposites filled with an organosilylated montmorillonite

    NASA Astrophysics Data System (ADS)

    Scarfato, Paola; Incarnato, Loredana; Di Maio, Luciano; Dittrich, Bettina; Niebergall, Ute; Böhning, Martin; Schartel, Bernhard

    2015-12-01

    In this work we report on the functionalization of a natural sodium montmorillonite (MMT) with (3-glycidyloxypropyl)trimethoxysilane by a silylation procedure and on its use as nanofiller in melt compounding of polyethylene nanocomposites. The obtained organosilylated clay showed higher interlayer spacing than the original MMT and higher thermal stability with respect to most of commercial organoclays modified with alkylammonium salts. Its addition (at 5wt%) to two different polyethylene matrices (a low density polyethylene, LDPE, and a high density polyethylene, HDPE), processed in a pilot-scale twin-screw extruder, allowed to produce hybrids with nanoscale dispersion of the filler, as demonstrated by X-ray diffraction. Thermogravimetric and differential scanning thermal analyses point out that the obtained nanocomposites do not show noticeable changes in the thermal behavior of both LDPE and HDPE, even if a slight reduction in the overall bulk crystallinity was observed in presence of the nanofillers.

  11. The Effect of Silane on the Microstructure, Corrosion, and Abrasion Resistances of the Anodic Films on Ti Alloy

    NASA Astrophysics Data System (ADS)

    Wang, Jinwei; Chen, Jiali

    2016-04-01

    Anodic oxide films on Ti-6Al-4V alloy are prepared using sodium hydroxide as the base electrolyte containing aminopropyl trimethoxysilane (APS) as an additive. Some APS undergo hydrolysis, adsorption, and chemical reaction with the TiO x to form Ti-O-Si bond as confirmed by ATR-FTIR and XPS spectra, and in turn their surface appearance and roughness are greatly changed with the addition of APS as observed by their SEM images. These amino anodic films possess much higher corrosive resistances since the formation of Ti-O-Si complex enhances the compactness of the anodic films and the existence of aminopropyl groups inside the pores provides additional blocking effects. Besides, their improvement in anti-abrasive capability is attributed to the toughening effect of the chemically bonded silanes and the lubrication functions from both the chemically bonded and physically absorbed silanes between the touched interfaces.

  12. Rational surface silane modification for immobilizing glucose oxidase.

    PubMed

    Tian, Feibao; Guo, Yi; Lin, Feifei; Zhang, Yumei; Yuan, Qipeng; Liang, Hao

    2016-06-01

    Glucose oxidase (GOx) has many significant applications in biosensor and biocatalysis. In this study, we firstly quantitatively analyzed the binding efficiency of (3-aminopropyl) trimethoxysilane (APTES) modified onto the surface of GOx. It was found that the contents of the grafted silane did not significantly influence the relative activities and tertiary structures of all surface modified GOxs. Immobilization ratio and relative activity of all instances of APTES modified GOx increased, compared with those of native enzyme. However, good stability of immobilized GOx at extreme pH and high temperature could only be obtained when modified protein with low binding silane content. At pH 2.0, the immobilized GOx with low binding content showed a more than 600% activity, compared to the free enzyme. Therefore, rational surface modification would be beneficial to improving the activity and stability of immobilized enzyme as well as increasing loading amount.

  13. Preparation and characterization of the transparent hybrids of silicone epoxy resin and titanium dioxide nanoparticles via sol-gel reactions.

    PubMed

    Lem, Kwok Wai; Nguyen, Dinh Huong; Kim, Han Na; Lee, Dai Soo

    2011-08-01

    In order to prepare transparent hybrid films of high refractive index, nanoparticles of TiO2 were prepared and dispersed in a silicone epoxy (SE) resin synthesized from diphenyl silane diol and [2-(3,4-epoxycyclohexyl)ethyl] trimethoxysilane by sol-gel reactions. It was found that amorphous TiO2 nanoparticles of about 5 nm modified with hexahydro-4-methyl phthalic anhydride [HMPA] were dispersed in the SE resin without agglomerations. The refractive index of the hybrids increased linearly with increasing the TiO2 contents. The hybrid containing 30 wt% of the TiO2 particles showed light transmittance of 94% at 450 nm and refractive index of 1.63. The fine dispersion of the TiO2 nanoparticles was attributable to the sol-gel reactions between the SE resin and TiO2 nanoparticles and the modification of the TiO2 particles with HMPA.

  14. Basic role of the fiber/matrix interface on the fatigue performance of unidirectional fiberglass-reinforced composites

    SciTech Connect

    Shih, C.

    1985-01-01

    The goal of this study was that of determining the fiber/matrix interface in affecting the static bending and flexural fatigue performance of oriented fiber composites, and of evaluating the performance of silicon phthalocyanine coupling agents. Untreated, commercial silane treated, and silicon phthalocyanine agent treated fiberglass composites, as well as boiling-water degraded composites, were used to get different fiber/matrix interface conditions. The dry flexural strength of all composites was about the same. The flexural strength and the fractography of N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane treated composites essentially remained the same after the hydrothermal treatment. Silicon phthalocyanine agent treated composites had a marginally high wet flexural strength retention as compared with that of the composites without coupling agent. When the interface degraded, the failure modes in a four-point bending (flexural) test changed from tensile flexural failure to compressive flexural failure, then to the shear failure mode.

  15. Fluorescence anisotropy metrology of electrostatically and covalently labelled silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Yip, Philip; Karolin, Jan; Birch, David J. S.

    2012-08-01

    We compare determining the size of silica nanoparticles using the time-resolved fluorescence anisotropy decay of dye molecules when electrostatically and covalently bound to stable silica nanoparticles. Covalent labelling is shown to offer advantages by simplifying the dye rotational kinetics and the appropriateness of various kinetic models is discussed. Silica nanoparticles produced using Stöber synthesis of tetraethylorthosilicate (TEOS) are found to be controllable between ˜3.1 and 3.8 nm radius by adjusting the relative water:TEOS concentration. Covalent labelling with fluorescein 5(6)-isothiocyanate (FITC) bound to (3-aminopropyl) trimethoxysilane (FITC-APS) predicts a larger particle than electrostatically labelling with rhodamine 6G. The difference is attributed to the presence of an additional depolarization mechanism to Brownian rotation of the nanoparticle and dye wobbling with electrostatic labelling in the form of dye diffusion on the surface of the nanoparticle.

  16. Covalent Modification of Organo-Functionalized Graphene Oxide and its Scope as Catalyst for One-Pot Pyrazolo-Pyranopyrimidine Derivatives.

    PubMed

    Rana, Surjyakanta; Maddila, Suresh; Yalagala, Kotaiah; Maddila, Suryanarayana; Jonnalagadda, Sreekantha B

    2015-12-01

    The surface of graphene oxide (GO) was modified using [3-(2-aminoethylamino)propyl]trimethoxysilane (diamine), which exhibited excellent catalytic activity for one-pot multicomponent reactions. The newly synthesized material was fully characterized by various instrumental techniques including Fourier-transfer infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The instrumental analysis confirmed the successful grafting of organic amine functional groups onto the graphene oxide surface. The diamine-functionalized GO proved to be an excellent catalyst for the synthesis of pyrazolo-pyranopyrimidine derivatives with 93 % yield and high selectivity. The catalytic activity almost remained unaltered up to three cycles. The newly synthesized pyrazolo-pyranopyrimidine derivatives have potential use as scaffolds in designing new pharmaceutical products.

  17. Covalent Immobilization and Characterization of a Novel Pullulanase from Fontibacillus sp. Strain DSHK 107 onto Florisil® and Nano-silica for Pullulan Hydrolysis.

    PubMed

    Alagöz, Dilek; Yildirim, Deniz; Güvenmez, Hatice Korkmaz; Sihay, Damla; Tükel, S Seyhan

    2016-08-01

    A novel pullulanase partially purified from Fontibacillus sp. was covalently immobilized on Florisil® and nano-silica through both glutaraldehyde and (3-glycidyloxypropyl)trimethoxysilane spacer arms. The pullulanase immobilized on Florisil® and nano-silica through glutaraldehyde spacer arm showed 85 and 190 % activity of its free form, respectively, whereas no activity was observed when it was immobilized on the same supports through (3-glycidyloxypropyl)trimethoxysilane spacer arm. The maximum working pHs of both the immobilized pullulanases on Florisil® and nano-silica through glutaraldehyde spacer arm were determined as 5.0; however, the maximum working pH of the free pullulanase was pH 6.0. The maximum temperatures of all the pullulanase preparations were determined as 35 °C. The apparent K m values were 1.49, 1.54, and 0.59 mg/mL pullunan, respectively, for the free and immobilized pullulanases on Florisil® and nano-silica. The corresponding apparent V max values were 0.59, 1.53, and 1.57 U mg prot.(-1) min.(-1). Thermal stability of pullulanases immobilized on Florisil® and nano-silica was enhanced 6.5- and 15.6-folds, respectively at 35 °C and 6.6- and 16.0-folds, respectively, at 50 °C. The pullulanases immobilized on Florisil® and nano-silica protected 71 and 90 % of their initial activities after 10 reuses.

  18. Thiol Functionalized Silica-Mixed Matrix Membranes for Silver Capture from Aqueous Solutions: Experimental Results and Modeling

    PubMed Central

    Ladhe, A. R.; Frailie, P.; Hua, D.; Darsillo, M.; Bhattacharyya, D.

    2009-01-01

    The study deals with an aqueous phase application of Mixed Matrix Membranes (MMMs) for silver ion (Ag+) capture. Silica particles were functionalized with 3-mercaptopropyltrimethoxy silane (MPTMS) to introduce free thiol (-SH) groups on the surface. The particles were used as the dispersed phase in the polysulfone or cellulose acetate polymer matrix. The membranes were prepared by the phase inversion method to create more open and interconnected porous structures suitable for liquid phase applications. The effects of the silica properties such as particle size, specific surface area, and porous/nonporous morphology on the silver ion capture capacity were studied. It was demonstrated that the membranes are capable of selectively capturing silver from a solution containing significant concentrations of other metal ions like Ca2+. The membranes were studied to quantify the dynamic capacity for silver ion capture and its dependence on residence time through the adjustment of transmembrane pressure. The thiol-Ag+ interaction was quantified with Quartz Crystal Microbalance in a continuous flow mode experiment and the observations were compared with the membrane results. One dimensional unsteady state model with overall volumetric mass transfer coefficient was developed and solved to predict the silver concentration in the liquid phase and the solid silica phase along the membrane thickness at varying time. The breakthrough data predicted using the model is comparable with the experimental observations. The study demonstrates successful application of the functionalized silica-mixed matrix membranes for selective aqueous phase Ag+ capture with high capacity at low transmembrane pressures. The technique can be easily extended to other applications by altering the functionalized groups on the silica particles. PMID:20098490

  19. Design of novel hybrid organic-inorganic nanostructured biomaterials for immunoassay applications.

    PubMed

    Andrade, G; Barbosa-Stancioli, E F; Piscitelli Mansur, A A; Vasconcelos, W L; Mansur, H S

    2006-12-01

    The purpose of this study was to develop novel hybrid organic-inorganic materials based on poly(vinyl alcohol) (PVA) polymer chemically crosslinked network to be tested as solid support on bovine herpesvirus immunoassay. Hybrids were synthesized by reacting PVA with three different alkoxysilanes modifying chemical groups: tetraethoxysilane (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-glycidoxypropyltrimethoxysilane (GPTMS). PVA-derived hybrids were also modified by chemically crosslinking with glutaraldehyde (GA) during the synthesis reaction. In order to investigate the structure in the nanometer-scale, PVA-derived hybrids were characterized by using small-angle x-ray scattering synchrotron radiation (SAXS) and x-ray diffraction (XRD). PVA hybrids' chemical functionalities and their interaction with herpesviruses were also characterized by Fourier transform infrared spectroscopy (FTIR). The bioactivity assays were tested through enzyme linked immunosorbent assay (ELISA). SAXS results have indicated nano-ordered disperse domains for PVA hybrids with different x-ray scattering patterns for PVA polymer and PVA-derived hybrids. FTIR spectra have shown major vibration bands associated with organic-inorganic chemical groups present in the PVA, PVA-derived by silane modifier and PVA chemically crosslinked by GA. The immunoassay results have shown that PVA hybrids with chemically functionalized structures regulated to some extent the specific bioimmobilization of herpesvirus onto solid phase. We think that it is due to the overall balance of forces associated with van der Waals interaction, hydrophilic and hydrophobic forces and steric hindrance acting at the surface. PVA and PVA-derived hybrid materials were successfully produced with GA crosslinking in a nanometer-scale network. Also, such a PVA-based material could be advantageously used in immunoassays with enhanced specificity for diagnosis.

  20. Chemical modification of nanometric TiO2 particles by anchoring functional silane molecules in supercritical CO2

    NASA Astrophysics Data System (ADS)

    López-Periago, Ana M.; Sandoval, Wendy; Domingo, Concepción

    2014-03-01

    Supercritical carbon dioxide (scCO2) was used as a green solvent for the grafting of complex functional organosilanes containing nitrogen moieties on titanium dioxide (TiO2) nanoparticles using two strategies. The first strategy involved the preparation of two functional silanes, 4-nitrophenyl-(3-(trimethoxysilyl)-propyl)methanimine (NPTMS) and 4-(((3-(trimethoxysilyl)propyl)imino)methyl)-benzaldehyde (FPTMS) and further deposited under anhydrous conditions and scCO2 onto the TiO2 surface. The second strategy involved the scCO2 anhydrous deposition of bifunctional commercial silanes on the TiO2 surface. Two structures were synthesized. The first consisted in grafted TiO2 nanoparticles prepared by addition of the ligand, ((1R,2R)-N-(pyridin-2-ylmethyl)-2-(((E)-pyridin-2-ylmethylene) amino)-cyclohexan-1-amine (LPy-red), and designated as Ti-Cl-LPy-red. The second structure was synthesized by the reaction of (1,2)-diaminocylohexane (Dac), through the reactive site of 3-(Trimethoxysilyl)propyl methacrylate (MPTMS) previously deposited on the TiO2 surface and designated as Ti-MP-Dac. The synthesized silanes were characterized by ATR-FT and NMR spectroscopies and mass spectrometry. ATR-FT spectroscopy confirmed the presence of the silanes on the surface of the hybrid nanoparticles. Thermogravimetic analysis was used to estimate the loading of the silane grafted through both hydrogen and covalent bonding on the TiO2 surface. Further characterization of the solid samples was done by N2 adsorption-desorption and UV-vis diffuse reflectance.

  1. Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

    SciTech Connect

    Yu, Xiaofang; Zou, Yongcun; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-06-15

    Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

  2. Highly efficient antibody immobilization with multimeric protein Gs coupled magnetic silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Lee, J. H.; Choi, H. K.; Chang, J. H.

    2011-10-01

    This work reports the immobilization of monomeric, dimeric and trimer protein Gs onto silica magnetic nanoparticles for self-oriented antibody immobilization. To achieve this, we initially prepared the silica-coated magnetic nanoparticle having about 170 nm diameters. The surface of the silica coated magnetic nanoparticles was modified with 3- aminopropyl-trimethoxysilane (APTMS) to chemically link to multimeric protein Gs. The conjugation of amino groups on the SiO2-MNPs to cysteine tagged in multimeric protein Gs was performed using a sulfo-SMCC coupling procedure. The binding efficiencies of monomer, dimer and trimer were 77 %, 67 % and 55 % respectively. However, the efficiencies of antibody immobilization were 70 %, 83 % and 95 % for monomeric, dimeric and trimeric protein G, respectively. To prove the enhancement of accessibility by using multimeric protein G, FITC labeled goat-anti-mouse IgG was treated to mouse IgG immobilized magnetic silica nanoparticles through multimeric protein G. FITC labeled goat anti-mouse IgGs were more easily bound to mouse IgG immobilized by trimeric protein G than others. Finally protein G bound silica magnetic nanoparticles were utilized to develop highly sensitive immunoassay to detect hepatitis B antigen.

  3. Preparation of Novel Europium Complex Doped Ag@SiO2 Nanoparticles with Intense Fluorescence.

    PubMed

    Liu, Bing; Yin, Dongguang; Song, Kailin; Yang, Juan Ou; Wang, Chengcheng; Wu, Minghong

    2015-01-01

    In this study, a new europium complex of 4,4'-bis (1",1",1",2",2",3",3"-heptafluoro-4",6"- hexanedion-6"-yl)-o-terpheny-Eu(3+)-4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid-(3-aminopropyl) trimethoxysilane (BHHT-Eu(3+)-DPPDA-APTMS) was prepared first. Then novel core-shell Ag@SiO2 nanoparticles with BHHT-Eu(3+)-DPPDA-APTMS doped in shell were synthesized by a facile water-in-oil microemulsion method. The properties of the prepared complex and nanoparticles, and the effect of metal enhanced fluorescence for the nanoparticles were investigated. The prepared nanopartilces exhibited intense fluorescence, uniform morphology and good water-solubility. The fluorescent intensities of silver core-present nanopartciles were significant higher than that of silver core-absent nanoparticles owing to the metal enhanced fluorescence of silver core. It is expectable that the as-prepared nanoparticles can serve as a potential fluorescent nanoprobe, applying in high sensitive biological and medical detections.

  4. Enhanced hydrolytic stability of dental composites by use of fluoroalkyltrimethoxysilanes.

    PubMed

    Nihei, T; Kurata, S; Kondo, Y; Umemoto, K; Yoshino, N; Teranaka, T

    2002-07-01

    The hydrolytic stability of a group of experimental composite materials was evaluated. Seven distinct composites were formed by the mixing of a resin monomer mixture with silica filler that had been pre-treated with one of 7 different ethanol solutions. In one case, the filler was treated with an ethanol solution that contained only 3-methacryloyloxypropyltrimethoxysilane. In 5 cases, it was treated with solution containing a mixture of 3-methacryloyloxypropyltrimethoxysilane and one of the following hydrophobic fluoroalkyltrimethoxysilanes: trifluoropropyl-, nonafluorohexyl-, tridecafluorooctyl-, heptadecafluorodecyl-, and henicosafluorododecyl-trimethoxysilane. The tensile strength, after being immersed in water for 1800 days, of 2 of the experimental composites, whose pre-treatment regimen had included a fluoroalkyltrimethoxysilane, was significantly higher than that of the composite whose pre-treatment regimen had not included a fluoroalkyltrimethoxysilane. Moreover, there was no significant difference between the tensile strength of fresh samples of these 2 composites and the tensile strength of identically produced samples that had remained under water for 1800 days or that had been subjected to 30,000 cycles of thermal stress.

  5. Linker-induced anomalous emission of organic-molecule conjugated metal-oxide nanoparticles.

    PubMed

    Turkowski, Volodymyr; Babu, Suresh; Le, Duy; Kumar, Amit; Haldar, Manas K; Wagh, Anil V; Hu, Zhongjian; Karakoti, Ajay S; Gesquiere, Andre J; Law, Benedict; Mallik, Sanku; Rahman, Talat S; Leuenberger, Michael N; Seal, Sudipta

    2012-06-26

    Semiconductor nanoparticles conjugated with organic- and dye-molecules to yield high efficiency visible photoluminescence (PL) hold great potential for many future technological applications. We show that folic acid (FA)-conjugated to nanosize TiO(2) and CeO(2) particles demonstrates a dramatic increase of photoemission intensity at wavelengths between 500 and 700 nm when derivatized using aminopropyl trimethoxysilane (APTMS) as spacer-linker molecules between the metal oxide and FA. Using density-functional theory (DFT) and time-dependent DFT calculations we demonstrate that the strong increase of the PL can be explained by electronic transitions between the titania surface oxygen vacancy (OV) states and the low-energy excited states of the FA/APTMS molecule anchored onto the surface oxygen bridge sites in close proximity to the OVs. We suggest this scenario to be a universal feature for a wide class of metal oxide nanoparticles, including nanoceria, possessing a similar band gap (∼3 eV) and with a large surface-vacancy-related density of electronic states. We demonstrate that the molecule-nanoparticle linker can play a crucial role in tuning the electronic and optical properties of nanosystems by bringing optically active parts of the molecule and of the surface close to each other. PMID:22559229

  6. Efficacy of surface-generated nitric oxide against Candida albicans adhesion and biofilm formation

    PubMed Central

    Privett, Benjamin J.; Nutz, Steven T.; Schoenfisch, Mark H.

    2013-01-01

    This report details the efficacy of nitric oxide (NO)-releasing xerogel surfaces composed of N-(6-aminohexyl)aminopropyl trimethoxysilane (AHAP3) and isobutyltrimethoxysilane (BTMOS) against Candida albicans adhesion, viability, and biofilm formation. A parallel plate flow cell assay was used to examine the effect of NO on planktonic fungal cells. Nitric oxide fluxes as low as 14 pmol cm−2 s−1 were sufficient to reduce fungal adhesion by ~49% over controls after 90 min. By utilizing a fluorescence live/dead assay and replicate plating, NO flux was determined to reduce fungal viability in a dose dependent manner. The formation of C. albicans biofilms on NO-releasing xerogel-coated silicon rubber (SiR) coupons was impeded when compared to control (non-NO-releasing) and bare SiR surfaces. Finally, the synergistic efficacy of NO and silver sulfadiazine against C. albicans adhered fungal cells and biofilms is reported with increased killing and biofilm inhibition over NO alone. PMID:21082455

  7. Gold electrode modified with a self-assembled glucose oxidase and 2,6-pyridinedicarboxylic acid as novel glucose bioanode for biofuel cells

    NASA Astrophysics Data System (ADS)

    Ammam, Malika; Fransaer, Jan

    2014-07-01

    In this study, we have constructed a gold electrode modified with (3-aminopropyl)trimethoxysilane/2,6-pyridinedicarboxylic acid/glucose oxidase (abbreviated as, Au/ATS/PDA/GOx) by sequential chemical adsorption. Au/ATS/PDA/GOx electrode was characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and Electrochemical Impedance Spectroscopy (EIS). The data from FT-IR illustrated deposition of ATS, PDA and GOx on the surface of gold electrode. The latter has been confirmed by EIS which showed that the electron transfer resistance of the electrode increases after adsorption of each supplementary layer. Linear sweep voltammetry (LSV) in phosphate buffer solution containing 5 mM glucose displayed that compared to Au/ATS/GOx, oxidation of glucose at Au/ATS/PDA/GOx electrode starts 461 mV earlier. This gain in potential is attributed to presence of PDA in the constructed Au/ATS/PDA/GOx electrode, which plays some sort of electron mediator for glucose oxidation. The Au/ATS/PDA/GOx electrode was stabilized by an outer layer of polystyrene sulfonate (PSS) and was connected to a Pt electrode as cathode and the non-compartmentalized cell was studied under air in phosphate buffer solution pH 7.4 containing 10 mM glucose. Under these conditions, the maximum power density reaches 0.25 μW mm-2 (25 μW cm-2) for the deposited GOx layer that has an estimated surface coverage of ∼70% of a monolayer.

  8. Characterization and decolorization applicability of xerogel matrix immobilized manganese peroxidase produced from Trametes versicolor IBL-04.

    PubMed

    Iqbal, Hafiz Muhammad Nasir; Asgher, Muhammad

    2013-05-01

    A novel manganese peroxidase (MnP) isolated from solid state culture of Trametes versicolor IBL-04 was immobilized using xerogel matrix composed of trimethoxysilane (TMOS) and propyltetramethoxysilane (PTMS). FTIR spectroscopy confirmed the successful entrapment of MnP into the xerogel matrix. An immobilization efficiency of 92.2% was achieved with a purified active fraction containing 2 mg/mL MnP. After 24 h incubation at varying pH and temperatures, the immobilized MnP retained 82 and 75% activity at pH 4 and 80°C, respectively. Xerogel matrix immobilization enhanced the catalytic efficiency of entrapped MnP. Metal ions including Cu2+, Mn2+ and Fe2+ stimulated enzyme activity while cysteine, EDTA and Ag+ inhibited the activity. MnP preserved 82% of its initial activity during oxidation of MnSO4 in 10 consecutive cycles, demonstrating the reusability of xerogel entrapped MnP. The immobilized MnP could be stored for up to 75 days at 4°C without significant activity loss. To explore the industrial applicability of MnP, the immobilized MnP was tested for decolorization of textile industry effluent in a Packed Bed Reactor System (PBRS). After five consecutive cycles, 98.8% decolorization of effluent was achieved within 5 h. The kinetic properties, storage stability and reusability of entrapped MnP from T. versicolor IBL-04 reflect its prospects as biocatalyst for bioremediation and other industrial applications.

  9. Silanization and antibody immobilization on SU-8

    NASA Astrophysics Data System (ADS)

    Joshi, Manoj; Pinto, Richard; Rao, V. Ramgopal; Mukherji, Soumyo

    2007-01-01

    SU-8, an epoxy based negative photoresist, has emerged as a structural material for microfabricated sensors due to its attractive mechanical properties like low Young's modulus and chemical properties like inertness to various chemicals used in microfabrication. It can be used to fabricate MEMS structures of high aspect ratio. However, the use of SU-8 in BioMEMS application has been limited by the fact that immobilization of biomolecules on SU-8 surfaces has not been reported. In this study, the epoxy groups on the SU-8 surface were hydrolyzed in the presence of sulphochromic solution. Following this, the surface was treated with [3-(2-aminoethyl) aminopropyl]-trimethoxysilane (AEAPS). The silanized SU-8 surface was used to incubate human immunoglobulin (HIgG). The immobilization of HIgG was proved by allowing FITC tagged goat anti-human IgG to react with HIgG. This process of antibody immobilization was used to immobilize HIgG on microfabricated SU-8 cantilevers.

  10. Nano-scaled hydroxyapatite/polymer composite IV. Fabrication and cell adhesion properties of a three-dimensional scaffold made of composite material with a silk fibroin substrate to develop a percutaneous device.

    PubMed

    Furuzono, Tsutomu; Yasuda, Shoji; Kimura, Tsuyoshi; Kyotani, Singo; Tanaka, Junzo; Kishida, Akio

    2004-01-01

    Nano-scaled sintered hydroxyapatite (HAp) particles with an a-axis length of 87 +/- 23 nm, a c-axis length of 236 +/- 81 nm, and a mean aspect ratio ( c/ a) of 2.72 were covalently linked onto a silk fibroin (SF) substrate chemically modified by graft polymerization with gamma-methacryloxypropyl trimethoxysilane (MPTS). Graft polymerization with poly(MPTS) on SF was conducted by free-radical initiation in a water solvent with pentaethylene glycol dodecyl ether as a nonionic surfactant. The alkoxysilyl groups of the graft polymers avoided hydrolysis and maintained their activity in coupling with the hydroxyl groups on the HAp surface despite the use of water as the reaction solvent. The weight gain of poly(MPTS) on SF increased with increasing the reaction time, eventually reaching a plateau value of about 15 wt% after 50 min of reaction time. After HAp covalent coating, the particles separated or aggregated into several crystals, as shown by scanning electron microscopic observation. L929 fibroblast cells adhered more plentifully on HAp-coated SF compared to untreated SF and hydrolyzed poly(MPTS)-grafted SF during 24 h or 48 h of incubation. The cells adhered only on the HAp surface but not at all on the dehydrated grafted surface of SF without HAp. A button-shaped prototype for a percutaneous device was manufactured by transplantation of HAp-coated SF fibers of about 100 microm in length onto silicone moldings using an adhesive, and the device showed good cell adhesiveness.

  11. Fabrication of a superhydrophobic coating with high adhesive effect to substrates and tunable wettability

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Zhang, Zhaozhu; Zhu, Xiaotao; Men, Xuehu; Ge, Bo; Zhou, Xiaoyan

    2015-02-01

    In this paper, a new superhydrophobic coating was successfully prefabricated by a facile sol-gel process which was made up of first the surface chemical reaction of (3-Glycidyloxypropyl) trimethoxysilane (A-187) and SiO2 particles and subsequent spray-coating onto the substrate. Further hardening treatment and surface fluorination allowed the SiO2 coating with the optimum mass ratio of 2.0:1 to exhibit nice superhydrophobic property and high adhesive effect to substrates. Our researches indicated that the mass ratio of A-187 and SiO2 particles could significantly control the surface morphology (or the wettability) and affect adhesion force of the superhydrophobic coating to substrates. In the process, hardening temperature was quite important for rapid evaporation of the solvent and then fast hardening of the coating despite the absence of the similar effect to the mass ratio of A-187 and SiO2 particles on the superhydrophobic coating, and moreover, a higher hardening temperature could also highly improve transparency of the superhydrophobic coating. These findings suggest that the superhydrophobic coating should have promising commercial applications as a self-cleaning product.

  12. Interfacial Characterizations of a Nickel-Phosphorus Layer Electrolessly Deposited on a Silane Compound-Modified Silicon Wafer Under Thermal Annealing

    NASA Astrophysics Data System (ADS)

    Lai, Kuei-Chang; Wu, Pei-Yu; Chen, Chih-Ming; Wei, Tzu-Chien; Wu, Chung-Han; Feng, Shien-Ping

    2016-10-01

    Front-side metallization of a Si wafer was carried out using electroless deposition of nickel-phosphorus (Ni-P) catalyzed by polyvinylpyrrolidone-capped palladium nanoclusters (PVP-nPd). A 3-[2-(2-Aminoethylamino)ethylamino] propyl-trimethoxysilane (ETAS) layer was covalently bonded on the Si surface as bridge linker to the Pd cores of PVP-nPd clusters for improving adhesion between the Ni-P layer and the Si surface. To investigate the effects of an interfacial ETAS layer on the Ni silicide formation at the Ni-P/Si contact, the Ni-P-coated Si samples were thermally annealed via rapid thermal annealing (RTA) from 500°C to 900°C for 2 min. To compare with the ETAS sample, the sputtered Ni layer on Si and electroless Ni-P layer on ion-Pd-catalyzed Si (both are standard processes) were also investigated. The microstructural characterizations for the Ni-P or Ni layer deposited on the Si wafer were performed using x-ray diffractometer, scanning electron microscopy, and transmission electron microscopy. Our results showed that the ETAS layer acted as a barrier to slow the atomic diffusion of Ni toward the Si side. Although the formation of Ni silicides required a higher annealing temperature, the adhesion strength and contact resistivity measurements of annealed Ni-P/Si contacts showed satisfactory results, which were essential to the device performance and reliability during thermal annealing.

  13. Linker-Induced Anomalous Emission of Organic-Molecule Conjugated Metal-Oxide Nanoparticles

    SciTech Connect

    Turkowski, Volodymyr; Babu, Suresh; Le, Duy; Kumar, Amit; Haldar, Manas K.; Wagh, Anil V.; Hu, Zhongjian; Karakoti, Ajay S.; Gesquiere, Andre J.; Law, Benedict; Mallik, Sanku; Rahman, Talat S.; Leuenberger, Michael N.; Seal, Sudipta

    2012-06-26

    Semiconductor nanoparticles conjugated with organic- and dye-molecules to yield high efficiency visible photoluminescence (PL) hold great potential for many future technological applications. We show that folic acid (FA)-conjugated to nanosize TiO2 and CeO2 particles demonstrates a dramatic increase of photoemission intensity at wavelengths between 500 and 700 nm when derivatized using aminopropyl trimethoxysilane (APTMS) as spacer-linker molecules between the metal oxide and FA. Using density-functional theory (DFT) and time-dependent DFT calculations we demonstrate that the strong increase of the PL can be explained by electronic transitions between the titania surface oxygen vacancy (OV) states and the low-energy excited states of the FA/APTMS molecule anchored onto the surface oxygen bridge sites in close proximity to the OVs. We suggest this scenario to be a universal feature for a wide class of metal oxide nanoparticles, including nanoceria, possessing a similar band gap (3 eV) and with a large surface-vacancy-related density of electronic states. We demonstrate that the molecule-nanoparticle linker can play a crucial role in tuning the electronic and optical properties of nanosystems by bringing optically active parts of the molecule and of the surface close to each other.

  14. A multiscale description of molecular adsorption on gold nanoparticles by nonlinear optical spectroscopy.

    PubMed

    Humbert, C; Pluchery, O; Lacaze, E; Tadjeddine, A; Busson, B

    2012-01-01

    Nonlinear optical Sum and Difference-Frequency spectroscopies are used to probe and model the surface of thiophenol-functionalised gold nanoparticles grafted on a Si(100) substrate through two different silanization procedures. By scanning the [980-1100 cm(-1)] infrared spectral range with the CLIO Free Electron Laser, ring deformation vibrations of adsorbed thiophenol are investigated. Quantitative data analysis addresses three levels of organization: microscopic, nanoscopic and molecular. Grafting with p-aminophenyl-trimethoxysilane shows an increase of around 40% in surface density of nanoparticles (N(s)) as compared to 3-aminopropyl-triethoxysilane. The relative amplitudes of the resonant and nonresonant contributions to the SFG and DFG spectra are discussed in terms of N(s), Fresnel reflectivity factors and local amplification of the nonlinear signals by coupling to the surface plasmon of the particles. They are shown to quantitatively scale with N(s), as measured by atomic force microscopy. Vibration mode assignment is performed through a critical analysis of literature data on IR and Raman spectroscopies coupled to DFT calculations, for which a methodology specific to molecules adsorbed on gold atoms is discussed. PMID:22083521

  15. Inorganic–organic hybrid materials through post-synthesis modification: Impact of the treatment with azides on the mesopore structure

    PubMed Central

    Keppeler, Miriam; Holzbock, Jürgen; Akbarzadeh, Johanna; Peterlik, Herwig

    2011-01-01

    Summary Hybrid, hierarchically organized, monolithic silica gels, comprising periodically arranged mesopores and a cellular macroscopic network, have been prepared through a co-condensation reaction of tetrakis(2-hydroxyethyl)orthosilicate with chloromethyl-trimethoxysilane or 3-(chloropropyl)-triethoxysilane. Subsequent conversion of the chloro groups into azido groups, by nucleophilic substitution with NaN3 in N,N-dimethylformamide, was conducted upon preservation of the monolithic structure. However, treatment with NaN3 had a strong influence on the structure in the mesoporous regime, with changes such as an increase of mesopore diameter, pore volume and lattice constants, as well as a concomitant decrease of the pore wall thickness, as confirmed by small angle X-ray scattering, transmission electron microscopy, and nitrogen sorption analysis. Similar effects were observed for unmodified silica gels by simple ageing in azide-containing media, whether a relatively small or a sterically demanding counter ion (Na+ or (H3C)4N+) was used. The structural modification did not seem to depend greatly on whether an organic aprotic solvent (N,N-dimethylformamide, 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone) or a protic solvent that can form hydrogen bonds, such as water, was used. PMID:22003454

  16. Silane modified starch for compatible reactive blend with poly(lactic acid).

    PubMed

    Jariyasakoolroj, Piyawanee; Chirachanchai, Suwabun

    2014-06-15

    A reactive blend of poly(lactic acid) (PLA) and a surface modified starch by silane coupling agent to achieve compatibility is proposed. A detailed structural analysis by using (1)H-(1)H TOCSY NMR spectrum clarifies, for the first time, that chloropropyl trimethoxysilane (CPMS) forms covalent bonds with starch during starch modification and consequently forms covalent bonds with PLA in the step of blending to produce a reactive blend of PLA and CP-starch. The CP-starch covalently bound with PLA provides the compatibility between PLA and starch and also plays the role as nucleating agent as identified from a significant increase of degree of crystallinity (as high as 10-15 times), as well as induces chain mobility, as identified from a slight decrease in glass transition temperature (∼5-10°C). The PLA/CP-starch film performed as well as neat PLA with slight increases in tensile strength and elongation at break, as compared to other PLA/silane modified starch films. PMID:24721076

  17. Surface engineering for long-term culturing of mesenchymal stem cell microarrays.

    PubMed

    Rasi Ghaemi, Soraya; Harding, Frances; Delalat, Bahman; Vasani, Roshan; Voelcker, Nicolas H

    2013-08-12

    The cell microarray format can recreate a multitude of cell microenvironments on a single chip using only minimal amounts of reagent. In this study, we describe surface modifications to passivate cell microarrays, aiming to adapt the platform to the study of stem cell behavior over long-term culture periods. Functionalization of glass slides with (3-glycidyloxypropyl) trimethoxysilane enabled covalent anchoring of extracellular matrix proteins on microscale spots printed by a robotic contact printer. Subsequently, the surface was passivated by bovine serum albumin (BSA) or poly(ethylene glycol)bisamine (A-PEG) with molecular weights of 3000, 6000, and 10 000 Da. Cloud-point conditions for A-PEG grafting were attained that were compatible with protein deposition. Passivation strategies were assessed by culturing mesenchymal stem cells on the microarray platform. While both BSA and A-PEG passivation initially blocked cell adhesion between the printed spots, only A-PEG grafting was able to maintain cell pattern integrity over the entire culture period of 3 weeks.

  18. Silica-modified monodisperse hexagonal lanthanide nanocrystals: synthesis and biological properties

    NASA Astrophysics Data System (ADS)

    Kostiv, U.; Janoušková, O.; Šlouf, M.; Kotov, N.; Engstová, H.; Smolková, K.; Ježek, P.; Horák, D.

    2015-10-01

    Oleic acid-stabilized hexagonal NaYF4:Yb3+/Er3+ nanocrystals, emitting green and red luminescence, were prepared by the high-temperature co-precipitation of lanthanide chlorides. By varying the reaction time and the Ln3+/Na+ ratio, the nanocrystal size can be controlled within the range 16-270 nm. The maximum upconversion quantum yield is achieved under 970 nm excitation. The reverse microemulsion technique using hydrolysis and condensation of tetraethoxysilane is a suitable method to coat the nanocrystal surface with a silica shell to make the particles dispersible and colloidally stable in aqueous media. During the subsequent functionalization, (3-aminopropyl)trimethoxysilane introduced amino groups onto the silica to enable future bioconjugation with the target molecules. All specimens were characterized by TEM microscopy, electron and X-ray diffraction, ATR FT-IR spectroscopy, and upconversion luminescence. Finally, in vitro cytotoxicity and intracellular nanoparticle uptake (using confocal microscopy) were determined with human cervical carcinoma HeLa and mRoGFP HeLa cells, respectively. From the investigated particles, amino-functionalized NaYF4:Yb3+/Er3+ nanocrystals internalized into the cells most efficiently. The nanoparticles proved to be nontoxic at moderate concentrations, which is important when considering their prospective application in biolabeling and luminescence imaging of various cell types.

  19. Sol-gel synthesis and luminescence of unexpected microrod crystalline Ca 5La 5(SiO 4) 3(PO 4) 3O 2:Dy 3+ phosphors employing different silicate sources

    NASA Astrophysics Data System (ADS)

    Yan, Bing; Huang, Honghua

    2007-08-01

    Ca5La5(SiO4)3(PO4)3O2 doped with Dy3+ were synthesized by sol-gel technology with hybrid precursor employed four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM diagraphs show that there exist some novel unexpected morphological structures of microrod owing to the crosslinking reagents than TEOS as silicate source for their amphipathy template effect. X-ray pictures confirm that Ca5La5(SiO4)3(PO4)3O2:Dy3+ compound is formed by a pure apatitic phase. The Dy3+ ions could emit white light in Ca5La5(SiO4)3(PO4)3O2 compound, and the ratio of Y/B is 1.1, when the Dy3+ doped concentration is 1.0 mol%.

  20. Three-phase molecularly imprinted sol-gel based hollow fiber liquid-phase microextraction combined with liquid chromatography-tandem mass spectrometry for enrichment and selective determination of a tentative lung cancer biomarker.

    PubMed

    Moein, Mohammad Mahdi; Javanbakht, Mehran; Karimi, Mohammad; Akbari-Adergani, Behrouz; Abdel-Rehim, Mohamed

    2015-07-15

    In the present study, the modification of a polysulfone hollow fiber membrane with in situ molecularly imprinted sol-gel process (as a novel and one-step method) was prepared and investigated. 3-(propylmethacrylate)trimethoxysilane (3PMTMOS) as an inorganic precursor was used for preparation of molecularly imprinted sol-gel. The modified molecularly imprinted sol-gel hollow fiber membrane (MSHM) was used for the liquid-phase microextraction (LPME) of hippuric acid (HA) in human plasma and urine samples. MSHM as a selective, robust, and durable tool was used for at least 50 extractions without significant decrease in the extraction efficiency. The non-molecularly imprinted sol-gel hollow fiber membrane (NSHM) as blank hollow fiber membrane was prepared by the same process, only without HA. To achieve the best condition, influential parameters on the extraction efficiency were thoroughly investigated. The capability of this robust, green, and simple method for extraction of HA was successfully accomplished with LC/MS/MS. The limits of detection (LOD) and quantification (LOQ) in human plasma and urine samples were 0.3 and 1.0nmolL(-1), respectively. The standard calibration curves were obtained within the concentration range 1-2000nmolL(-1) for HA in human plasma and urine. The coefficients of determination (r(2)) were ≥0.998. The obtained data exhibited recoveries were higher than 89% for the extraction of HA in human plasma and urine samples.

  1. Molecularly imprinted polymer-sol-gel tablet toward micro-solid phase extraction: I. Determination of methadone in human plasma utilizing liquid chromatography-tandem mass spectrometry.

    PubMed

    El-Beqqali, Aziza; Abdel-Rehim, Mohamed

    2016-09-14

    In the present work molecularly imprinted sol-gel tablet (MIP-Tablet) was prepared. The MIP-sol-gel was prepared as a thin layer on polyethylene material in a tablet form. Methadone-d9 was selected as the template and 3-(propylmethacrylate)-trimethoxysilane was used as precursor. MIP-Tablet was applied for micro-solid phase extraction (μ-SPE). The MIP-Tablet was used for the determination of methadone in human plasma samples utilizing liquid chromatography-tandem mass spectrometry; and each tablet could be used twenty times. The extraction time was 10 min while desorption time was 6 min. Factors affecting the extraction efficiency such as desorption solvents, sample pH, salt addition, extraction time, desorption time and adsorption capacity were investigated. The calibration curves were obtained within the range of 5-5000 ng/mL using methadone in human plasma samples. The coefficients of determination (r(2)) values were ≥0.999 for all runs and the extraction recovery was >80%. The accuracy values for quality control samples varied from +3.6 to +9.7% and the inter-day precision (RSD %) values were ranged from 5.0 to 8.0%. The limit of detection was 1.0 ng/mL and the lower limit of quantification was 5 ng/mL utilizing methadone in human plasma samples.

  2. Surface confined ionic liquid as a stationary phase for HPLC

    SciTech Connect

    Wang, Qian; Baker, Gary A; Baker, Sheila N; Colon, Luis

    2006-01-01

    Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of the ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.

  3. Increase in stability of cellulase immobilized on functionalized magnetic nanospheres

    NASA Astrophysics Data System (ADS)

    Zhang, Wenjuan; Qiu, Jianhui; Feng, Huixia; Zang, Limin; Sakai, Eiichi

    2015-02-01

    Functionalized magnetic nanospheres were prepared by co-condensation of tetraethylorthosilicate with three different amino-silanes: 3-(2-aminoethylamino propyl)-triethoxysilane (AEAPTES), 3-(2-aminoethylamino propyl)-trimethoxysilane (AEAPTMES) and 3-aminopropyltriethoxysilane (APTES). Then three functionalized magnetic nanospheres were used as supports for immobilization of cellulase. The three functionalized magnetic nanospheres with core-shell morphologies exhibited higher capacity for cellulase immobilization than unfunctionalized magnetic nanospheres. The increasing of surface charge of functionalized magnetic nanospheres leads to an enhancement of the capacity of cellulase immobilization. Particularly, AEAPTMES with methoxy groups was favored to be hydrolyzed and grafted on unfunctionalized magnetic nanospheres than the others. AEAPTMES functionalized magnetic nanospheres with the highest zeta potential (29 mV) exhibited 87% activity recovery and the maximum amount of immobilized cellulase was 112 mg/g support at concentration of initial cellulase of 8 mg/mL. Immobilized cellulase on AEAPTMES functionalized magnetic nanospheres had higher temperature stability and broader pH stability than other immobilized cellulases and free cellulase. In particular, it can be used in about 40 °C, demonstrating the potential of biofuel production using this immobilized cellulase.

  4. Patterned surface with controllable wettability for inkjet printing of flexible printed electronics.

    PubMed

    Nguyen, Phuong Q M; Yeo, Lip-Pin; Lok, Boon-Keng; Lam, Yee-Cheong

    2014-03-26

    Appropriate control of substrate surface properties prior to inkjet printing could be employed to improve the printing quality of fine resolution structures. In this paper, novel methods to fabricate patterned surfaces with a combination of hydrophilic and hydrophobic properties are investigated. The results of inkjet printing of PEDOT/PSS conductive ink on these modified surfaces are presented. Selective wetting was achieved via a two-step hydrophilic-hydrophobic coating of 3-aminopropyl trimethoxysilane (APTMS) and 3M electronic grade chemical respectively on PET surfaces; this was followed by a selective hydrophilic treatment (either atmospheric O2/Ar plasma or UV/ozone surface treatment) with the aid of a Nickel stencil. Hydrophobic regions with water contact angle (WCA) of 105° and superhydrophilic regions with WCA <5° can be achieved on a single surface. During inkjet printing of the treated surfaces, PEDOT/PSS ink spread spontaneously along the hydrophilic areas while avoiding the hydrophobic regions. Fine features smaller than the inkjet droplet size (approximately 55 μm in diameter) can be successfully printed on the patterned surface with high wettability contrast. PMID:24571607

  5. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10‑4 S cm‑1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  6. Air-Stable, Cross-Linkable, Hole-Injecting/Transporting Interlayers for Improved Charge Injection in Organic Light-Emitting Diodes

    SciTech Connect

    Li,J.; Marks, T.

    2008-01-01

    Modification of inorganic electrode surfaces has attracted great attention in the quest to optimize organic optoelectronic devices. An air-stable, cross-linkable trimethoxysilane functionalized hole-transporting triarylamine (4,4'-bis[(p-trimethoxysilylpropylphenyl)phenylamino]biphenyl, TPD-[Si(OMe)3]2) has been synthesized and self-assembled or spin-coated onto tin-doped indium oxide (ITO) anode surfaces to form monolayers or multilayer siloxane films, respectively. The modified ITO surfaces were characterized by advancing aqueous contact angle, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV). Increased surface work function and enhanced ITO-hole transport layer (HTL) contact via robust covalent bonding are expected to facilitate hole injection from the ITO anode, resulting in organic light-emitting diode (OLED) performance enhancement versus that of a device without such interlayers. For a device having the structure ITO/spin-coated-TPD-[Si(OMe)3]2 from aqueous alcohol + acetic acid blend solution (40 nm)/NPB (20 nm)/Alq (60 nm)/LiF (1 nm)/Al (100 nm), a maximum light output of 32800 cd/m2, a 4.25 V turn-on voltage, and a maximum current efficiency of 5.8 cd/A is achieved. This performance is comparable to or superior to that of analogous devices prepared with analogous trichorosilyl precursors. The air-stable interlayer material developed here is also applicable to large-area coating techniques.

  7. Investigation of Diffusion Characteristics through Microfluidic Channels for Passive Drug Delivery Applications.

    PubMed

    Goudie, Marcus J; Ghuman, Alyssa P; Collins, Stephanie B; Pidaparti, Ramana M; Handa, Hitesh

    2016-01-01

    Microfluidics has many drug delivery applications due to the ability to easily create complex device designs with feature sizes reaching down to the 10s of microns. In this work, three different microchannel designs for an implantable device are investigated for treatment of ocular diseases such as glaucoma, age-related macular degeneration (AMD), and diabetic retinopathy. Devices were fabricated using polydimethylsiloxane (PDMS) and soft lithography techniques, where surface chemistry of the channels was altered using 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (PEG-silane). An estimated delivery rate for a number of common drugs was approximated for each device through the ratio of the diffusion coefficients for the dye and the respective drug. The delivery rate of the model drugs was maintained at a physiological condition and the effects of channel design and surface chemistry on the delivery rate of the model drugs were recorded over a two-week period. Results showed that the surface chemistry of the device had no significant effect on the delivery rate of the model drugs. All designs were successful in delivering a constant daily dose for each model drug. PMID:27313895

  8. Preparation of Gold Nanoparticles Deposited Silicon Thin Film Electrode by Self-Assembly Method for the Employment of an Anode Material for Lithium Secondary Batteries.

    PubMed

    Halim, Martin; Kim, Jung Sub; Nguyen, Si Hieu; Jeon, Bup Ju; Lee, Joong Kee

    2015-10-01

    This work describes a self-assembly method of gold nanoparticles coating on the surface of silicon thin films for the anode material of lithium secondary batteries. The preparation of the silicon thin films was carried out by electron cyclotron resonance metal organic chemical vapor deposition (ECR-MOCVD) process. The obtained films were further coated with (3-aminopropyl)-trimethoxysilane (APTMS) which has a role to bind the oxygen functional groups on Si surface and the gold nanoparticles. The dispersed gold nanoparticles on the surface of silicon thin films could be prepared due to self-assembly phenomena which interact between attraction and repulsion in gold nanoparticles colloidal solution (GNCS). The use of reducing agent of sodium citrate and tannic acid in GNCS significantly affected the size of gold nanoparticle in our experimental range. Based on our experimental results, the higher reversible capacity was exhibited for the silicon that was immersed in the GNCS consisted of only sodium citrate. The GNCS consisted of both sodium citrate and tannic acid produced severe coagulated nanoparticles when deposited on the silicon surface and thus inhibited the lithium movement from electrolyte to silicon surface. Consequently, the reversible capacity of silicon anode material with coagulated gold nanoparticles coating showed the reduced performance. PMID:26726492

  9. Detection of prostate-specific antigen with biomolecule-gated AlGaN/GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Li, Jia-dong; Cheng, Jun-jie; Miao, Bin; Wei, Xiao-wei; Xie, Jie; Zhang, Jin-cheng; Zhang, Zhi-qiang; Wu, Dong-min

    2014-07-01

    In order to improve the sensitivity of AlGaN/GaN high electron mobility transistor (HEMT) biosensors, a simple biomolecule-gated AlGaN/GaN HEMT structure was designed and successfully fabricated for prostate specific antigen (PSA) detection. UV/ozone was used to oxidize the GaN surface and then a 3-aminopropyl trimethoxysilane (APTES) self-assembled monolayer was bound to the sensing region. This monolayer serves as a binding layer for attachment of the prostate specific antibody (anti-PSA). The biomolecule-gated AlGaN/GaN HEMT sensor shows a rapid and sensitive response when the target prostate-specific antigen in buffer solution was added to the antibody-immobilized sensing area. The current change showed a logarithm relationship against the PSA concentration from 0.1 pg/ml to 0.993 ng/ml. The sensitivity of 0.215% is determined for 0.1 pg/ml PSA solution. The above experimental result of the biomolecule-gated AlGaN/GaN HEMT biosensor suggested that this biosensor might be a useful tool for prostate cancer screening.

  10. Hydrophobic high surface area zeolites derived from fly ash for oil spill remediation.

    PubMed

    Sakthivel, Tamilselvan; Reid, David L; Goldstein, Ian; Hench, Larry; Seal, Sudipta

    2013-06-01

    Fly ash, a coal combustion byproduct with a predominantly aluminosilicate composition, is modified to develop an inexpensive sorbent for oil spill remediation. The as-produced fly ash is a hydrophilic material with poor sorption capacity. A simple two-step chemical modification process is designed to improve the oil sorption capacity. First, the fly ash was transformed to a zeolitic material via an alkali treatment, which increased the specific surface area up to 404 m(2) g(-1). Then, the material was surface functionalized to form a hydrophobic material with high contact angle up to 147° that floats on the surface of an oil-water mixture. The reported oil sorption capacities of X-type zeolite sorbent with different surface functionalization (propyl-, octyl-, octadecyl-trimethoxysilane and esterification) were estimated to 1.10, 1.02, 0.86, and 1.15 g g(-1), respectively. Oil sorption was about five times higher than the as-received fly ash (0.19 g g(-1)) and also had high buoyancy critical for economic cleanup of oil over water.

  11. Synthesis of Pt-immobilized on silica and polystyrene-encapsulated silica and their applications as electrocatalysts in the proton exchange membrane fuel cell

    SciTech Connect

    Yi, Sung-Chul; Kim, Chang Young; Jung, Chi Young; Jeong, Sung Hoon; Kim, Wha Jung

    2011-01-15

    Nano sized Pt particles were successfully immobilized onto SiO{sub 2} and polystyrene-encapsulated silica core shell (SiO{sub 2}@PS). To make the immobilization of Pt onto both silica and polystyrene-encapsulated silica core shell, SiO{sub 2} was first functionalized with -NH{sub 2} using 3-amino propyl trimethoxysilane (APTMS) while for core shell, the negatively charged surface of polystyrene (PS) was changed with positive charge by cationic surfactant such as cetyltrimethylammonium chloride (CTACl) to make the formation of SiO{sub 2} shell on preformed PS sphere. Transmission electron micrograph (TEM) images shows that Pt nanoparticles immobilized onto SiO{sub 2} and SiO{sub 2}@PS were to be 3-4 nm without agglomeraiton. The energy dispersive spectroscope (EDS) shows that Pt contents on both SiO{sub 2} and SiO{sub 2}@PS were to be 21.45% and 20.28%, respectively. In case of Pt-SiO{sub 2}@PS, it is believed that Pt should have been immobilized onto PS surface and pore within SiO{sub 2} shell as well as SiO{sub 2} surface. The MEA fabricated with Pt-SiO{sub 2}@PS shows better cell performance than of Pt-SiO{sub 2}.

  12. 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.

  13. Synthesis of cubic Ia-3d mesoporous silica in anionic surfactant templating system with the aid of acetate.

    PubMed

    Deng, Shao-Xin; Xu, Xue-Yan; He, Wen-Chao; Wang, Jin-Gui; Chen, Tie-Hong

    2014-08-01

    Mesoporous silica with three-dimensional (3D) bicontinuous cubic Ia-3d structure and fascinating caterpillar-like morphology was synthesized by using anionic surfactant N-lauroylsarcosine sodium (Sar-Na) as the template and 3-amionpropyltrimethoxysilane (APS) as the co-structure-directing agent (CSDA) with the aid of acetate. A phase transformation from high interfacial curvature 2D hexagonal to low interfacial curvature 3D cubic Ia-3d occurred in the presence of a proper amount of acetate. Other species of salts (excluding acetate) had the ability to induce the caterpillar-like morphology, but failed to induce the cubic Ia-3d mesostructure. Furthermore, [3-(2-aminoethyl)-aminopropyl]trimethoxysilane (DAPS) was also used as the CSDA to synthesize Ia-3d mesostructured silica under the aid of sodium acetate. After extraction of the anionic surfactants, amino and di-amine functionalized 3D bicontinuous cubic Ia-3d mesoporous silicas were obtained and used as supports to immobilize Pd nanoparticles for supported catalysts. The catalytic activity of the catalysts was tested by catalytic hydrogenation of allyl alcohol.

  14. Flexible poly(amic acid) conducting polymers: effect of chemical composition on structural, electrochemical, and mechanical properties.

    PubMed

    Du, Nian; Wong, Cheuk; Feurstein, Michael; Sadik, Omowunmi A; Umbach, Christopher; Sammakia, Bahgat

    2010-09-01

    A new approach for creating flexible, mechanically strong poly(amic acid) (PAA) hybrid copolymers is described. The reduction of gold salts to gold nanoparticles by PAA coupled with its copolymerization in the presence of various silanes (e.g., N-[3-(trimethoxysilyl)-propyl] aniline (TMOSPA), 3-aminopropyl-trimethoxysilane (APTMOS), dichlorodimethylsilane (DCMS), and tetramethoxysilane (TMOS)) has enabled the design of a series of polymeric films. The resulting poly(amic acid), silane, and gold (PSG) solutions were employed for the fabrication of flexible, ternary polymers with a minimum bend ratio of 3 mm using thermal desolvation and/or wet-phase inversion techniques. By controlling the composition and synthesis conditions, porous PSG films were produced that are flexible or rigid, transparent or opaque, and/or mechanically strong. (1)H NMR, (13)C NMR, and Fourier transform infrared spectroscopy (FTIR) characterization results showed that the carboxylic acid moieties were retained in the PSG copolymer. Thermal stabilities with degradation characteristics of the polymers were determined using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Although structurally and morphologically different from the parent PAA, copolymerization with silanes had significantly improved the mechanical and interfacial property of the PSG class of films.

  15. Novel Active Surface Prepared by Embedded Functionalized Clays in an Acrylate Coating.

    PubMed

    Xia, Yining; Ghasemlou, Mehran; Rubino, Maria; Auras, Rafael; Baghdachi, Jamil

    2015-11-11

    The research on a self-decontaminating surface has received significant attention because of the growth of pathogenic microorganisms on surfaces. In this study, a novel and simple technique for producing an active surface with antimicrobial functionality is demonstrated. A tethering platform was developed by grafting the biocide ampicillin (Amp) to a nanoclay and dispersing the nanoclay in a UV-curable acrylate coating applied on polypropylene films as the substrate. A coupling agent, [3-(glycidyloxy)propyl]trimethoxysilane, was used as a linker between the nanoclay and Amp. The Amp-functionalized clay was further modified with an organic surfactant to improve the compatibility with the coating. Several characterization assays, such as Fourier infrared transform analysis, thermogravimetric analysis, and X-ray diffraction, were conducted to confirm the presence of Amp in the nanoclay. Transmission electron microscopy images revealed that the clay particles were well dispersed in the coating and had a partial exfoliated morphology. The active coating surface was effective in inhibiting the growth of Gram-positive Listeria monocytogenes and Gram-negative Salmonella Typhimurium via contact. These findings suggest the potential for the development of active surfaces with the implementation of nanotechnology to achieve diverse functionalities. PMID:26488557

  16. Combinatorial materials research applied to the development of new surface coatings XVI: fouling-release properties of amphiphilic polysiloxane coatings.

    PubMed

    Stafslien, Shane J; Christianson, David; Daniels, Justin; VanderWal, Lyndsi; Chernykh, Andrey; Chisholm, Bret J

    2015-01-01

    High-throughput methods were used to prepare and characterize the fouling-release (FR) properties of an array of amphiphilic polysiloxane-based coatings possessing systematic variations in composition. The coatings were derived from a silanol-terminated polydimethylsiloxane, a silanol-terminated polytrifluorpropylmethylsiloxane (CF3-PDMS), 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane (TMS-PEG), methyltriacetoxysilane and hexamethyldisilazane-treated fumed silica. The variables investigated were the concentration of TMS-PEG and the concentration of CF3-PDMS. In general, it was found that the TMS-PEG and the CF3-PDMS had a synergist effect on FR properties with these properties being enhanced by combining both compounds into the coating formulations. In addition, reattached adult barnacles removed from coatings possessing both TMS-PEG and relatively high levels of CF3-PDMS displayed atypical base-plate morphologies. The majority of the barnacles removed from these coatings exhibited a cupped or domed base-plate as compared to the flat base-plate observed for the control coating that did not contain TMS-PEG or CF3-PDMS. Coating surface analysis using water contact angle measurements indicated that the presence of CF3-PDMS facilitated migration of TMS-PEG to the coating/air interface during the film formation/curing process. In general, coatings containing both TMS-PEG and relatively high levels of CF3-PDMS possessed excellent FR properties.

  17. Modification of Substrates for Improved Chemical Bonding at Epoxy Interfaces

    NASA Astrophysics Data System (ADS)

    Schoch, Andrew B.; Fischer, Daniel A.; Lenhart, Joseph L.

    2010-03-01

    Near-edge X-ray absorption fine structure (NEXAFS) is exploited to investigate the interface between epoxy resins and a solid substrate, which is critical for many industrial and defense related composite structures. The goal is to link the interfacial chemistry, structure and resulting properties to the adhesive properties, enabling the design of interfaces with tunable strength, energy dissipation, and impact performance. Silicon surfaces were chosen as a model substrate and were coated sequentially through reactions with glycidyl propyl trimethoxysilane (GPS), various polyoxyalkyleneamines (POAAs), and finally diglycidyl ether of bisphenol-A (DGEBA). By controlling the molecular ratios of the POAAs, which have varying functionality and molecular weight the reactivity of these surfaces toward epoxies can be controlled. In addition to NEXAFS which provides insight regarding the molecular organization and chemistry at the interface, mechanical testing will also be explored to determine the impact on interfacial properties. Asymmetric dual cantilever beam testing was chosen for these samples because it drives the crack to the interface and allows for ease of characterization with surface science techniques after failure. A combination of NEXAFS and XPS will be utilized to interrogate the fracture surfaces and provide insight into the adhesive failure mechanisms and location.

  18. Highly uniform polyhedral colloids formed by colloidal crystal templating

    NASA Astrophysics Data System (ADS)

    Wang, Yifan; McGinley, James; Crocker, John; Crocker Research Group Team

    2015-03-01

    We seek to create polyhedral solid particles by trapping oil droplets in a colloidal crystal, and polymerizing them in situ, resulting in polyhedral particles containing spherical dimples in an ordered arrangement. Specifically, highly monodisperse, micron-sized droplets of 3-methacryloxypropyl trimethoxysilane (TPM) were first prepared through a poly condensation reaction, following well established methods. The droplets were mixed with an excess of polystyrene(PS) particles (diameter in 2.58 μm), which formed close packed (FCC or HCP) colloidal crystals by natural sedimentation and compression under partial drying to an extent, with TPM oil droplets trapped into their tetrahedral and octahedral interstitial sites and wet PS particles. Depending on the initial particle volume fraction and extent of drying, a high yield of dimpled particles having different shapes including tetrahedra and cubes were obtained after oil initiated polymerization and dissolution of the host PS particles, as seen under SEM. The effects of TPM to PS particles size ratio, drying time, and other factors in relation to the yield of tetrahedral and cubic dimpled particles will be presented. Finally, fractionation techniques were used to obtain suspensions of uniform polyhedral particles of high purity.

  19. Constructing covalent interface in rubber/clay nanocomposite by combining structural modification and interlamellar silylation of montmorillonite.

    PubMed

    Zha, Chao; Wang, Wencai; Lu, Yonglai; Zhang, Liqun

    2014-11-12

    Strong interfacial interaction and nanodispersion are necessary for polymer nanocomposites with expectations on mechanical performance. In this work, montmorillonite (MMT) was first structurally modified by acid treatment to produce more silanol groups on the layer surface. This was followed by chemical modification of γ-methacryloxy propyl trimethoxysilane molecule (KH570) through covalent grafting with the silanol groups. (29)Si and (27)Al magic angle spinning (MAS) NMR results revealed the microstructural changes of MMT after acid treatment and confirmed the increase of silanol groups on acid-treated MMT surfaces. Thermogravimetric analysis indicated an increase in the grafted amount of organosilane on the MMT surface. X-ray diffraction (XRD) showed that the functionalization process changed the highly ordered stacking structure of the MMT mineral into a highly disordered structure, indicating successful grafting of organosilane to the interlayer surface of the crystalline sheets. The styrene-butadiene rubber (SBR)/MMT nanocomposites were further prepared by co-coagulating with SBR latex and grafted-MMT aqueous suspension. During vulcanization, a covalent interface between modified MMT and rubber was established through peroxide-radical-initiated reactions, and layer aggregation was effectively prevented. The SBR/MMT nanocomposites had highly and uniformly dispersed MMT layers, and the covalent interfacial interaction was finally achieved and exhibited high performance. PMID:25322875

  20. Preparation of inorganic-organic hybrid titania sol-gel nanocomposite films, and their dielectric properties

    NASA Astrophysics Data System (ADS)

    Kim, Hoon; Pramanik, Nimai Chand; Yeop Ahn, Bok; Seok, Sang Il

    2006-06-01

    Hybrid titania materials were prepared by a process involving the phase separation of TiO2 by hydrolysis and polycondensation from hybrids between titanium tetraisopropoxide (TTIP) and 3-(methacryloyloxy)propyl trimethoxysilane (MPTS) with excess acidic water at an elevated temperature (80 °C). The formation of TiO2 nanoparticles within the hybrid materials was studied as a function of the ageing time as well as the Ti/Si molar ratio. The crystalline phases of the TiO2 nanoparticles formed in situ within the inorganic-organic hybrid matrix were characterized by X-ray diffraction and Fourier transform infrared studies. The microstructures and the morphologies of thick films of the hybrid materials were studied using scanning and transmission electron microscopy, which showed the existence of nanocrystalline TiO2 within the crack-free hybrid matrix. The dielectric constants of the composites were found to be in the range 5.0-7.1, depending on the measuring frequency and the composite composition.

  1. Surface decoration of carbon nanosheets with amino-functionalized organosilica nanoparticles

    NASA Astrophysics Data System (ADS)

    Baikousi, M.; Dimos, K.; Bourlinos, A. B.; Zbořil, R.; Papadas, I.; Deligiannakis, Y.; Karakassides, M. A.

    2012-02-01

    Carbonaceous nanosheets decorated with amino-functionalized organosilica nanoparticles have been synthesized by a direct pyrolysis of betaine at 400 °C in air, followed by a simple surface treatment with ([3-(2-aminoethylamino) propyl]trimethoxysilane under reflux conditions. Both pristine and organosilica modified carbon nanosheets (OMCNs), were characterized by Fourier-transform infrared (FTIR), Raman, and electron paramagnetic resonance (EPR) spectroscopies, transmission electron microscopy and thermal analysis methods. The experimental data reveal a dramatic increase in the number of radical centers on the surface of the developed OMCN hybrid. The organosilica nanoparticles, ranging in size between 3 and 15 nm, are spherical and homogenously anchored on the surface of carbon nanosheets. The formation of Csbnd Osbnd Si bridges between carbon sheets and the organosilica nanoparticles has been supported by FTIR and EPR. These nanoparticles are bound to the nanosheet surface together with individual functional organosilane groups at a spacing of about 4 Å distance. The final hybrid is the complex nanosystem composed of 2D carbon nanosheets, spherical organosilica nanoparticles and immobilized amino organosilane molecules.

  2. Functionalization of PDMS modified and plasma activated two-component polyurethane coatings by surface attachment of enzymes

    NASA Astrophysics Data System (ADS)

    Kreider, Alexej; Richter, Katharina; Sell, Stephan; Fenske, Mandus; Tornow, Christian; Stenzel, Volkmar; Grunwald, Ingo

    2013-05-01

    This article describes a new strategy for coupling the enzyme horseradish peroxidase to a two-component polyurethane (2C-PUR) coating. A stable polymer conjugate was achieved by combining the enzyme and the 2C-PUR coating which was modified with poly(dimethylsiloxane) (PDMS), located at the surface. An atmospheric pressure plasma jet system was used to convert alkyl groups from the PDMS into polar silanol functionalities. This conversion was proven by X-ray photoelectron spectroscopy and dynamic contact angle measurements. In addition, the stability of the activated 2C-PUR surface containing silanol groups was determined by measuring the contact angle as a function of time. Compared to the non-modified 2C-PUR systems the one with PDMS displayed a higher stability over a time period over 28 h. In a silanization process the coating was treated with (3-aminopropyl) trimethoxysilane and the enzyme was subsequently immobilized to the coating via the cross linker glutaraldehyde to receive new biomimetic catalytic/enzymatic functions. The chemical immobilization (chemisorption) of the enzyme to the surface showed statistically significant higher biological activity as compared to references samples without using a cross linker (physisorption). The presented technique offers the opportunity to design new and smart multifunctional surface coatings which employ biomimetic capabilities.

  3. Investigation of Diffusion Characteristics through Microfluidic Channels for Passive Drug Delivery Applications

    PubMed Central

    Ghuman, Alyssa P.; Collins, Stephanie B.; Handa, Hitesh

    2016-01-01

    Microfluidics has many drug delivery applications due to the ability to easily create complex device designs with feature sizes reaching down to the 10s of microns. In this work, three different microchannel designs for an implantable device are investigated for treatment of ocular diseases such as glaucoma, age-related macular degeneration (AMD), and diabetic retinopathy. Devices were fabricated using polydimethylsiloxane (PDMS) and soft lithography techniques, where surface chemistry of the channels was altered using 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (PEG-silane). An estimated delivery rate for a number of common drugs was approximated for each device through the ratio of the diffusion coefficients for the dye and the respective drug. The delivery rate of the model drugs was maintained at a physiological condition and the effects of channel design and surface chemistry on the delivery rate of the model drugs were recorded over a two-week period. Results showed that the surface chemistry of the device had no significant effect on the delivery rate of the model drugs. All designs were successful in delivering a constant daily dose for each model drug. PMID:27313895

  4. Lysine adsorption on the silanized SiO 2-surface for immobilization of the estrogen receptor hER α

    NASA Astrophysics Data System (ADS)

    Cherkouk, C.; Rebohle, L.; Skorupa, W.

    2011-03-01

    We investigated the adsorption of the L-lysine (200 mmol) molecule to a silanized SiO 2 surface as a function of the pH value. The SSC (Spraying Spin Coating) method [Cherkouk et al., J. Colloid Interf. Sci. 337 (2009) 375-380] was applied to functionalize the SiO 2 surface by using the (3-aminopropyl)trimethoxysilane (APMS) as coupling agent with a NH 2 functional group. We adsorbed lysine molecules to the silane film for pH-values of 2.5, 7.5, 8.7, 9.5 and 13, which correspond to the di-cationic, cationic, zwitterinonic (pH 8.7 and 9.5) and the anionic charge state of lysine, respectively. The infrared spectroscopy is not suitable to investigate the system because the NH 3+ signal at 1600 cm -1 originating from the silane film overlaps with the infrared signal of the deprotonated carboxyl group of the lysine molecule. X-ray photoelectron spectroscopy (XPS) was used to measure the binding energies C 1s and N 1s as function of the pH value. This pH change affects the charge state which was fitted in the XPS spectra to obtain the optimal adsorption conditions at pH 7.5 of the lysine to the functionalized SiO 2 surface.

  5. Shear bond strength between autopolymerizing acrylic resin and Co-Cr alloy using different primers.

    PubMed

    Sanohkan, Sasiwimol; Urapepon, Somchai; Harnirattisai, Choltacha; Sirisinha, Chakrit; Sunintaboon, Panya

    2012-01-01

    This study aimed to examine the shear bond strength between cobalt chromium alloy and autopolymerizing acrylic resin using experimental primers containing 5, 10, and 15 wt% of 4-methacryloxyethyl trimellitic anhydride or 1, 2, and 3 wt% of 3-methacryloxypropyl-trimethoxysilane comparison to 5 commercial primers (ML primers, Alloy primer, Metal/Zirconia primer, Monobond S, and Monobond plus). Sixty alloy specimens were sandblasted and treated with each primer before bonded with an acrylic resin. The control group was not primed. The shear bond strengths were tested and statistically compared. Specimens treated with commercial primers significantly increased the shear bond strength of acrylic resin to cobalt chromium alloy (p<0.05). The highest shear bond strength was found in the Alloy primer group. Among experimental group, using 10 wt% of 4-methacryloxyethyl trimellitic anhydride -or 2 wt% of 3-methacryloxypropyltrimethoxysilane enhanced highest shear bond strength. The experimental and commercial primers in this study all improved bonding of acrylic resin to cobalt chromium alloy.

  6. Combinatorial materials research applied to the development of new surface coatings XVI: fouling-release properties of amphiphilic polysiloxane coatings.

    PubMed

    Stafslien, Shane J; Christianson, David; Daniels, Justin; VanderWal, Lyndsi; Chernykh, Andrey; Chisholm, Bret J

    2015-01-01

    High-throughput methods were used to prepare and characterize the fouling-release (FR) properties of an array of amphiphilic polysiloxane-based coatings possessing systematic variations in composition. The coatings were derived from a silanol-terminated polydimethylsiloxane, a silanol-terminated polytrifluorpropylmethylsiloxane (CF3-PDMS), 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane (TMS-PEG), methyltriacetoxysilane and hexamethyldisilazane-treated fumed silica. The variables investigated were the concentration of TMS-PEG and the concentration of CF3-PDMS. In general, it was found that the TMS-PEG and the CF3-PDMS had a synergist effect on FR properties with these properties being enhanced by combining both compounds into the coating formulations. In addition, reattached adult barnacles removed from coatings possessing both TMS-PEG and relatively high levels of CF3-PDMS displayed atypical base-plate morphologies. The majority of the barnacles removed from these coatings exhibited a cupped or domed base-plate as compared to the flat base-plate observed for the control coating that did not contain TMS-PEG or CF3-PDMS. Coating surface analysis using water contact angle measurements indicated that the presence of CF3-PDMS facilitated migration of TMS-PEG to the coating/air interface during the film formation/curing process. In general, coatings containing both TMS-PEG and relatively high levels of CF3-PDMS possessed excellent FR properties. PMID:25647177

  7. Application of Self-Assembled Monolayers to the Electroless Metallization of High Aspect Ratio Vias for Microelectronics

    NASA Astrophysics Data System (ADS)

    Bernasconi, R.; Molazemhosseini, A.; Cervati, M.; Armini, S.; Magagnin, L.

    2016-10-01

    All-wet electroless metallization of through-silicon vias (TSVs) with a width of 5 μm and a 1:10 aspect ratio was carried out. Immersion in a n-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPTMS) self-assembled monolayer (SAM) was used to enhance the adhesion between the metal film and substrate. Contact angle variation and atomic force microscopy were used to verify the formation of a SAM layer. A PdCl2 solution was later used to activate the silanized substrates, exploiting the affinity of the -NH3 functional group of AEAPTMS to palladium. A nickel-phosphorus-boron electroless bath was employed to deposit the first barrier layer onto silicon. The NiPB growth rate was evaluated on flat silicon wafers, while the structure of the coating obtained was investigated via glow discharge optical emission spectroscopy. Cross-sectional scanning electron microscope observations were carried out on metallized TSVs to characterize the NiPB seed, the Cu seed layer deposited with a second electroless step, and the Cu superfilling obtained with a commercial solution. Complete filling of TSV was achieved.

  8. Development of sol-gel icephobic coatings: effect of surface roughness and surface energy.

    PubMed

    Fu, Qitao; Wu, Xinghua; Kumar, Divya; Ho, Jeffrey W C; Kanhere, Pushkar D; Srikanth, Narasimalu; Liu, Erjia; Wilson, Peter; Chen, Zhong

    2014-12-10

    Sol-gel coatings with different roughness and surface energy were prepared on glass substrates. Methyl triethoxysilane (MTEOS), 3-Glycidyloxypropyl trimethoxysilane (GLYMO) and fluoroalkylsilane (FAS) were used to obtain a mechanically robust icephobic coating. Different amount of hydrophobic silica nano particles was added as fillers to introduce different roughness and surface energy to the coatings. The microstructure, roughness, and surface energy, together with elemental information and surface chemical state, were investigated at room temperature. The contact angle and sliding angle were measured at different temperatures to correlate the wetting behavior at low temperature with the anti-icing performance. The ice adhesion shear strength was measured inside an ice chamber using a self-designed tester. The factors influencing the ice adhesion were discussed, and the optimum anti-icing performance found in the series of coatings. It was found that lower surface energy leads to lower ice adhesion regardless of the roughness, while the roughness plays a more complicated role. The wetting behavior of the droplet on surface changes as temperature decreases. The anti-icing performance is closely related to the antiwetting property of the surfaces at subzero temperatures.

  9. Silica-based monolithic capillary columns modified by liposomes for characterization of analyte-liposome interactions by capillary liquid chromatography.

    PubMed

    Moravcová, Dana; Planeta, Josef; Wiedmer, Susanne K

    2013-11-22

    This study introduces a silica-based monolith in a capillary format (0.1 mm × 100 mm) as a support for immobilization of liposomes and its characterization in immobilized liposome chromatography. Silica-based monolithic capillary columns prepared by acidic hydrolysis of tetramethoxysilane in the presence of polyethylene glycol and urea were modified by (3-aminopropyl)trimethoxysilane, whereby amino groups were introduced to the monolithic surface. These groups undergo reaction with glutaraldehyde to form an iminoaldehyde, allowing covalent binding of pre-formed liposomes containing primary amino groups. Two types of phospholipid vesicles were used for column modification; these were 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphatidyl choline with and without 1,2-diacyl-sn-glycero-3-phospho-L-serine. The prepared columns were evaluated under isocratic separation conditions employing 20mM phosphate buffer at pH 7.4 as a mobile phase and a set of unrelated drugs as model analytes. The liposome layer on the synthesized columns significantly changed the column selectivity compared to the aminopropylsilylated monolithic stationary phase. Monolithic columns modified by liposomes were stable under the separation conditions, which proved the applicability of the suggested preparation procedure for the synthesis of capillary columns dedicated to study analyte-liposome interactions. The column efficiency originating from the silica monolith was preserved and reached, e.g., more than 120,000 theoretical plates/m for caffeine as a solute. PMID:23978749

  10. Interfacial Characterizations of a Nickel-Phosphorus Layer Electrolessly Deposited on a Silane Compound-Modified Silicon Wafer Under Thermal Annealing

    NASA Astrophysics Data System (ADS)

    Lai, Kuei-Chang; Wu, Pei-Yu; Chen, Chih-Ming; Wei, Tzu-Chien; Wu, Chung-Han; Feng, Shien-Ping

    2016-06-01

    Front-side metallization of a Si wafer was carried out using electroless deposition of nickel-phosphorus (Ni-P) catalyzed by polyvinylpyrrolidone-capped palladium nanoclusters (PVP-nPd). A 3-[2-(2-Aminoethylamino)ethylamino] propyl-trimethoxysilane (ETAS) layer was covalently bonded on the Si surface as bridge linker to the Pd cores of PVP-nPd clusters for improving adhesion between the Ni-P layer and the Si surface. To investigate the effects of an interfacial ETAS layer on the Ni silicide formation at the Ni-P/Si contact, the Ni-P-coated Si samples were thermally annealed via rapid thermal annealing (RTA) from 500°C to 900°C for 2 min. To compare with the ETAS sample, the sputtered Ni layer on Si and electroless Ni-P layer on ion-Pd-catalyzed Si (both are standard processes) were also investigated. The microstructural characterizations for the Ni-P or Ni layer deposited on the Si wafer were performed using x-ray diffractometer, scanning electron microscopy, and transmission electron microscopy. Our results showed that the ETAS layer acted as a barrier to slow the atomic diffusion of Ni toward the Si side. Although the formation of Ni silicides required a higher annealing temperature, the adhesion strength and contact resistivity measurements of annealed Ni-P/Si contacts showed satisfactory results, which were essential to the device performance and reliability during thermal annealing.

  11. Epoxidation of soybean oil catalyzed by peroxo phosphotungstic acid supported on modified halloysite nanotubes

    NASA Astrophysics Data System (ADS)

    Jiang, Junqing; Zhang, Yanwu; Yan, Liwei; Jiang, Pingkai

    2012-06-01

    {PO4[W(O)(O2)2]4}3- was supported onto modified halloysite nanotubes (HNTs) to prepare heterogeneous catalysts and these catalysts were applied in epoxidation of soybean oil. To enhance the cohesive force between {PO4[W(O)(O2)2]4}3- and HNTs, quaternary amino groups were anchored onto HNTs through silylation of N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and alkylation of amino groups. Further {PO4[W(O)(O2)2]4}3- was supported onto HNTs by ion exchange. The heterogeneous catalysts were characterized by FTIR, TGA, XRF and TEM-EDS. Then the catalytic behaviour to epoxidation of soybean oil was studied in detail. The results show that the introduction of phase transfer agent during preparation of the catalysts is very effective to improve catalytic activity and mechanical agitation combining with ultrasonic agitation is the best agitation way. The catalytic reactivity increased as reaction time increased. Moreover, the catalysts can be easily recovered from the reaction system by centrifugation as deposit and recycled three times without obviously decreasing the catalytic activity. Through re-exchange of {PO4[W(O)(O2)2]4}3-, the heterogeneous catalyst can be regenerated without catalytic activity loss.

  12. Bioadhesive film formed from a novel organic-inorganic hybrid gel for transdermal drug delivery system.

    PubMed

    Guo, Ruiwei; Du, Xiaoyan; Zhang, Rui; Deng, Liandong; Dong, Anjie; Zhang, Jianhua

    2011-11-01

    A novel organic-inorganic hybrid film-forming agent for TDDS was developed by a modified poly(vinyl alcohol) (PVA) gel using γ-(glycidyloxypropyl)trimethoxysilane (GPTMS) as an inorganic-modifying agent, poly(N-vinyl pyrrolidone) (PVP) as a tackifier and glycerol (GLY) as a plasticizer. The prepared gels can be applied to the skin by a coating method and in situ form very thin and transparent films with good performance, comfortable feel and cosmetic attractiveness. The key properties of the bioadhesive films produced from the hybrid gels were investigated and the results showed that the incorporation of appropriate GPTMS (GPTMS/(PVA+GPTMS) in the range of 20-30%) into the PVA matrix not only can significantly enhance mechanical strength and skin adhesion properties of the resultant film, but also can decrease the crystalline regions of PVA and hence facilitate the diffusion of water vapor and drug. Furthermore, the investigations into in vivo skin irritation suggested the films caused non-irritation to skin after topical application for 120 h. In conclusion, the bioadhesive films formed from organic-inorganic hybrid gels possessed very good qualities for application on the skin and may provide a promising formulation for TDDS, especially when the patient acceptability from an aesthetic perspective of the dosage form is a prime consideration. PMID:21723945

  13. Nicalon/siliconoxycarbide ceramic composites

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Gyekenyesi, John Z.; Conroy, Paula J.; Rivera, Ann L.

    1990-01-01

    A series of silsesquioxane copolymers was synthesized by acid hydrolysis and condensation of trimethoxysilanes of the form RSi(OCH3)3, where R = methyl or phenyl. By varying pH, water/methoxy and methyl/phenyl ratios, the molecular structure, polymer rheology and ceramic composition can be controlled. The polymers form an amorphous siliconoxycarbide on pyrolysis. Composites of Nicalon/siliconoxycarbide were fractured in four-point flexure and in tension to evaluate the influence of matrix composition, final fabrication temperature and use of filler on composite mode of failure, modulus, strain capability and strength. Incorporation of filler was found to increase matrix compressive strength. Employment of processing temperatures of 1375 to 1400 C enhanced strain to failure and reduced the tendency toward brittle fracture. Mixed mode (compression/shear and tension/shear) failures were observed in flexural samples processed to the higher temperatures, giving rise to nonlinear stress-strain curves. Tensile samples pyrolyzed to 1400 C showed linear-elastic behavior and failed by fracture of fiber bundles. Matrix material was found to be adherent to the fiber surface after failure. These results demonstrate the need for tensile testing to establish composite behavior.

  14. RGDS- and TAT-Conjugated Upconversion of NaYF4:Yb(3+)/Er(3+)&SiO2 Nanoparticles: In Vitro Human Epithelioid Cervix Carcinoma Cellular Uptake, Imaging, and Targeting.

    PubMed

    Kostiv, Uliana; Kotelnikov, Ilya; Proks, Vladimír; Šlouf, Miroslav; Kučka, Jan; Engstová, Hana; Ježek, Petr; Horák, Daniel

    2016-08-10

    Starting NaYF4:Yb(3+)/Er(3+) nanoparticles with size tuned from 24 to 33 nm were prepared by high-temperature coprecipitation of lanthanide chlorides in high-boiling organic solvents. To enhance colloidal stability in aqueous medium, an aminosilica shell was introduced on the surface by hydrolysis and condensation of tetramethyl orthosilicate and (3-aminopropyl)trimethoxysilane using a reverse microemulsion technique; to form alkyne groups, reaction with 4-pentynoic acid followed. Finally, the cell adhesive and cell penetrating azidopentanoyl-GGGRGDSGGGY-NH2 (RGDS) and azidopentanoyl-GGGRKKRRQRRR-NH2 (TAT) peptides were conjugated to the upconversion particles via Cu(I)-catalyzed alkyne-azide cycloaddition. The concentrations of the peptides bound to the nanoparticle surfaces and amount of adsorbed residual Cu(I) catalyst were determined using an (125)I-radiolabeled RGDS peptide and a (64)Cu(I)-doped catalyst, respectively. Targeting and uptake of the RGDS- and TAT-conjugated NaYF4:Yb(3+)/Er(3+)&SiO2 nanoparticles by human cervix carcinoma HeLa cells were monitored by confocal microscopy. RGDS-conjugated nanoparticle probes were mainly localized on the cell plasma membrane due to specific binding of the peptide to the corresponding integrins. In contrast, the TAT-conjugated nanoparticles were able to cross the cell membrane and accumulate in the cell cytoplasm. Thus, this new peptide bioconjugation approach supported both extra- and intracellular nanoparticle uptake, enabling targeting and imaging of the specific tumor phenotypes. PMID:27428386

  15. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10-4 S cm-1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  16. Degradation of the electrospun silica nanofiber in a biological medium for primary hippocampal neuron – effect of surface modification

    PubMed Central

    Feng, Z Vivian; Chen, Wen Shuo; Keratithamkul, Khomson; Stoick, Michael; Kapala, Brittany; Johnson, Eryn; Huang, An-Chi; Chin, Ting Yu; Chen-Yang, Yui Whei; Yang, Mong-Lin

    2016-01-01

    In this work, silica nanofibers (SNFs) were prepared by an electrospinning method and modified with poly-d-lysine (PDL) or (3-aminopropyl) trimethoxysilane (APTS) making biocompatible and degradable substrates for neuronal growth. The as-prepared SNF, modified SNF-PDL, and SNF-APTS were evaluated using scanning electron microscopy, nitrogen adsorption/desorption isotherms, contact angle measurements, and inductively coupled plasma atomic emission spectroscopy. Herein, the scanning electron microscopic images revealed that dissolution occurred in a corrosion-like manner by enlarging porous structures, which led to loss of structural integrity. In addition, covalently modified SNF-APTS with more hydrophobic surfaces and smaller surface areas resulted in significantly slower dissolution compared to SNF and physically modified SNF-PDL, revealing that different surface modifications can be used to tune the dissolution rate. Growth of primary hippocampal neuron on all substrates led to a slower dissolution rate. The three-dimensional SNF with larger surface area and higher surface density of the amino group promoted better cell attachment and resulted in an increased neurite density. This is the first known work addressing the degradability of SNF substrate in physiological conditions with neuron growth in vitro, suggesting a strong potential for the applications of the material in controlled drug release. PMID:27013873

  17. Mesochanneled hierarchically porous aluminosiloxane aerogel microspheres as a stable support for pH-responsive controlled drug release.

    PubMed

    Vazhayal, Linsha; Talasila, Sindhoor; Abdul Azeez, Peer Mohamed; Solaiappan, Ananthakumar

    2014-09-10

    The molecular-scale self-assembly of a 3D aluminosiloxane (Al-O-Si) hybrid gel network was successfully performed via the cocondensation of hydrolyzed alumina (AlOOH) and (3-aminopropyl)trimethoxysilane (APS). It was transformed into a microspherical aerogel framework of Al-O-Si containing mesochannels with tunable hierarchically bimodal meso/macroporosities by a subcritical drying technique. Good homogeneity of AlOOH and APS brought during the synthesis guaranteed a uniform distribution of two metal oxides in a single body. A systematic characterization of the aerogel support was carried out using FTIR, SEM, TEM, nitrogen adsorption/desorption analysis, WAXS, SAXS, and ξ-potential measurement in order to explore the material for drug uptake and release. The drug loading and release capacity and chemical stability of an aluminosiloxane aerogel were studied using two nonsteroidal antiinflammatory drugs, ibuprofen and aspirin. A comprehensive evaluation of the aluminosiloxane aerogel with ordered mesoporous MCM-41 was also performed. Aerogel supports showed a high drug loading capacity and a pH-responsive controlled-release property compared to MCM-41. Meanwhile, kinetic modeling studies indicate that the drug releases with a zero-order profile following the Korsmeyer-Peppas model. The biocompatibility of aluminosiloxane aerogels was established via ex vivo and in vivo studies. We also outline the use of aluminosiloxane aerogel as a support for a possible 3D matrix for an osteoconductive structure for bone tissue engineering.

  18. Preparation and properties of acrylic resin coating modified by functional graphene oxide

    NASA Astrophysics Data System (ADS)

    Dong, Rui; Liu, Lili

    2016-04-01

    To improve the dispersion and the strength of filler-matrix interface in acrylic resin, the functional graphene oxide (FGO) was obtained by surface modification of graphene oxide (GO) by γ-methacryloxypropyl trimethoxysilane (KH-570) and then the acrylic nanocomposites containing different loadings of GO and FGO were prepared. The structure, morphology and dispersion/exfoliation of the FGO were characterized by XRD, FT-IR, Raman, XPS, SEM and TEM. The results demonstrated that the KH-570 was successfully grafted onto the surface of GO sheets. Furthermore, the corresponding thermal, mechanical and chemical resistance properties of the acrylic nanocomposites filled with the FGO were studied and compared with those of neat acrylic and GO/acrylic nanocomposites. The results revealed that the loading of FGO effectively enhanced various properties of acrylic resin. These findings confirmed that the dispersion and interfacial interaction were greatly improved by incorporation of FGO, which might be the result of covalent bonds between the FGO and the acrylic matrix. This work demonstrates an in situ polymerization method to construct a flexible interphase structure, strong interfacial interaction and good dispersion of FGO in acrylic nanocomposites, which can reinforce the polymer properties and be applied in research and industrial areas.

  19. Application of Self-Assembled Monolayers to the Electroless Metallization of High Aspect Ratio Vias for Microelectronics

    NASA Astrophysics Data System (ADS)

    Bernasconi, R.; Molazemhosseini, A.; Cervati, M.; Armini, S.; Magagnin, L.

    2016-07-01

    All-wet electroless metallization of through-silicon vias (TSVs) with a width of 5 μm and a 1:10 aspect ratio was carried out. Immersion in a n-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPTMS) self-assembled monolayer (SAM) was used to enhance the adhesion between the metal film and substrate. Contact angle variation and atomic force microscopy were used to verify the formation of a SAM layer. A PdCl2 solution was later used to activate the silanized substrates, exploiting the affinity of the -NH3 functional group of AEAPTMS to palladium. A nickel-phosphorus-boron electroless bath was employed to deposit the first barrier layer onto silicon. The NiPB growth rate was evaluated on flat silicon wafers, while the structure of the coating obtained was investigated via glow discharge optical emission spectroscopy. Cross-sectional scanning electron microscope observations were carried out on metallized TSVs to characterize the NiPB seed, the Cu seed layer deposited with a second electroless step, and the Cu superfilling obtained with a commercial solution. Complete filling of TSV was achieved.

  20. Molecularly imprinted polymer-sol-gel tablet toward micro-solid phase extraction: I. Determination of methadone in human plasma utilizing liquid chromatography-tandem mass spectrometry.

    PubMed

    El-Beqqali, Aziza; Abdel-Rehim, Mohamed

    2016-09-14

    In the present work molecularly imprinted sol-gel tablet (MIP-Tablet) was prepared. The MIP-sol-gel was prepared as a thin layer on polyethylene material in a tablet form. Methadone-d9 was selected as the template and 3-(propylmethacrylate)-trimethoxysilane was used as precursor. MIP-Tablet was applied for micro-solid phase extraction (μ-SPE). The MIP-Tablet was used for the determination of methadone in human plasma samples utilizing liquid chromatography-tandem mass spectrometry; and each tablet could be used twenty times. The extraction time was 10 min while desorption time was 6 min. Factors affecting the extraction efficiency such as desorption solvents, sample pH, salt addition, extraction time, desorption time and adsorption capacity were investigated. The calibration curves were obtained within the range of 5-5000 ng/mL using methadone in human plasma samples. The coefficients of determination (r(2)) values were ≥0.999 for all runs and the extraction recovery was >80%. The accuracy values for quality control samples varied from +3.6 to +9.7% and the inter-day precision (RSD %) values were ranged from 5.0 to 8.0%. The limit of detection was 1.0 ng/mL and the lower limit of quantification was 5 ng/mL utilizing methadone in human plasma samples. PMID:27566346

  1. Functionalized hexagonal boron nitride nano-coatings for protection of transparent plastics

    NASA Astrophysics Data System (ADS)

    Van Tran, Thu; Usta, Aybala; Asmatulu, Ramazan

    2016-04-01

    Nanocoating is the result of a coating application of nanomaterials to build a consistent network of molecules in a paint to protect the surfaces of various materials and devices. Hexagonal Boron Nitride (h-BN) is in two dimensional form with excellent thermal, mechanical and chemical properties. These BN nanocoatings are also a thermally insulating material for heat management. After adding functionalized h-BNs into paints or other coatings, they will absorb the harmful UV part of sunlight and prevent coating against the environmental degradations. The impacts of the environmental factors on the coatings can be substantially eliminated. In the present study, h-BNs were modified with [2-(2-Aminoethylamino) propyl] trimethoxysilane and uniformly dispersed into the polyurethane coatings with different amounts, such as 0.1, 0.2, 0.4, and 0.8wt% to increase hardness and water resistance, and decrease the UV degradation level of coatings and transparent plastics. The prepared samples were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), UV-Vis Spectroscopy, Scanning Electron Microscope (SEM), Water Contact Angle, and Differential Scanning Calorimeter (DSC). The test results showed that the nanocoatings with functionalized h-BN provided excellent physical and chemical behaviors against the UV and other physical degradations on the substrates.

  2. A core-shell surface magnetic molecularly imprinted polymers with fluorescence for λ-cyhalothrin selective recognition.

    PubMed

    Gao, Lin; Wang, Jixiang; Li, Xiuying; Yan, Yongsheng; Li, Chunxiang; Pan, Jianming

    2014-11-01

    In this study, we report here a general protocol for making core-shell magnetic Fe3O4/SiO2-MPS/MIPs (MPS = 3-(methacryloxyl) propyl trimethoxysilane, MIPs = molecularly imprinted polymers, Fe3O4/SiO2-MPS as core, MIPs as shell) via a surface molecular imprinting technique for optical detection of trace λ-cyhalothrin. The fluorescent molecularly imprinted polymer shell was first prepared by copolymerization of acrylamide with a small quantity of allyl fluorescein in the presence of λ-cyhalothrin to form recognition sites without doping. The magnetic Fe3O4/SiO2-MPS/MIPs exhibited paramagnetism, high fluorescence intensity, and highly selective recognition. Using fluorescence quenching as a detecting tool, Fe3O4/SiO2-MPS/MIPs were successfully applied to selectively and sensitively detect λ-cyhalothrin, and a linear relationship could be obtained covering a wide concentration range of 0-50 nM with a correlation coefficient of 0.9962 described by the Stern-Volmer equation. The experimental results of practical detection revealed that magnetic Fe3O4/SiO2-MPS/MIPs as an attractive recognition element was satisfactory for determination of trace λ-cyhalothrin in honey samples. This study, therefore, demonstrated the potential of MIPs for detection of λ-cyhalothrin in food. PMID:25200071

  3. Synthesis and properties of side-chain-type ion exchange membrane PEEK-g-StSO 3Na for bipolar membranes

    NASA Astrophysics Data System (ADS)

    Huang, Xuehong; Huang, Dengbin; Ou, Xiaojuan; Ding, Fuchuan; Chen, Zhen

    2012-01-01

    Side-chain-type ion exchange membranes (PEEK-g-StSO3Na) were prepared by grafting poly (ether ether ketone) (PEEK) containing propenyl groups with sodium sulfonic styrene (StSO3Na) and KH570. PEEK was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4‧-difluorobenzophenone, bisphenol A and diallylbisphenol A. The synthesized copolymers with the -SO3Na group on the side chain of polymers possessed high molecular weights. The cross-linking reaction was carried out through a sol-gel reaction of the trimethoxysilane group. The copolymer membranes exhibited excellent mechanical properties due to their aromatic structure extending through the backbone and flexible StSO3Na aliphatic chains. The ion exchange capacities (IECs) of the membranes ranged from 2.27 to 2.50 mmol g-1 and the water content ranged from 107.2 to 126.1%, with both parameters increasing with StSO3Na grafting degree. The H+ permeability of copolymer membranes increased with increasing IEC, reaching value above 0.3056 mol/L at 2 h, which is higher than that of Nafion® 117 at the same measurement condition. They displayed reasonably high H+ permeability due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water occupation, and the lower AC impedance of the bipolar membrane.

  4. Thermoresponsive mesoporous silica nanoparticles as a carrier for skin delivery of quercetin.

    PubMed

    Ugazio, Elena; Gastaldi, Lucia; Brunella, Valentina; Scalarone, Dominique; Jadhav, Sushilkumar A; Oliaro-Bosso, Simonetta; Zonari, Daniele; Berlier, Gloria; Miletto, Ivana; Sapino, Simona

    2016-09-10

    Recently, mesoporous silica nanoparticles (MSNs) have emerged as promising drug delivery systems able to preserve the integrity of the carried substance and/or to selectively reach a target site; however, they have rarely been explored for skin application. In this study, thermoresponsive MSNs, designed to work at physiologic cutaneous temperature, are proposed as innovative topical carriers for quercetin (Q), a well-known antioxidant. The thermosensitive nanoparticles were prepared by functionalizing two different types of matrices, with pore size of 3.5nm (MSNsmall) and 5.0nm (MSNbig), carrying out a free radical copolymerization of N-isopropylacrylamide (NIPAM) and 3-(methacryloxypropyl)trimethoxysilane (MPS) inside the mesopores. The obtained copolymer-grafted MSNs (copoly-MSNs) were physico-chemically characterized and their biocompatibility was attested on a human keratinocyte cell line (HaCaT). The release profiles were assessed and the functional activity of Q, free or loaded, was evaluated in terms of antiradical and metal chelating activities. Ex vivo accumulation and permeation through porcine skin were also investigated. The characterization confirmed the copolymer functionalization of the MSNs. In addition, both the bare and functionalized silica matrices were found to be biocompatible. Among the copolymer-grafted complexes, Q/copoly-MSNbig exhibited more evident thermoresponsive behavior proving the potential of these thermosensitive systems for advanced dermal delivery. PMID:27421910

  5. Silane modified starch for compatible reactive blend with poly(lactic acid).

    PubMed

    Jariyasakoolroj, Piyawanee; Chirachanchai, Suwabun

    2014-06-15

    A reactive blend of poly(lactic acid) (PLA) and a surface modified starch by silane coupling agent to achieve compatibility is proposed. A detailed structural analysis by using (1)H-(1)H TOCSY NMR spectrum clarifies, for the first time, that chloropropyl trimethoxysilane (CPMS) forms covalent bonds with starch during starch modification and consequently forms covalent bonds with PLA in the step of blending to produce a reactive blend of PLA and CP-starch. The CP-starch covalently bound with PLA provides the compatibility between PLA and starch and also plays the role as nucleating agent as identified from a significant increase of degree of crystallinity (as high as 10-15 times), as well as induces chain mobility, as identified from a slight decrease in glass transition temperature (∼5-10°C). The PLA/CP-starch film performed as well as neat PLA with slight increases in tensile strength and elongation at break, as compared to other PLA/silane modified starch films.

  6. Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu3+ red phosphor with enhanced quantum yield

    NASA Astrophysics Data System (ADS)

    Jain, Akhil; Hirata, G. A.; Farías, M. H.; Castillón, F. F.

    2016-02-01

    We report the surface modification of nanocrystalline Gd2O3:Eu3+ phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu3+ nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

  7. Preparation and properties of UV-cured acrylated silane intercalated polymer/LDH nanocomposite

    SciTech Connect

    Yuan, Yan; Shi, Wenfang

    2011-01-15

    A novel UV-cured polymer/layered double hydroxide (LDH) nanocomposite was prepared by modifying the LDH with sodium dodecyl sulfate (SDS) and [3-(methyl-acroloxy)propyl]trimethoxysilane (KH570) followed by UV irradiation after blended into a acrylate system. From the XRD analyses, the SDS-modified LDH-DS presented the basal spacing of 2.67 nm, whereas the further KH570-intercalated LDH-KH showed a slight decrease to 2.41 nm. After UV irradiated the exfoliated microstructure was formed, and observed by TEM and HR-TEM, showing the fine dispersion and random orientation of LDH in the polymer matrix. The storage modulus and glass transition temperature of the nanocomposite containing 5% LDH-KH increased to 47.5 MPa and 67.8 {sup o}C, respectively, from 39.7 MPa and 66 {sup o}C of the pure polymer from DMTA measurements. The tensile strength and Persoz hardness were enhanced to 10.6 MPa and 111 s, respectively, from 7.7 MPa and 85 s of the pure polymer.

  8. Modification of TiO₂ electrode with organic silane interposed layer for high-performance of dye-sensitized solar cells.

    PubMed

    Sewvandi, Galhenage A; Tao, Zhuoqi; Kusunose, Takafumi; Tanaka, Yasuhiro; Nakanishi, Shunsuke; Feng, Qi

    2014-04-23

    Back electron transfer from the TiO2 electrode surface to the electrolyte is the main reason behind the low-open circuit potential (Voc) and the low-fill factor (FF) of the dye-sensitized solar cells (DSSCs). Modifications to the TiO2 electrode, fabricated using {010}-faceted TiO2 nanoparticles with six different kinds of silane, are reported to decrease the back electron transfer on the TiO2 surface. The effect of alkyl chain length of hydrocarbon silanes and fluorocarbon silanes on adsorption parameters of surface coverage and adsorption constant, interfacial resistance, and photovoltaic performances were investigated. Adsorption isotherms, impedance analysis, and photovoltaic measurements were used as the investigation techniques. The reduction of back electron transfer depended on the TiO2 surface coverage by silane, alkyl chain length, and the molecular structure of the silane. Even though Voc and FF were improved, significant reduction in short-circuit photocurrent density (Jsc) was observed after silanization because of desorption of dye during silanization. A new approach, sequential adsorption process of silane and dye, was introduced to enhance Voc and FF without lowering Jsc. Heptadecafluorodecyl trimethoxy-silane showed the highest coverage on the surface of the TiO2 and had the highest effect on the performance improvement of the DSSC, where Voc, FF, and efficiency (η) were improved by 22, 8.0, and 22%, respectively.

  9. Application of a nanostructured platform and imprinted sol-gel film for determination of chlorogenic acid in food samples.

    PubMed

    Ribeiro, Carla M; Miguel, Eliane M; Silva, Jonadab Dos S; Silva, Cristian B da; Goulart, Marília O F; Kubota, Lauro T; Gonzaga, Fabiano B; Santos, Wilney J R; Lima, Phabyanno R

    2016-08-15

    Chlorogenic acid (CGA) is a polyphenol derivative that widely exists in higher plants like fruits, vegetables, black teas, and some traditional Chinese medicines. In this work, we have proposed a sensitive and selective electrochemical sensor for detection of CGA. The sensor was based on a glassy carbon electrode (GCE) modified with a functional platform by grafting vinyltrimethoxysilane (VTMS) in multi-walled carbon nanotubes (MWCNTs) and covered by a molecularly imprinted siloxane (MIS) film prepared using the sol-gel process. The VTMS was grafted onto the surface of the MWCNTs via in situ free radical polymerization. The MIS was obtained from the acid-catalyzed hydrolysis/condensation of a solution consisting of tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS), (3-aminopropyl)trimethoxysilane (APTMS), and CGA as a template molecule. The modification procedure was evaluated by differential pulse voltammetry (DPV) and scanning electron microscopy (SEM). Under optimized operational conditions, a linear response was obtained covering a concentration ranging from 0.08μmolL(-1) to 500μmolL(-1) with a detection limit (LOD) of 0.032μmolL(-1). The proposed sensor was applied to CGA determination in coffee, tomato, and apple samples with recoveries ranging from 99.3% to 108.6%, showing a promising potential application in food samples. Additionally, the imprinted sensor showed a significantly higher affinity for target CGA than the non-imprinted siloxane (NIS) sensor. PMID:27260443

  10. Degradation of the electrospun silica nanofiber in a biological medium for primary hippocampal neuron - effect of surface modification.

    PubMed

    Feng, Z Vivian; Chen, Wen Shuo; Keratithamkul, Khomson; Stoick, Michael; Kapala, Brittany; Johnson, Eryn; Huang, An-Chi; Chin, Ting Yu; Chen-Yang, Yui Whei; Yang, Mong-Lin

    2016-01-01

    In this work, silica nanofibers (SNFs) were prepared by an electrospinning method and modified with poly-d-lysine (PDL) or (3-aminopropyl) trimethoxysilane (APTS) making biocompatible and degradable substrates for neuronal growth. The as-prepared SNF, modified SNF-PDL, and SNF-APTS were evaluated using scanning electron microscopy, nitrogen adsorption/desorption isotherms, contact angle measurements, and inductively coupled plasma atomic emission spectroscopy. Herein, the scanning electron microscopic images revealed that dissolution occurred in a corrosion-like manner by enlarging porous structures, which led to loss of structural integrity. In addition, covalently modified SNF-APTS with more hydrophobic surfaces and smaller surface areas resulted in significantly slower dissolution compared to SNF and physically modified SNF-PDL, revealing that different surface modifications can be used to tune the dissolution rate. Growth of primary hippocampal neuron on all substrates led to a slower dissolution rate. The three-dimensional SNF with larger surface area and higher surface density of the amino group promoted better cell attachment and resulted in an increased neurite density. This is the first known work addressing the degradability of SNF substrate in physiological conditions with neuron growth in vitro, suggesting a strong potential for the applications of the material in controlled drug release. PMID:27013873

  11. Enhancing the biological activity of chitosan and controlling the degradation by nanoscale interaction with bioglass.

    PubMed

    Ravarian, Roya; Craft, Michaela; Dehghani, Fariba

    2015-09-01

    A nonuniform degradation of physical mixture of organic-inorganic biomaterials increases their risk of failure. In this study a chemical bonding between chitosan and bioglass was used as an alternative product to address this issue. To prepare a homogenous composite, chitosan was functionalized with γ-glycidoxypropyl trimethoxysilane and chemically bonded with bioglass during sol-gel method. The gelation time of these hybrids samples was optimized by varying parameters such as composition of chitosan and temperature. It was shown that gelation time was reduced from 7 days for pure bioglass at 25°C to less than six minutes at 70°C for chitosan 40 vol % bioglass hybrid. Furthermore, the enzymatic degradation after 4 weeks was decreased from 80% mass loss for pure chitosan to 32% for chitosan 40 vol % bioglass hybrid. The results of in vitro study demonstrated that the presence of nanoscale interaction enhanced the bioactivity of chitosan. Additionally, hybrid scaffolds were fabricated with pore sizes in the range of 200-400 µm. These scaffolds were prepared by the addition of sodium bicarbonate during sol-gel method as a gas foaming agent and a neutralizer that resulted in decreasing the gelation time of hybrids to less than three minutes. The hybrids fabricated in this study possessed superior characteristics compared to chitosan, also physical mixture of chitosan-bioglass and are promising alternatives for bone tissue engineering applications. PMID:25690303

  12. Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu(3+) red phosphor with enhanced quantum yield.

    PubMed

    Jain, Akhil; Hirata, G A; Farías, M H; Castillón, F F

    2016-02-12

    We report the surface modification of nanocrystalline Gd2O3:Eu(3+) phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu(3+) nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications. PMID:26684579

  13. Monomolecular layers and thin films of silane coupling agents by vapor-phase adsorption on oxidized aluminum

    SciTech Connect

    Kurth, D.G.; Bein, T.

    1992-08-06

    Thin films of tetraethoxysilane [TEOS], (3-bromopropyl)trimethoxysilane [BPS], trimethoxyvinylsilane [VS], and 3-(trimethoxysilyl) propyl methacrylate [TPM] on oxidized aluminum surfaces have been investigated by reflection-absorption FTIR spectroscopy, ellipsometry, contact angle, and quartz crystal microbalance (QCM) measurements. Gravimetric measurements with the QCM can reveal quantitative aspects of adsorption and film formation, even for films as thin as monolayers. Adsorption of these silane coupling agents from solution typically produces multilayer films. Vapor-phase adsorption of TEOS and TPM at room temperature results in monomolecular layers. The coupling agents VS and BPS require additional heating after the vapor-phase adsorption to initiate the hydrolysis and condensation reactions necessary for the surface attachment, which produces one to three layers. For vapor adsorbed films a packing density of 4-7 molecules/nm{sup 2} was found. The data strongly suggest that the organic moieties in several of these films have a preferential orientation on the surface; they can be viewed as two-dimensional, oligomeric siloxane networks with oriented organic chains. Subsequent heating of TPM films results in structural rearrangements; heating of TEOS results in complete condensation to SiO{sub 2} films. 43 refs., 6 figs., 4 tabs.

  14. Simple surface modification of a titanium alloy with silanated zwitterionic phosphorylcholine or sulfobetaine modifiers to reduce thrombogenicity

    PubMed Central

    Ye, Sang-Ho; Johnson, Carl A.; Woolley, Joshua R.; Murata, Hironobu; Gamble, Lara J.; Ishihara, Kazuhiko; Wagner, William R.

    2011-01-01

    Thrombosis and thromboembolism remain problematic for a large number of blood contacting medical devices and limit broader application of some technologies due to this surface bioincompatibility. In this study we focused on the covalent attachment of zwitterionic phosphorylcholine (PC) or sulfobetaine (SB) moieties onto a TiAl6V4 surface with a single step modification method to obtain a stable blood compatible interface. Silanated PC or SB modifiers (PCSi or SBSi) which contain an alkoxy silane group and either PC or SB groups were prepared respectively from trimethoxysilane and 2-methacryloyloxyethyl phosphorylcholine (MPC) or N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SMDAB) monomers by a hydrosilylation reaction. A cleaned and oxidized TiAl6V4 surface was then modified with the PCSi or SBSi modifiers by a simple surface silanization reaction. The surface was assessed with x-ray photoelectron spectroscopy (XPS), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and contact angle goniometry. Platelet deposition and bulk phase activation were evaluated following contact with anticoagulated ovine blood. XPS results verified successful modification of the PCSi or SBSi modifiers onto TiAl6V4 based on increases in surface phosphorous or sulfur respectively. Surface contact angles in water decreased with the addition of hydrophilic PC or SB moieties. Both the PCSi and SBSi modified TiAl6V4 surfaces showed decreased platelet deposition and bulk phase platelet activation compared to unmodified TiAl6V4 and control surfaces. This single step modification with PCSi or SBSi modifiers offers promise for improving the surface hemocompatibility of TiAl6V4 and is attractive for its ease of application to geometrically complex metallic blood contacting devices. PMID:20547042

  15. Organic-inorganic hybrid polymer electrolytes based on polyether diamine, alkoxysilane, and trichlorotriazine: Synthesis, characterization, and electrochemical applications

    NASA Astrophysics Data System (ADS)

    Saikia, Diganta; Wu, Cheng-Gang; Fang, Jason; Tsai, Li-Duan; Kao, Hsien-Ming

    2014-12-01

    A new type of highly conductive organic-inorganic hybrid polymer electrolytes has been synthesized by the reaction of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), 2,4,6-trichloro-1,3,5-triazine and alkoxysilane precursor 3-(glycidyloxypropyl)trimethoxysilane, followed by doping of LiClO4. The 13C and 29Si solid-sate NMR results confirm the successful synthesis of the organic-inorganic hybrid structure. The solid hybrid electrolyte thus obtained exhibits a maximum ionic conductivity of 1.6 × 10-4 S cm-1 at 30 °C, which is the highest among the organic-inorganic hybrid electrolytes. The hybrid electrolytes are electrochemically stable up to 4.2 V. The prototype electrochromic device with such a solid hybrid electrolyte demonstrates a good coloration efficiency value of 183 cm2 C-1 with a cycle life over 200 cycles. For the lithium-ion battery test, the salt free solid hybrid membrane is swelled with a LiPF6-containing electrolyte solution to reach an acceptable ionic conductivity value of 6.5 × 10-3 S cm-1 at 30 °C. The battery cell carries an initial discharge capacity of 100 mAh g-1 at 0.2C-rate and a coulombic efficiency of about 95% up to 30 cycles without the sign of cell failure. The present organic-inorganic hybrid electrolytes hold promise for applications in electrochromic devices and lithium ion batteries.

  16. Multifunctional nanosheets based on folic acid modified manganese oxide for tumor-targeting theranostic application

    NASA Astrophysics Data System (ADS)

    Hao, Yongwei; Wang, Lei; Zhang, Bingxiang; Zhao, Hongjuan; Niu, Mengya; Hu, Yujie; Zheng, Cuixia; Zhang, Hongling; Chang, Junbiao; Zhang, Zhenzhong; Zhang, Yun

    2016-01-01

    It is highly desirable to develop smart nanocarriers with stimuli-responsive drug-releasing and diagnostic-imaging functions for cancer theranostics. Herein, we develop a reduction and pH dual-responsive tumor theranostic platform based on degradable manganese dioxide (MnO2) nanosheets. The MnO2 nanosheets with a size of 20-60 nm were first synthesized and modified with (3-Aminopropyl) trimethoxysilane (APTMS) to get amine-functionalized MnO2, and then functionalized by NH2-PEG2000-COOH (PEG). The tumor-targeting group, folic acid (FA), was finally conjugated with the PEGylated MnO2 nanosheets. Then, doxorubicin (DOX), a chemotherapeutic agent, was loaded onto the modified nanosheets through a physical adsorption, which was designated as MnO2-PEG-FA/DOX. The prepared MnO2-PEG-FA/DOX nanosheets with good biocompatibility can not only efficiently deliver DOX to tumor cells in vitro and in vivo, leading to enhanced anti-tumor efficiency, but can also respond to a slightly acidic environment and high concentration of reduced glutathione (GSH), which caused degradation of MnO2 into manganese ions enabling magnetic resonance imaging (MRI). The longitudinal relaxation rate r 1 was 2.26 mM-1 s-1 at pH 5.0 containing 2 mM GSH. These reduction and pH dual-responsive biodegradable nanosheets combining efficient MRI and chemotherapy provide a novel and promising platform for tumor-targeting theranostic application.

  17. Remarkably enhanced thermal stability of an irradiation-crosslinked ethylene-octene copolymer by incorporation of a novel organic/inorganic hybrid nano-sensitizer

    NASA Astrophysics Data System (ADS)

    Zhang, Sideng; Sun, Bin; Jiang, Xiaoze; Li, Lili; Meng, Zhouqi; Zhu, Meifang

    2015-01-01

    We report a novel method to improve the anti-thermal-deformation performance of an ethylene-octene copolymer (POE) using vinyl functionalized silica nanoparticles (M-SiO2) as a sensitizer to enhance radiation-induced crosslinking. The M-SiO2 nanoparticles were prepared by coupling commercially available silica nanoparticles with KH570 (γ-methacryloxypropyl-trimethoxysilane, γ-MPS) and were blended with POE by melt blending. Then, the mixture was irradiated with γ-rays under a nitrogen atmosphere to form the crosslinked POE/M-SiO2 nanocomposite. The novel nanocomposites were characterized, and the results showed that the gel fraction was proportional to the content of M-SiO2 in the loading range studied in this work. When the content of M-SiO2 was 10 wt%, the gel fraction of POE was increased by approximately 50%, and the softening temperature (T0.5D) increased from 104.4 °C to 224.6 °C after a 120 kGy dose of radiation. The tensile strength of the POE/M-SiO2-10 nanocomposite was better than that of the neat POE copolymer irradiated with an absorption dose up to 100 kGy. In contrast, the elongation of the POE/M-SiO2-10 nanocomposite was lower than that of the neat POE irradiated under the same conditions, due to the increased degree of crosslinking by radiation. These results clearly demonstrated that the use of M-SiO2 as an irradiation sensitizer effectively enhanced the radiation-induced crosslinking of POE.

  18. Subtle cytotoxicity and genotoxicity differences in superparamagnetic iron oxide nanoparticles coated with various functional groups

    PubMed Central

    Hong, Seong Cheol; Lee, Jong Ho; Lee, Jaewook; Kim, Hyeon Yong; Park, Jung Youn; Cho, Johann; Lee, Jaebeom; Han, Dong-Wook

    2011-01-01

    Superparamagnetic iron oxide nanoparticles (SPIONs) have been widely utilized for the diagnosis and therapy of specific diseases, as magnetic resonance imaging (MRI) contrast agents and drug-delivery carriers, due to their easy transportation to targeted areas by an external magnetic field. For such biomedical applications, SPIONs must have multifunctional characteristics, including optimized size and modified surface. However, the biofunctionality and biocompatibility of SPIONs with various surface functional groups of different sizes have yet to be elucidated clearly. Therefore, it is important to carefully monitor the cytotoxicity and genotoxicity of SPIONs that are surfaced-modified with various functional groups of different sizes. In this study, we evaluated SPIONs with diameters of approximately 10 nm and 100~150 nm, containing different surface functional groups. SPIONs were covered with −O− groups, so-called bare SPIONs. Following this, they were modified with three different functional groups – hydroxyl (−OH), carboxylic (−COOH), and amine (−NH2) groups – by coating their surfaces with tetraethyl orthosilicate (TEOS), (3-aminopropyl)trimethoxysilane (APTMS), TEOS-APTMS, or citrate, which imparted different surface charges and sizes to the particles. The effects of SPIONs coated with these functional groups on mitochondrial activity, intracellular accumulation of reactive oxygen species, membrane integrity, and DNA stability in L-929 fibroblasts were determined by water-soluble tetrazolium, 2′,7′-dichlorodihydrofluorescein, lactate dehydrogenase, and comet assays, respectively. Our toxicological observations suggest that the functional groups and sizes of SPIONs are critical determinants of cellular responses, degrees of cytotoxicity and genotoxicity, and potential mechanisms of toxicity. Nanoparticles with various surface modifications and of different sizes induced slight, but possibly meaningful, changes in cell cytotoxicity and

  19. Facile development of Au-ring microelectrode for in vivo analysis using non-toxic polydopamine as multifunctional material.

    PubMed

    Lin, Yuqing; Wang, Keqing; Xu, Yanan; Li, Linbo; Luo, Jingxuan; Wang, Chao

    2016-04-15

    In this study, we describe a facile and fast wet deposition technique to bottom-up fabricate Au-ring microelectrodes (Au-RMEs) using non-toxic polydopamine as multifunctional grafting material instead of commonly used (3-aminopropyl)-trimethoxysilane (APTMS). The Au-RMEs are fabricated by growing Au film uniformly inside of a pulled glass capillary. Au-RMEs with tip apex diameter ranging from 15 to 50 μm were fabricated involving four consequent steps, i.e. hydroxylating the inside wall of a pulled glass capillaries, grafting adhesive polydopamine (PDA) film to hydroxyl group surface, seeding gold nanoparticles (AuNPs) onto PDA surface and finally growing thickness-tunable gold layer on top of gold nanoparticles. After 3-mercaptopropionic acid (MPA) self-assembled monolayers (SAMs) modification, the Au-RMEs obtain improved specificity and sensitivity for monitoring of dopamine (DA) with respect to alleviating ascorbic acid (AA) interference. The current response is in wide linearity to DA concentration in the range of 0.2-100.0 μM with a correlation coefficient of 0.998 and the detection limit as low as 50.0 nM (S/N=3). In addition, the designed glass substrates of Au-RMEs were mechanically stronger and their tips can be further sharped by adjusting the pulling program. In order to demonstrate the utility of these fabricated microelectrodes in neurochemistry, Au-RMEs were used for electrochemical monitoring of DA release stimulated by K(+) in the striatum of rats. Thus, this study offers a novel and reliable strategy for preparing Au microelectrodes and maybe an attractive alternative to the traditional options for continuous and in vivo electrochemical monitoring of DA in various physiological processes.

  20. Organic-inorganic hybrid compounds containing polyhedral oligomeric silsesquioxane for conservation of stone heritage.

    PubMed

    Son, Seunghwan; Won, Jongok; Kim, Jeong-Jin; Jang, Yun Deuk; Kang, Yong Soo; Kim, Sa Dug

    2009-02-01

    Alkoxysilane solutions based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying heritage stone surfaces. TEOS-based products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the grains of stone components. However, they suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developing capillary force and dense gel fractures left inside of the stone. In this study, a TEOS-based stone consolidant containing functional (3-glycidoxypropyl)trimethoxysilane (GPTMS) and polyhedral oligomeric silsesquioxane (POSS) has been prepared in order to reduce gel crack formation during the drying phase. The addition of nanometer-sized POSS and/or GPTMS having a flexible segment reduces the capillary force developed during solvent evaporation. The properties of the TEOS/GPTMS/POSS composite solutions were compared with those of commercial products (Wacker OH and Unil sandsteinfestiger OH 1:1). The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/POSS solution was stable over a period of up to 6 months. The addition of POSS and GPTMS provided a crack-free gel, while the gel from the commercial consolidants exhibited cracks after drying. The surface hydrophobicity of the treated decayed granite increased with the addition of POSS and GPTMS, and it was higher than that of the commercial product, implying the possibility of POSS and GPTMS as barriers to the penetration of water. This result implies that the TEOS/GPTMS/POSS solution showed a high suitability for the consolidation of granite heritage.

  1. Anti-flammable vinyl ester resin nano-composite with nano-titania

    NASA Astrophysics Data System (ADS)

    Das, Rajib

    Anti-flammable material is a common expectation for any industry and household applications to protect the material from fire accident. Polymer composites also play a significant role in preparing anti flammable materials. Vinyl ester resins (VERs) are thermosetting resins that have excellent mechanical and thermal properties of epoxy resins and Nanotitania is an inexpensive, nontoxic and biocompatible inorganic material. In this paper to investigate the flame retardency of polymer nanocomposites VER is used as polymer matrix and TiO2 is used as inorganic nanofiller.3-[2-(2-aminoethylamino) ethylamino]propyl-trimethoxysilane (TATMS), a kind of silane is used as a coupling agent to functionalize the surface of nanoTiO2 to improve its flame retardency by adding Si and N2 group. TGA test and FTIR test have been performed and different peaks for Si and N2 in the modified nanofiller and weight loss of fabricated nanofiller confirmed that fabrication method was successful. After that, nanocomposite sample of VERs reinforced with nano TiO2 prepared and the effects of different loadings on mechanical and flame retardant properties are investigated after and before the modification of nanofillers. From tensile test result it is found that up to 5% loading of modified nanofiller the tensile strength is 62 MPa that is almost as same as pure VER and the tensile strength of unmodified nanofiller based PNC is 68 MPa which is not significant improvement in its mechanical property. From MCC test of flame retardancy it is found that the normalized heat release capacity of modified nanofiller based nanocomposite is decreased by 27.7% than unmodified nanofiller based PNC that is 9.8%. Also the normalized total heat release of modified nanofiller based PNC is 21.4% than unmodified PNC that is 12.4%.

  2. Beta-cyclodextrins conjugated magnetic Fe3O4 colloidal nanoclusters for the loading and release of hydrophobic molecule

    NASA Astrophysics Data System (ADS)

    Lv, Shaonan; Song, Yubei; Song, Yaya; Zhao, Zhigang; Cheng, Changjing

    2014-06-01

    Herein, we report a facile method to prepare beta-cyclodextrin (β-CD)-conjugated magnetic Fe3O4 colloidal nanocrystal clusters (Fe3O4@GLY-CD) using (3-glycidyloxypropyl) trimethoxysilane (GLY) as the intermediate linker. The resulting Fe3O4@GLY-CD was characterized by several methods including Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM). In addition, the loading and release properties of the synthesized Fe3O4@GLY-CD for the hydrophobic molecule 8-anilino-1-naphthalenesulfonic acid ammonium salt (ANS) were also investigated. The results show that the Fe3O4@GLY-CD has a spherical structure with an average diameter of 186 nm and high saturated magnetism of 51.2 emu/g. The grafting of β-CD onto Fe3O4 colloidal nanocrystal clusters can markedly increase the loading capacity of ANS because of β-CD/ANS inclusion complex formation. The in vitro delivery profile shows that the release of ANS from the Fe3O4@GLY-CD nanosystem exhibits an initial burst followed by a slow and steady release. Moreover, Fe3O4@GLY-CD also demonstrates a temperature-dependent release behavior for ANS owing to the effect of temperature on the association constants of β-CD/ANS inclusion complexes. The developed magnetic hybrid nanomaterial is expected to find potential applications in several fields including separation science and biomedicine.

  3. XNBR-grafted halloysite nanotube core-shell as a potential compatibilizer for immiscible polymer systems

    NASA Astrophysics Data System (ADS)

    Paran, S. M. R.; Naderi, G.; Ghoreishy, M. H. R.

    2016-09-01

    Halloysite nanotubes (HNTs) grafted with carboxylated nitrile byutadiene rubber (XNBR) were synthesized via a sol-gel method. The HNTs as an inorganic cores were pre-treated with 3-Glycidoxypropyl trimethoxysilane, then successfully coated with the XNBR as an organic shell. The properties of XNBR-grafted HNTs were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results suggested that the XNBR grafted to the surfaces of HNTs successfully. Then the TPE nanocomposites based on polyamide-6 (PA6) and nitrile butadiene rubber (NBR) containing various XNBR-grafted and pristine HNTs were prepared via a direct melt mixing method. The morphology, mechanical, dynamic mechanical and rheological properties of the prepared TPE nanocomposites were investigated. The results show that the XNBR-grafted HNTs can effectively improve the morphology and mechanical properties of the PA6/NBR TPEs. The morphology study of the prepared nanocomposites show that the effect of XNBR-grafted HNTs on the size reduction of NBR phase is markedly more effective than the pristine HNTs and rose by 50% in the same concentrations. Mechanical measurements show that the Young's modulus of the TPE nanocomposites rose by 60% in just 7 wt% of XNBR-grafted HNT loading. The results indicate that the introduction of HNT/XNBR core-shells into the PA6/NBR TPEs can enhances the interfacial interactions and provides a more fine rubber phase morphology and controlled mechanical properties in comparison with the accordingly TPE nanocomposites containing pristine HNTs.

  4. Advanced Functional Thin Films Prepared by Plasma CVD

    NASA Astrophysics Data System (ADS)

    Takai, Osamu

    1998-10-01

    Recently water repellency has been required for many types of substrate (e.g. glass, plastics, fibers, ceramics and metals) in various industrial fields. This paper reports on the preparation of highly water-repellent thin films by plasma CVD (PCVD). We have prepared transparent water-repellent thin films at low substrate temperatures by two types of PCVD, rf PCVD and microwave PCVD, using fluoro-alkyl silanes (FASs) as source gases. Silicon oxide thin films contained fluoro-alkyl functions were deposited onto glass and plastics, and realized the excellent water repellency like polytetrafluoroetylene (PTFE) and the high transparency like glass. Increasing the deposition pressure we have formed ultra water-repellent (contact angle for a water drop of over about 150 degrees) thin films by microwave PCVD using a multiple gas mixture of tetramethylsilane (TMS), (heptadecafluoro-1,1,2,2-tetrahydro-decyl)-1-trimethoxysilane (FAS-17) and argon. Ultra water-repellency appears at higher total pressures over 40 Pa because the surface becomes rough due to the growth of large particles. The color of these ultra water-repellent films is slightly white because of the scattering of light by the large particles. Recently we have also deposited transparent ultra water-repellent thin films at low substrate temperatures by microwave PCVD using organosilicon compounds without fluorine as source gases. We evaluated water repellency, optical transmittance, surface morphology and chemical composition of the deposited films. At the suitable substrate position the deposited film gave the contact angle of about 150 degrees and the transmittance of over 80 visible region for a coated glass (thickness was about 1 micron). The control of the surface morphology of the deposited films is most important to obtain the transparent ultra water-repellent films.

  5. Layered double hydroxide catalyst for the conversion of crude vegetable oils to a sustainable biofuel

    NASA Astrophysics Data System (ADS)

    Mollaeian, Keyvan

    Over the last two decades, the U.S. has developed the production of biodiesel, a mixture of fatty acid methyl esters, using chiefly vegetable oils as feedstocks. However, there is much concern about the availability of high-quality vegetable oils for longterm biodiesel production. Problems have also risen due to the production of glycerol, an unwanted byproduct, as well as the need for process wash water. Therefore, this study was initiated to produce not only fatty acid methyl esters (FAMEs) but also fatty acid glycerol carbonates (FAGCs) by replacing methanol with dimethyl carbonate (DMC). The process would have no unnecessary byproducts and would be a simplified process compared to traditional biodiesel. In addition, this altering of the methylating agent could convert triglycerides, free fatty acids, and phospholipids to a sustainable biofuel. In this project, Mg-Al Layered Double Hydroxide (LDH) was optimized by calcination in different temperature varied from 250°C to 450°C. The gallery between layers was increased by intercalating sodium dodecylsulfate (SDS). During catalyst preparation, the pH was controlled ~10. In our experiment, triazabicyclodecene (TBD) was attached with trimethoxysilane (3GPS) as a coupling agent, and N-cetyl-N,N,N-trimethylammonium bromide (CTAB) was added to remove SDS from the catalyst. The catalyst was characterized by XRD, FTIR, and Raman spectroscopy. The effect of the heterogeneous catalyst on the conversion of canola oil, corn oil, and free fatty acids was investigated. To analyze the conversion of lipid oils to biofuel an in situ Raman spectroscopic method was developed. Catalyst synthesis methods and a proposed mechanism for converting triglycerides and free fatty acids to biofuel will be presented.

  6. Significant Improvement in Thermal and UV Resistances of UHMWPE Fabric through in Situ Formation of Polysiloxane-TiO2 Hybrid Layers.

    PubMed

    Hu, Jiangtao; Gao, Qianhong; Xu, Lu; Zhang, Mingxing; Xing, Zhe; Guo, Xiaojing; Zhang, Kuo; Wu, Guozhong

    2016-09-01

    Anatase nanocrystalline titanium dioxide coatings were produced on ultrahigh molecular weight polyethylene (UHMWPE) fabric by radiation-induced graft polymerization of γ-methacryloxypropyl trimethoxysilane (MAPS) and subsequent cohydrolysis of the graft chains (PMAPS) with tetrabutyl titanate, followed by boiling water treatment for 180 min. The resulting material was coded as UHMWPE-g-PMAPS/TiO2 and characterized by attenuated total reflection infrared spectrometry, differential scanning calorimetry, X-ray diffraction, thermal gravimetry, and ultraviolet absorption spectroscopy, among others. The predominant form of TiO2 in the thin film was anatase. The coating layer was composed of two sublayers: an inner part consisting of an organic-inorganic hybrid layer to prevent photocatalytic degradation of the matrix by TiO2 film, and an outer part consisting of anatase nanocrystalline TiO2 capable of UV absorption. This UHMWPE-g-PMAPS/TiO2 composite exhibited much better thermal resistance than conventional UHMWPE fabric, as reflected by the higher melting point, decreased maximum degradation rate, and higher char yield at 700 °C. Compared with UHMWPE fabric, UHMWPE-g-PMAPS/TiO2 exhibited significantly enhanced UV absorption and excellent duration of UV illumination. Specifically, the UV absorption intensity was 2.4-fold higher than that of UHMWPE fabric; the retention of the break strength of UHMWPE-g-PMAPS/TiO2 reached 92.3% after UV irradiation. This work provides an approach for addressing the issue of self-degradation of TiO2-coated polymeric materials due to the inherent photoactivity of TiO2. PMID:27513017

  7. Spectroscopic Investigation of the Mechanisms Responsible for the Superior Stability of Hybrid Class 1/Class 2 CO2 Sorbents: A New Class 4 Category.

    PubMed

    Wilfong, Walter Christopher; Kail, Brian W; Jones, Christopher W; Pacheco, Carlos; Gray, McMahan L

    2016-05-25

    Hybrid Class 1/Class 2 supported amine CO2 sorbents demonstrate superior performance under practical steam conditions, yet their amine immobilization and stabilization mechanisms are unclear. Uncovering the interactions responsible for the sorbents' robust features is critical for further improvements and can facilitate practical applications. We employ solid state (29)Si CP-MAS and 2-D FSLG (1)H-(13)C CP HETCOR NMR spectroscopies to probe the overall molecular interactions of aminosilane/silica, polyamine [poly(ethylenimine), PEI]/silica, and hybrid aminosilane/PEI/silica sorbents. A unique, sequential impregnation sorbent preparation method is executed in a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) setup to decouple amine binding mechanisms at the amine-silica interface from those within bulk amine layers. These mechanisms are correlated with each sorbents' resistance to accelerated liquid H2O and TGA steam treatments (H2O stability) and to oxidative degradation (thermal stability). High percentages of CO2 capture retained (PCR) and organic content retained (OCR) values after H2O testing of N-(3-(trimethoxysilyl)propyl)ethylenediamine (TMPED)/PEI and (3-aminopropyl)trimethoxysilane (APTMS)/PEI hybrid sorbents are associated with a synergistic stabilizing effect of the amine species observed during oxidative degradation (thermal gravimetric analysis-differential scanning calorimetry, TGA-DSC). Solid state NMR spectroscopy reveals that the synergistic effect of the TMPED/PEI mixture is manifested by the formation of hydrogen-bonded PEI-NH2···NH2-TMPED and PEI-NH2···HO-Si/O-Si-O (TMPED, T(2)) linkages within the sorbent. DRIFTS further determines that PEI enhances the grafting of TMPED to silica and that PEI is dispersed among a stable network of polymerized TMPED in the bulk, utilizing H-bonded linkages. These findings provide the scientific basis for establishing a Class 4 category for aminosilane/polyamine/silica hybrid sorbents

  8. Preparation of Proton Exchange Membranes and Lithium Batteries from Melamine-containing Ormosils

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

    Our laboratory has recently reported a series of rodcoil polymers for lithium batteries that display dimensionally stable films with good ionic conductivity. The rod segments consist of rigid linear and branched polyimides and the coil segments are polyethylene oxides (PEO). It has been proposed that good mechanical and transport properties are due to phase separation between the rod and coil segments. It was also observed that increased branching and molecular weight lead to increased conductivity. The following study was undertaken to assess the effects of phase separation in polyalkylene oxides connected by melamine linkages. Melamine was chosen as the linking unit because it provides a branching site, cation binding sites to help ionic transport between polymer chains, and the opportunity for self assembly through hydrogen bonding. Polymers were made by the reaction of cyanuric chloride with a series of amine-terminated alkylene oxides. A linear polymer was first made, followed by reaction of the third site on cyanuric chloride with varying ratios of monofunctional Jeffamine and (3-aminopropyl)triethoxysilane. The lithium trifluoromethane sulfonamide-doped polymers are then crosslinked through a sol-gel process to form free-standing films. Initial results have shown mechanically strong films with lithium conductivities on the order of 2 x 10(exp -5) S/cm at ambient temperature. In a separate study, organically modified silanes (Ormosils) that contain sulfonic acid derivatized melamines have been incorporated into proton exchange membranes. The membranes are made by reaction of the primary amine groups of various ratios of melamine derivative and difunctional Jeffamine (MW = 2000) with the epoxide group of (3-Glycidyloxypropyl)trimethoxysilane. The films were then cross-linked through a sol-gel process. Resulting sulfuric acid doped films are strong, flexible, and have proton conductivities on the order of 2 x l0(exp -2) S/cm (120 C, 25% relative humidity). Our

  9. Polysiloxane layers created by sol-gel and photochemistry: ideal surfaces for rapid, low-cost and high-strength bonding of epoxy components to polydimethylsiloxane.

    PubMed

    Wilhelm, Elisabeth; Deshpande, Kaustubh; Kotz, Frederik; Schild, Dieter; Keller, Nico; Heissler, Stefan; Sachsenheimer, Kai; Länge, Kerstin; Neumann, Christiane; Rapp, Bastian E

    2015-04-01

    In this article we introduce and compare three techniques for low-cost and rapid bonding of stereolithographically structured epoxy components to polydimethylsiloxane (PDMS). In short, we first create a polysiloxane layer on the epoxy surface via silane surface coupling and polymerization. Afterwards, the modified epoxy surface can be bonded to a PDMS component at room temperature using a handheld corona discharger, which is a commonly used low-cost technique for bonding two PDMS components. Using these methods bonds of desirable strength can be generated within half an hour. Depending on the epoxy resin, we found it necessary to modify the silanization procedure. Therefore, we provide a total of three different silanization techniques that allow bonding of a wide variety of stereolithographically structurable epoxy resins. The first technique is a UV-light induced silanization process which couples a silane that contains an epoxy-ring ((3-glycidoxypropyl)trimethoxysilane (GPTMS)). For surfaces that cannot be modified with this silane we use dimethoxydimethylsilane (DMDMS). This silane can either be coupled to the surface by a sol-gel process or UV-light induced polymerisation. The sol-gel process which is a heat induced surface modification technique results in high bond strengths. Because of the heat which triggers the sol-gel process, this technique is limited to epoxy polymers with high glass transition temperatures. For the majority of stereolithographically structured epoxy resins which typically have glass transition temperatures of around 60 °C the light-induced bonding technique is preferable. For all three techniques we performed DIN EN-conform tensile testing demonstrating maximum bond strengths of up to 350 kPa which is comparable with bond strengths reported for PDMS-to-PDMS bonds. For all bond methods, long-term stability as well as hydrolytic stability was assessed.

  10. Use of silane-functionalized graphene oxide in organic photovoltaic cells and organic light-emitting diodes.

    PubMed

    Lee, Chang Yeong; Le, Quyet Van; Kim, Cheolmin; Kim, Soo Young

    2015-04-14

    Graphene oxide (GO) and silane-functionalized GO (sGO) sheets obtained through a simple sonication exfoliation method are employed as hole transport layers to improve the efficiency of organic photovoltaic (OPV) cells and organic light-emitting diodes (OLED). GO was functionalized using (3-glycidyl oxypropyl)trimethoxysilane (GPTMS) and triethoxymethylsilane (MTES). The appearance of new peaks in the Fourier-transform infrared spectra of the sGOs indicates the formation of Si-O-C, Si-O-Si, Si-H, and Si-O-C moieties, which provide evidence of the addition of silane to the GO surface. Furthermore, the appearance of Si-O-Si bonds in the synchrotron radiation photoelectron spectra (SRPES) of the MTES-sGO and GPTMS-sGO samples suggests that silane groups were effectively functionalized onto the GO sheets. An OPV cell with GO layers showed a lower performance with a power conversion efficiency (PCE) of 2.06%; in contrast, OPV cells based on GPTMS-sGO and MTES-sGO have PCE values of 3.00 and 3.08%, respectively. The OLED devices based on GPTMS-sGO and MTES-sGO showed a higher maximum luminance efficiency of 13.91 and 12.77 cd A(-1), respectively, than PEDOT:PSS-based devices (12.34 cd A(-1)). The SRPES results revealed that the work functions of GO, GPTMS-sGO, and MTES-sGO were 4.8, 4.9, and 5.0 eV, respectively. Therefore, the increase in the PCE value is attributed to improved band-gap alignment. It is thought that sGO could be used as an interfacial layer in OPV and OLED devices.

  11. Highly flexible, proton-conductive silicate glass electrolytes for medium-temperature/low-humidity proton exchange membrane fuel cells.

    PubMed

    Lee, Hyeon-Ji; Kim, Jung-Hwan; Won, Ji-Hye; Lim, Jun-Muk; Hong, Young Taik; Lee, Sang-Young

    2013-06-12

    We demonstrate highly flexible, proton-conductive silicate glass electrolytes integrated with polyimide (PI) nonwoven fabrics (referred to as "b-SS glass electrolytes") for potential use in medium-temperature/low-humidity proton exchange membrane fuel cells (PEMFCs). The b-SS glass electrolytes are fabricated via in situ sol-gel synthesis of 3-trihydroxysilyl-1-propanesulfonic acid (THPSA)/3-glycidyloxypropyl trimethoxysilane (GPTMS) mixtures inside PI nonwoven substrates that serve as a porous reinforcing framework. Owing to this structural uniqueness, the b-SS glass electrolytes provide noticeable improvements in mechanical bendability and membrane thickness, in comparison to typical bulk silicate glass electrolytes that are thick and easily fragile. Another salient feature of the b-SS glass electrolytes is the excellent proton conductivity at harsh measurement conditions of medium temperature/low humidity, which is highly important for PEMFC-powered electric vehicle applications. This beneficial performance is attributed to the presence of a highly interconnected, proton-conductive (THPSA/GPTMS-based) silicate glass matrix in the PI reinforcing framework. Notably, the b-SS glass electrolyte synthesized from THPSA/GPTMS = 9/1 (mol/mol) exhibits a higher proton conductivity than water-swollen sulfonated polymer electrolyte membranes (here, sulfonated poly(arylene ether sulfone) and Nafion are chosen as control samples). This intriguing behavior in the proton conductivity of the b-SS glass electrolytes is discussed in great detail by considering its structural novelty and Grotthuss mechanism-driven proton migration that is strongly affected by ion exchange capacity (IEC) values and also state of water.

  12. Surface forces and protein adsorption on dextran- and polyethylene glycol-modified polydimethylsiloxane.

    PubMed

    Farrell, Megan; Beaudoin, Stephen

    2010-12-01

    Dextran and polyethylene glycol (PEG) are often covalently bound to the surface of polydimethylsiloxane (PDMS) for the purpose of modifying its hydrophilicity and biocompatibility. In this work, the effects of the dextran and PEG on the morphology, wetting, and surface charge of the resulting surfaces were quantified and correlated with changes in the amount of fibrinogen and albumin adsorbed from aqueous solution. PDMS films were functionalized in a microwave oxygen plasma to create surface hydroxyl groups that were subsequently aminated by incubation in a (3-aminopropyl)trimethoxysilane (APTES) solution. Oxidized dextran and PEG-aldehyde were linked to the surface amines via reductive amination. This process resulted in low surface coverage of immobilized PEG in the end-on conformation and a more uniform and dense distribution of side-on immobilized dextran. The immobilized dextran reduced the contact angle of the PDMS film from 109° to 80° and neutralized the zeta potential over the pH range from 3 to 11. An atomic force microscope was used to measure the interaction force between the modified PDMS and a model hydrophobic surface (polystyrene latex) and a model hydrophilic surface (silica) in aqueous solution to show that van der Waals and hydrophobic attractive forces are the dominant forces for protein adsorption in this system. The PEG- and dextran-modified PDMS were exposed to BSA and fibrinogen to test their resistance to protein adsorption. The coatings were ineffective at reducing the adsorption of either molecule, and the dextran-modification of the PDMS caused more BSA to adsorb than in the case of the unmodified PDMS. PMID:20801620

  13. Microcystin-LR detection in water by the Fabry-Pérot interferometer using an optical fibre coated with a sol-gel imprinted sensing membrane.

    PubMed

    Queirós, Raquel B; Silva, S O; Noronha, J P; Frazão, O; Jorge, P; Aguilar, G; Marques, P V S; Sales, M G F

    2011-05-15

    Cyanobacteria deteriorate the water quality and are responsible for emerging outbreaks and epidemics causing harmful diseases in Humans and animals because of their toxins. Microcystin-LR (MCT) is one of the most relevant cyanotoxin, being the most widely studied hepatotoxin. For safety purposes, the World Health Organization recommends a maximum value of 1 μg L(-1) of MCT in drinking water. Therefore, there is a great demand for remote and real-time sensing techniques to detect and quantify MCT. In this work a Fabry-Pérot sensing probe based on an optical fibre tip coated with a MCT selective thin film is presented. The membranes were developed by imprinting MCT in a sol-gel matrix that was applied over the tip of the fibre by dip coating. The imprinting effect was obtained by curing the sol-gel membrane, prepared with (3-aminopropyl) trimethoxysilane (APTMS), diphenyl-dimethoxysilane (DPDMS), tetraethoxysilane (TEOS), in the presence of MCT. The imprinting effect was tested by preparing a similar membrane without template. In general, the fibre Fabry-Pérot with a Molecular Imprinted Polymer (MIP) sensor showed low thermal effect, thus avoiding the need of temperature control in field applications. It presented a linear response to MCT concentration within 0.3-1.4 μg L(-1) with a sensitivity of -12.4±0.7 nm L μg(-1). The corresponding Non-Imprinted Polymer (NIP) displayed linear behaviour for the same MCT concentration range, but with much less sensitivity, of -5.9±0.2 nm L μg(-1). The method shows excellent selectivity for MCT against other species co-existing with the analyte in environmental waters. It was successfully applied to the determination of MCT in contaminated samples. The main advantages of the proposed optical sensor include high sensitivity and specificity, low-cost, robustness, easy preparation and preservation.

  14. Boronic acid-modified magnetic materials for antibody purification

    PubMed Central

    Dhadge, Vijaykumar L.; Hussain, Abid; Azevedo, Ana M.; Aires-Barros, Raquel; Roque, Ana C. A.

    2014-01-01

    Aminophenyl boronic acids can form reversible covalent ester interactions with cis-diol-containing molecules, serving as a selective tool for binding glycoproteins as antibody molecules that possess oligosaccharides in both the Fv and Fc regions. In this study, amino phenyl boronic acid (APBA) magnetic particles (MPs) were applied for the magnetic separation of antibody molecules. Iron oxide MPs were firstly coated with dextran to avoid non-specific binding and then with 3-glycidyloxypropyl trimethoxysilane to allow further covalent coupling of APBA (APBA_MP). When contacted with pure protein solutions of human IgG (hIgG) and bovine serum albumin (BSA), APBA_MP bound 170 ± 10 mg hIgG g−1 MP and eluted 160 ± 5 mg hIgG g−1 MP, while binding only 15 ± 5 mg BSA g−1 MP. The affinity constant for the interaction between hIgG and APBA_MP was estimated as 4.9 × 105 M−1 (Ka) with a theoretical maximum capacity of 492 mg hIgG adsorbed g−1 MP (Qmax), whereas control particles bound a negligible amount of hIgG and presented an estimated theoretical maximum capacity of 3.1 mg hIgG adsorbed g−1 MP (Qmax). APBA_MPs were also tested for antibody purification directly from CHO cell supernatants. The particles were able to bind 98% of IgG loaded and to recover 95% of pure IgG (purity greater than 98%) at extremely mild conditions. PMID:24258155

  15. 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.

  16. An ion-imprinted amino-functionalized silica gel sorbent prepared by hydrothermal assisted surface imprinting technique for selective removal of cadmium (II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Fan, Hong-Tao; Li, Jing; Li, Zhan-Chao; Sun, Ting

    2012-02-01

    A new ion-imprinted amino-functionalized silica gel sorbent was synthesized by the hydrothermal-assisted surface imprinting technique using Cd2+ as the template, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (AAAPTS) as the functional monomer, and epichlorohydrin as the cross-linking agent (IIP-AAAPTS/SiO2) for the selective removal of Cd2+ from aqueous solution, and was characterized by FTIR, SEM, nitrogen adsorption and the static adsorption-desorption experiment method. The specific surface area of the IIP-AAAPTS/SiO2 sorbents was found to be 149 m2 g-1. The results showed that the maximum static adsorption capacities of IIP-AAAPTS/SiO2 sorbents by hydrothermal heating method and by the conventional heating method were 57.4 and 31.6 mg g-1, respectively. The IIP-AAAPTS/SiO2 sorbents offered a fast kinetics for the adsorption and desorption of Cd(II). The relative selectivity coefficients of IIP-AAAPTS/SiO2 sorbents for Cd2+/Co2+, Cd2+/Ni2+, Cd2+/Zn2+, Cd2+/Pb2+ and Cd2+/Cu2+ were 30.68, 14.02, 3.00, 3.12 and 6.17, respectively. IIP-AAAPTS/SiO2 sorbents had a substantial binding capacity in the range of pH 4-8 and could be used repeatedly. Equilibrium data fitted perfectly with Langmuir isotherm model compared to Freundlich isotherm model. Kinetic studies indicated that adsorption followed a pseudo-second-order model. Negative values of ΔG° indicated spontaneous adsorption and the degree of spontaneity of the reaction increased with increasing temperature. ΔH° of 26.13 kJ mol-1 due to the adsorption of Cd2+ on the IIP-AAAPTS/SiO2 sorbents indicated that the adsorption was endothermic in the experimental temperature range.

  17. Sensitive determination of As (III) and As (V) by magnetic solid phase extraction with Fe@polyethyleneimine in combination with hydride generation atomic fluorescence spectrometry.

    PubMed

    Zhou, Qingxiang; Zheng, Zhenwen; Xiao, Junping; Fan, Huili

    2016-08-15

    The magnetic nanomaterial Fe@polyethyleneimine (Fe@PEI) was successfully synthesized and used as an effective adsorbent material for magnetic solid phase extraction(MSPE) of As(III) and As(V) from water samples. Fe@SiO2 nanoparticles were prepared by one pot synthetic method using a borohydride reduction method, then modified with (3-chloropropyl)trimethoxysilane to obtain Fe@SiO2-Cl by chloropropylation, which was reacted with PEI to achieve Fe@polyethyleneimine (Fe@PEI). The microstructure and morphology of Fe@PEI were characterized by transmission electron microscoscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The experimental results showed that Fe@PEI demonstrated excellent adsorption for As(III) and As(V). Based on this fact, the determination method for these two arsenic species earned good limits of detection (LODs) of 0.002μgL(-1) and wide calibration curves in the concentration range from 0.008 to 0.2μgL(-1). The precisions of As (III) and As (V)were 1.95% and 2.55% (RSD, n=6), respectively. The proposed method was validated with real samples and the spiked recoveries were in the range of 82.7-98.3% and the accuracies were in the range of 2-13.3%. The results demonstrated that the developed MSPE method had good advantages such as simplicity, rapid separation, low cost, easy to reuse and high-quality analytical performances, which made it attractive for rapid and efficient extraction of inorganic arsenic species in the environmental water samples. PMID:27260453

  18. Immunoassay for tumor markers in human serum based on Si nanoparticles and SiC@Ag SERS-active substrate.

    PubMed

    Zhou, Lu; Zhou, Jun; Feng, Zhao; Wang, Fuyan; Xie, Shushen; Bu, Shizhong

    2016-04-21

    Based on a sandwich structure consisting of nano-Si immune probes and a SiC@Ag SERS-active immune substrate, a kind of ultra-sensitive immunoassay protocol is presented to detect tumor markers in human serum. The nano-Si immune probes were prepared by immobilizing the detecting antibodies onto the surfaces of SiO2-coated Si nanoparticles (NPs) which were modified with 3-(aminopropyl)trimethoxysilane, and the SiC@Ag SERS-active immune substrates were prepared by immobilizing the captured antibodies on Ag film sputtered on SiC sandpaper. To the best of our knowledge, it is the first time that Si NPs are directly used as Raman tags in an immunoassay strategy. And, the SiC@Ag SERS-active substrates exhibit excellent surface enhanced Raman scattering (SERS) performances with an enhancement factor of ∼10(5), owing to the plasmonic effect of the Ag film on the rough surface of the SiC sandpaper. In our experiments, the sandwich immunoassay structure has been successfully applied to detect prostate specific antigen (PSA), α-fetoprotein (AFP) and carbohydrate antigen 19-9 (CA19-9) in a human serum sample and the limit of detections are as low as 1.79 fg mL(-1), 0.46 fg mL(-1) and 1.3 × 10(-3) U mL(-1), respectively. It reveals that the proposed immunoassay protocol has demonstrated a high sensitivity for tumor markers in human serum and a potential practicability in biosensing and clinical diagnostics. PMID:27003871

  19. Determination of methicillin-resistant and methicillin-susceptible Staphylococcus aureus bacteria in blood by capillary zone electrophoresis.

    PubMed

    Horká, Marie; Tesařová, Marie; Karásek, Pavel; Růžička, Filip; Holá, Veronika; Sittová, Martina; Roth, Michal

    2015-04-01

    Serious bloodstream infections are a significant complication in critically ill patients. The treatment of these infections has become more difficult because of the increasing prevalence of multiresistant strains, especially methicillin-resistant Staphylococcus aureus (MRSA). Rapid differentiation of low number of MRSA from methicillin-susceptible S. aureus (MSSA) cells (10(1)-10(2) cells mL(-1)) in blood is necessary for fast effective antibiotic therapy. Currently, three groups of techniques, phenotyping, genotyping, and mass spectrometry, are used for MRSA and MSSA strains differentiation. Most of these techniques are time-consuming. PCR and other molecular techniques allow the detection and differentiation between MSSA and MRSA directly from blood cultures. These methods alone are rapid and they have good reproducibility and repeatability. Potential disadvantages of the genotyping methods include their discrimination ability, technical complexity, financial costs, and difficult interpretation of the results. Recently, capillary electrophoresis (CZE) was successfully used to differentiate between the agar-cultivated MRSA and MSSA strains in fused silica capillaries etched with supercritical water and modified with (3-glycidyloxypropyl)trimethoxysilane. The possible use of CZE as a fast and low-cost method for distinguishing between the blood-incubated MRSA or MSSA cells has been tested in this manuscript. Our goal was to test low amounts of bacteria (∼10(2) cell mL(-1)) similar to those in clinical samples. The migration times of the purified blood-incubated cells and the agar-cultivated cells were different from each other. However, their isoelectric point was the same for all strains.

  20. Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

    PubMed

    Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

    2015-02-01

    A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.

  1. Significant Improvement in Thermal and UV Resistances of UHMWPE Fabric through in Situ Formation of Polysiloxane-TiO2 Hybrid Layers.

    PubMed

    Hu, Jiangtao; Gao, Qianhong; Xu, Lu; Zhang, Mingxing; Xing, Zhe; Guo, Xiaojing; Zhang, Kuo; Wu, Guozhong

    2016-09-01

    Anatase nanocrystalline titanium dioxide coatings were produced on ultrahigh molecular weight polyethylene (UHMWPE) fabric by radiation-induced graft polymerization of γ-methacryloxypropyl trimethoxysilane (MAPS) and subsequent cohydrolysis of the graft chains (PMAPS) with tetrabutyl titanate, followed by boiling water treatment for 180 min. The resulting material was coded as UHMWPE-g-PMAPS/TiO2 and characterized by attenuated total reflection infrared spectrometry, differential scanning calorimetry, X-ray diffraction, thermal gravimetry, and ultraviolet absorption spectroscopy, among others. The predominant form of TiO2 in the thin film was anatase. The coating layer was composed of two sublayers: an inner part consisting of an organic-inorganic hybrid layer to prevent photocatalytic degradation of the matrix by TiO2 film, and an outer part consisting of anatase nanocrystalline TiO2 capable of UV absorption. This UHMWPE-g-PMAPS/TiO2 composite exhibited much better thermal resistance than conventional UHMWPE fabric, as reflected by the higher melting point, decreased maximum degradation rate, and higher char yield at 700 °C. Compared with UHMWPE fabric, UHMWPE-g-PMAPS/TiO2 exhibited significantly enhanced UV absorption and excellent duration of UV illumination. Specifically, the UV absorption intensity was 2.4-fold higher than that of UHMWPE fabric; the retention of the break strength of UHMWPE-g-PMAPS/TiO2 reached 92.3% after UV irradiation. This work provides an approach for addressing the issue of self-degradation of TiO2-coated polymeric materials due to the inherent photoactivity of TiO2.

  2. Boronic acid-modified magnetic materials for antibody purification.

    PubMed

    Dhadge, Vijaykumar L; Hussain, Abid; Azevedo, Ana M; Aires-Barros, Raquel; Roque, Ana C A

    2014-02-01

    Aminophenyl boronic acids can form reversible covalent ester interactions with cis-diol-containing molecules, serving as a selective tool for binding glycoproteins as antibody molecules that possess oligosaccharides in both the Fv and Fc regions. In this study, amino phenyl boronic acid (APBA) magnetic particles (MPs) were applied for the magnetic separation of antibody molecules. Iron oxide MPs were firstly coated with dextran to avoid non-specific binding and then with 3-glycidyloxypropyl trimethoxysilane to allow further covalent coupling of APBA (APBA_MP). When contacted with pure protein solutions of human IgG (hIgG) and bovine serum albumin (BSA), APBA_MP bound 170 ± 10 mg hIgG g(-1) MP and eluted 160 ± 5 mg hIgG g(-1) MP, while binding only 15 ± 5 mg BSA g(-1) MP. The affinity constant for the interaction between hIgG and APBA_MP was estimated as 4.9 × 10(5) M(-1) (Ka) with a theoretical maximum capacity of 492 mg hIgG adsorbed g(-1) MP (Qmax), whereas control particles bound a negligible amount of hIgG and presented an estimated theoretical maximum capacity of 3.1 mg hIgG adsorbed g(-1) MP (Qmax). APBA_MPs were also tested for antibody purification directly from CHO cell supernatants. The particles were able to bind 98% of IgG loaded and to recover 95% of pure IgG (purity greater than 98%) at extremely mild conditions.

  3. The effects of silane network structure on their resistance to water-assisted crack growth.

    SciTech Connect

    Kramer, Edward J.; Benkoski, Jason J.; Hall, Jessica S.; Kent, Michael Stuart; Yim, Hyun

    2003-07-01

    Silane adhesion promoters are commonly used to improve the adhesion, durability, and corrosion resistance of polymer-oxide interfaces. The current study investigates a model interface consisting of the natural oxide of 100 Si and an epoxy cured from diglycidyl ether of bisphenol A (DGEBA) and triethylenetetraamine (TETA). The thickness of (3-glycidoxypropyl)trimethoxysilane (GPS) films placed between the two materials provided the structural variable. Five surface treatments were investigated: a bare interface, a rough monolayer film, a smooth monolayer film, a 5 nm thick film, and a 10 nm thick film. Previous neutron reflection experiments revealed large extension ratios (>2) when the 5 and 10 nm thick GPS films were exposed to deuterated nitrobenzene vapor. Despite the larger extension ratio for the 5 nm thick film, the epoxy/Si fracture energy (G{sub c}) was equal to that of the 10 nm thick film under ambient conditions. Even the smooth monolayer exhibited the same G{sub c}. Only when the monolayer included a significant number of agglomerates did the G{sub c} drop to levels closer to that of the bare interface. When immersed in water at room temperature for 1 week, the threshold energy release rate (G{sub th}) was nearly equal to G{sub c} for the smooth monolayer, 5 nm thick film, and 10 nm thick film. While the G{sub th} for all three films decreased with increasing water temperature, the G{sub th} of the smooth monolayer decreased more rapidly. The bare interface was similarly sensitive to temperature; however, the G{sub th} of the rough monolayer did not change significantly as the temperature was raised. Despite the influence of pH on hydrolysis, the G{sub th} was insensitive to the pH of the water for all surface treatments.

  4. Control of shell thickness in silica-coating of Au nanoparticles and their X-ray imaging properties.

    PubMed

    Kobayashi, Yoshio; Inose, Hiromitsu; Nakagawa, Tomohiko; Gonda, Kohsuke; Takeda, Motohiro; Ohuchi, Noriaki; Kasuya, Atsuo

    2011-06-15

    This paper describes a performance of precise control of shell thickness in silica-coating of Au nanoparticles based on a sol-gel process, and an investigation into X-ray imaging properties for the silica-coated Au (Au/SiO(2)) particles. The Au nanoparticles with a size of 16.9±1.2 nm prepared through a conventional citrate reduction method were used as core particles. The Au nanoparticles were silica-coated with a sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica source, sodium hydroxide (NaOH) as a catalyst, and (3-aminopropyl) trimethoxysilane (APMS) as a silane coupling agent. An increase in TEOS concentration resulted in an increase in shell thickness. Under certain concentrations of Au, H(2)O, NaOH, and APMS, the Au/SiO(2) particles with silica shell thickness of 6.0-61.0 nm were produced with varying TEOS concentration. Absorption peak wavelength of surface plasmon resonance of the Au/SiO(2) colloid solution depended on silica shell thickness, which agreed approximately with the predictions by Mie theory. The as-prepared colloid solution could be concentrated up to an Au concentration of 0.19 M with salting-out and centrifugation. The concentrated colloid solution showed an X-ray image with high contrast, and a computed tomography value for the colloid solution with an Au concentration of 0.129 M was achieved 1329.7±52.7 HU. PMID:21458820

  5. Preparation of surface imprinted material of single enantiomer of mandelic acid with a new surface imprinting technique and study on its chiral recognition and resolution properties.

    PubMed

    Gao, Baojiao; Chen, Lulu; Li, Yanbin

    2016-04-22

    A surface imprinted material of the single enantiomer of mandelic acid with high performance was successfully prepared with a new surface imprinting technique of synchronously graft-polymerizing and molecule imprinting, and its enantiomeric recognition and resolution properties were investigated. Micro-sized silica gel particles were first modified with coupling agent γ-mercaptopropyl trimethoxysilane (MPMS), obtaining the modified particles MPMS-SiO2 on which mercapto groups were introduced. A surface initiating system of -SH/BPO was constituted with the mercapto group (-SH) on MPMS-SiO2 particles and dibenzoyl peroxide (BPO) in N,N-dimethyl formamide (DMF) solution. In DMF solution, (R)-mandelic acid molecule was used as the template and the functional monomer hydroxyethyl methylacrylate (HEMA) were combined together by right of multi-site hydrogen bonds. The free radicals produced on MPMS-SiO2 particles initiate HEMA molecules around (R)-mandelic acid molecules and the crosslinking agent N,N'-Methylenebisacrylamide (MBA) to produce graft/crosslinking-polymerization. At the same time, the template (R)-mandelic acid molecules were enveloped within the thin grafted polymer layer on the surfaces of SiO2 particles, obtaining (R)-mandelic acid surface imprinted material MIP-PHEMA/SiO2. The experimental results show that MIP-PHEMA/SiO2 particles have excellent enantiomeric recognition and resolution ability. The binding capacity of MIP-PHEMA/SiO2 particles for (R)-mandelic acid reaches up to 278 mg/g. As the resolution experiment of a racemic mixture was carried out with MIP-PHEMA/SiO2 particles as solid adsorbent, relative another enantiomer, (S)-mandelic acid, the selectivity coefficient of the imprinted particles for (R)-mandelic acid is 5.02. As a consequence, the two enantiomers were well separated, and the optical purities (ee values) of the supernatant and eluant get up to 44% (corresponding to (S)-mandelic acid excess) and 85% (corresponding to (R

  6. Improvement of Catalytic Efficiency, Thermo-stability and Dye Decolorization Capability of Pleurotus ostreatus IBL-02 laccase by Hydrophobic Sol Gel Entrapment

    PubMed Central

    2012-01-01

    Background In serious consideration of the worldwide environmental issues associated with the extensive use of the textile dyes and effluents generated thereof, the scientists across the world are in search for potential treatment technologies for their treatment. In such scenario the ligninolytic enzymes provide a potential alternative because they are cost effective, eco-friendly and can be applied to wide range of dye containing industrial effluents. Results Laccase produced from Pleurotus ostreatus IBL-02 during decolorization of the reactive textile dye Drimarene brilliant red K-4BL (DBR K-4BL) was purified and immobilized by hydrophobic gel entrapment. The crude laccase was 4.2-fold purified with specific activity of 573.52 U/mg after passing through the DEAE-Sepharose ion exchange and Sephadex-G-100 chromatography columns. P. ostreatus IBL-02 laccase was found to be a homogenous monomeric protein as evident by single band corresponding to 67 kDa on native and sodium dodesylsulfate polyacrylamide gel electrophoresis (PAGE). The laccase was immobilized by entrapment in Sol–gel matrix of trimethoxysilane (T) and proplytetramethoxysilane (P) prepared using different T:P molar ratios. The free and immobilized laccases were compared to investigate the effect of immobilization on catalytic efficiency and thermo-stability features. Laccase immobilized in the Sol–gel of 1:5 T:P ratio was optimally active and thermo-stable fraction at pH 5, 60°C with half-life of 3 h and 50 min. Laccases immobilized in 1:2 and 1:5 T:P ratio gels had significantly higher Km (83 and100mM) and Vmax (1000 and 1111 mM/mg) values as compared to free laccase. After 5 h reaction time varying decolorization percentages with a maximum of 100% were achieved for different dyes and effluents. Conclusions In summary, P. ostreatus IBL-02 laccase was immobilized by entrapping in a Sol–gel matrix with an objective to enhance its catalytic and stability properties. Sol–gel entrapped laccase

  7. Hygrothermal degradation of 3-glycidoxypropyltrimethoxysilane films studied by neutron and X-ray reflectivity and attenuated total reflection infrared spectroscopy.

    SciTech Connect

    Tallant, David Robert; Garcia, Manuel Joseph; Majewski, Jaroslaw; Kent, Michael Stuart; Yim, Hyun

    2005-05-01

    Thin films of organosilanes have great technological importance in the areas of adhesion promotion, durability, and corrosion resistance. However, it is well-known that water can degrade organosilane films, particularly at elevated temperatures. In this work, X-ray and neutron reflectivity (XR and NR) were combined with attenuated total reflection infrared (ATR-IR) spectroscopy to study the chemical and structural changes within thin films of (3-glycidoxypropyl)trimethoxysilane (GPS) after exposure for various periods of time to air saturated with either D{sub 2}O or H{sub 2}O at 80 C. For NR and XR, ultrathin ({approx}100 {angstrom}) films were prepared by spin-coating. Both D{sub 2}O and H{sub 2}O provide neutron scattering contrast with GPS. Variations in the neutron scattering length density (SLD) profiles (a function of mass density and atomic composition) with conditioning time were measured after drying the samples out and also swelled with H{sub 2}O or D{sub 2}O vapor at room temperature. For samples that were dried out prior to measurement, little or no change was observed for H{sub 2}O conditioning up to 3.5 days, but large changes were observed after 30 days of conditioning. The range of conditioning time for this structural change was narrowed to between 4 and 10 days with XR. The SLD profiles indicated that the top portion of the GPS film was transformed into a thick low-density layer after conditioning, but the bottom portion showed little structural change. A previous NR study of as-prepared GPS films involving swelling with deuterated nitrobenzene showed that the central portion of the film has much lower cross-link density than the region nearest the substrate. The present data show that the central portion also swells to a much greater extent with water and hydrolyzes more rapidly. The chemical degradation mechanism was identified by IR as hydrolysis of siloxane bonds. For ATR-IR, GPS films were prepared by dip-coating, which resulted in a greater

  8. Core-shell hybrid upconversion nanoparticles carrying stable nitroxide radicals as potential multifunctional nanoprobes for upconversion luminescence and magnetic resonance dual-modality imaging

    NASA Astrophysics Data System (ADS)

    Chen, Chuan; Kang, Ning; Xu, Ting; Wang, Dong; Ren, Lei; Guo, Xiangqun

    2015-03-01

    Nitroxide radicals, such as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its derivatives, have recently been used as contrast agents for magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI). However, their rapid one-electron bioreduction to diamagnetic N-hydroxy species when administered intravenously has limited their use in in vivo applications. In this article, a new approach of silica coating for carrying stable radicals was proposed. A 4-carboxyl-TEMPO nitroxide radical was covalently linked with 3-aminopropyl-trimethoxysilane to produce a silanizing TEMPO radical. Utilizing a facile reaction based on the copolymerization of silanizing TEMPO radicals with tetraethyl orthosilicate in reverse microemulsion, a TEMPO radicals doped SiO2 nanostructure was synthesized and coated on the surface of NaYF4:Yb,Er/NaYF4 upconversion nanoparticles (UCNPs) to generate a novel multifunctional nanoprobe, PEGylated UCNP@TEMPO@SiO2 for upconversion luminescence (UCL) and magnetic resonance dual-modality imaging. The electron spin resonance (ESR) signals generated by the TEMPO@SiO2 show an enhanced reduction resistance property for a period of time of up to 1 h, even in the presence of 5 mM ascorbic acid. The longitudinal relaxivity of PEGylated UCNPs@TEMPO@SiO2 nanocomposites is about 10 times stronger than that for free TEMPO radicals. The core-shell NaYF4:Yb,Er/NaYF4 UCNPs synthesized by this modified user-friendly one-pot solvothermal strategy show a significant enhancement of UCL emission of up to 60 times more than the core NaYF4:Yb,Er. Furthermore, the PEGylated UCNP@TEMPO@SiO2 nanocomposites were further used as multifunctional nanoprobes to explore their performance in the UCL imaging of living cells and T1-weighted MRI in vitro and in vivo.Nitroxide radicals, such as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its derivatives, have recently been used as contrast agents for magnetic resonance imaging (MRI) and electron

  9. Core-shell hybrid upconversion nanoparticles carrying stable nitroxide radicals as potential multifunctional nanoprobes for upconversion luminescence and magnetic resonance dual-modality imaging

    NASA Astrophysics Data System (ADS)

    Chen, Chuan; Kang, Ning; Xu, Ting; Wang, Dong; Ren, Lei; Guo, Xiangqun

    2015-03-01

    Nitroxide radicals, such as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its derivatives, have recently been used as contrast agents for magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI). However, their rapid one-electron bioreduction to diamagnetic N-hydroxy species when administered intravenously has limited their use in in vivo applications. In this article, a new approach of silica coating for carrying stable radicals was proposed. A 4-carboxyl-TEMPO nitroxide radical was covalently linked with 3-aminopropyl-trimethoxysilane to produce a silanizing TEMPO radical. Utilizing a facile reaction based on the copolymerization of silanizing TEMPO radicals with tetraethyl orthosilicate in reverse microemulsion, a TEMPO radicals doped SiO2 nanostructure was synthesized and coated on the surface of NaYF4:Yb,Er/NaYF4 upconversion nanoparticles (UCNPs) to generate a novel multifunctional nanoprobe, PEGylated UCNP@TEMPO@SiO2 for upconversion luminescence (UCL) and magnetic resonance dual-modality imaging. The electron spin resonance (ESR) signals generated by the TEMPO@SiO2 show an enhanced reduction resistance property for a period of time of up to 1 h, even in the presence of 5 mM ascorbic acid. The longitudinal relaxivity of PEGylated UCNPs@TEMPO@SiO2 nanocomposites is about 10 times stronger than that for free TEMPO radicals. The core-shell NaYF4:Yb,Er/NaYF4 UCNPs synthesized by this modified user-friendly one-pot solvothermal strategy show a significant enhancement of UCL emission of up to 60 times more than the core NaYF4:Yb,Er. Furthermore, the PEGylated UCNP@TEMPO@SiO2 nanocomposites were further used as multifunctional nanoprobes to explore their performance in the UCL imaging of living cells and T1-weighted MRI in vitro and in vivo.Nitroxide radicals, such as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its derivatives, have recently been used as contrast agents for magnetic resonance imaging (MRI) and electron

  10. Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Singh, Jagdeep

    , carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to

  11. Characterization of purified and Xerogel immobilized Novel Lignin Peroxidase produced from Trametes versicolor IBL-04 using solid state medium of Corncobs

    PubMed Central

    2012-01-01

    Background Cost-effective production of industrially important enzymes is a key for their successful exploitation on industrial scale. Keeping in view the extensive industrial applications of lignin peroxidase (LiP), this study was performed to purify and characterize the LiP from an indigenous strain of Trametes versicolor IBL-04. Xerogel matrix enzyme immobilization technique was applied to improve the kinetic and thermo-stability characteristics of LiP to fulfil the requirements of the modern enzyme consumer sector of biotechnology. Results A novel LiP was isolated from an indigenous T. versicolor IBL-04 strain. T. versicolor IBL-04 was cultured in solid state fermentation (SSF) medium of corn cobs and maximum LiP activity of 592 ± 6 U/mL was recorded after five days of incubation under optimum culture conditions. The crude LiP was 3.3-fold purified with specific activity of 553 U/mg after passing through the DEAE-cellulose and Sephadex-G-100 chromatography columns. The purified LiP exhibited a relatively low molecular weight (30 kDa) homogenous single band on native and SDS-PAGE. The LiP was immobilized by entrapping in xerogel matrix of trimethoxysilane (TMOS) and proplytetramethoxysilane (PTMS) and maximum immobilization efficiency of 88.6% was achieved. The free and immobilized LiPs were characterized and the results showed that the free and immobilized LiPs had optimum pH 6 and 5 while optimum temperatures were 60°C and 80°C, respectively. Immobilization was found to enhance the activity and thermo-stability potential of LiP significantly and immobilized LiP remained stable over broad pH and temperature range as compare to free enzyme. Kinetic constants Km and Vmax were 70 and 56 μM and 588 and 417 U/mg for the free and immobilized LiPs, respectively. Activity of this novel extra thermo-stable LiP was stimulated to variable extents by Cu2+, Mn2+ and Fe2+ whereas, Cystein, EDTA and Ag+ showed inhibitory effects. Conclusions The indigenously

  12. Nanoclay-Based Solid-Amine Adsorbents for Carbon Dioxide Capture

    NASA Astrophysics Data System (ADS)

    Roth, Elliot A.

    The objective of this research was to develop an efficient, low cost, recyclable solid sorbent for carbon dioxide adsorption from large point sources, such as coal-fired power plants. The current commercial way to adsorb CO 2 is to use a liquid amine or ammonia process. These processes are used in industry in the "sweetening" of natural gas, but liquid based technologies are not economically viable in the adsorption of CO2 from power plants due to the extremely large volume of CO2 and the inherent high regeneration costs of cycling the sorbent. Therefore, one of the main objectives of this research was to develop a novel sorbent that can be cycled and uses very little energy for regeneration. The sorbent developed here is composed of a nanoclay (montmorillonite), commonly used in the production of polymer nanocomposites, grafted with commercially available amines. (3-aminopropyl) trimethoxysilane (APTMS) was chemically grafted to the edge hydroxyl groups of the clay. While another amine, polyethylenimine (PEI), was attached to the surface of the clay by electrostatic interactions. To confirm the attachment of amines to the clay, the samples were characterized using FTIR and the corresponding peaks for amines were observed. The amount of amine loaded onto the support was determined by TGA techniques. The treated clay was initially analyzed for CO2 adsorption in a pure CO 2 stream. The adsorption temperatures that had the highest adsorption capacity were determined to be between 75°C and 100°C for all of the samples tested at atmospheric pressure. The maximum CO2 adsorption capacity observed was with nanoclay treated with both APTMS and PEI at 85°C. In a more realistic flue gas of 10% CO2 and 90% N2, the adsorbents had essentially the same overall CO2 adsorption capacity indicating that the presence of nitrogen did not hinder the adsorption of CO2. Adsorption studies in pure CO2 at room temperature under pressure from 40-300 PSI were also conducted. The average

  13. Gas phase condensation of superparamagnetic iron oxide-silica nanoparticles - control of the intraparticle phase distribution

    NASA Astrophysics Data System (ADS)

    Stötzel, C.; Kurland, H.-D.; Grabow, J.; Müller, F. A.

    2015-04-01

    consisting of a γ-Fe2O3 and a SiO2 hemisphere to γ-Fe2O3 NPs each carrying one small SiO2 lens on its surface, (ii) the multiple γ-Fe2O3 inclusions accumulate at the NPs' inner surfaces, and (iii) all composite NPs are covered by a thin layer of amorphous SiO2. These morphological characteristics are attributed to (i) the phase segregation of iron oxide and silica within the condensed Fe2O3-SiO2 droplets, (ii) the temperature gradient within these droplets which arises during rapid cooling in the CoLAVA process, and (iii) the significantly lower surface energy of silica when compared to iron oxide. The proposed growth mechanism of these Fe2O3-SiO2 composite NPs during gas phase condensation can be transferred to other systems comprising a glass-network former and another component that is insoluble in the regarding glass. Thus, our model will facilitate the development of novel functional composite NPs for applications in biomedicine, optics, electronics, or catalysis. Electronic supplementary information (ESI) available: Infrared absorption of the raw powders hematite and quartz (section S1), TEM investigation of the spatial distribution of the γ-Fe2O3 inclusions (section S2), particle size distributions of the Fe2O3@SiO2 nanopowder samples (section S3), ζ-potentials of aqueous dispersions of all γ-Fe2O3@SiO2 nanopowder samples (section S4), silanization of Fe2O3@SiO2 composite nanopowders with [3-(2,3-epoxypropoxy)-propyl]trimethoxysilane (section S5), and animation composed of TEM micrographs of Fe2O3@SiO2 NPs recorded at incrementally altered tilt angles (``Rotating Fe2O3@SiO2 NP.avi''). See DOI: 10.1039/c5nr00845j

  14. Characterization of medium-range order in organic-inorganic hybrid nanomaterials by fluctuation x-ray microscopy.

    SciTech Connect

    Fan, L.; Paterson, D.; McNulty, I.; Treacy, M. M. J.; Kumar, D.; Du, P.; Wiesner, U.; Gibson, J. M.; Experimental Facilities Division; Arizona State Univ.; Cornell Univ.

    2006-01-01

    Medium-range order (MRO) is crucial for understanding the nature of defects, mechanical behaviors, rheology in polymers, order-disorder processes and nucleation, etc. Measuring MRO is a challenging problem. Recently, we have developed fluctuation x-ray microscopy (FXM), which offers quantitative insight into MRO in materials at the micrometer scale. In this paper, we have applied our further-developed technique for characterization of MRO in nanomaterials. The study of mesostructured polymer-inorganic hybrid materials is an exciting, emerging research area offering enormous scientific and technological promise. The ability to control the shape, size and order of hybrid materials is a key requirement for their future development. By choice of the appropriate block copolymer system and inorganic precursors, the shape and size of the hybrid materials can be controlled at the nanometer scale. However, the control of formation and ordering of the nanostructures with medium to long range order remains a challenge that limits advances in many fields of nanotechnology. By using FXM here we examine the influence of sol-gel process variables on medium range order. The FXM method is described elsewhere. Two hybrids of PI-b-PEO/aluminosilicates with {approx}20nm phase separation length scale were prepared using known procedures. The PI-b-PEO amphiphilic block copolymer was synthesized via anionic polymerization techniques. Hybrids were fabricated by dissolving 0.05 g of PI-b-PEO in tetrahydrofuran (THF) (sample A) or a THF/chloroform mixture (28/72 v/v) (sample B) and adding 0.3 g of pre-hydrolyzed sol-gel inorganic precursors (3-glycidyloxypropyl-trimethoxysilane and aluminum-tri-secbutoxide). Samples were spin coated onto Si{sub 3}N{sub 4} windows on Si substrate. Both samples were UV/ozone treated for degrading the isoprene components in order to increase contrast for x-ray scattering experiments. The sample A was further cacinated at 350 C to remove all organic components