Science.gov

Sample records for poly allylamine synthesized

  1. Poly(styrenesulfonate)/poly(allylamine) multilayers: a route to favor endothelial cell growth on expanded poly(tetrafluoroethylene) vascular grafts.

    PubMed

    Moby, Vanessa; Boura, Cédric; Kerdjoudj, Halima; Voegel, Jean-Claude; Marchal, Luc; Dumas, Dominique; Schaaf, Pierre; Stoltz, Jean-François; Menu, Patrick

    2007-07-01

    Small-diameter synthetic vascular grafts of expanded poly(tetrafluoroethylene) (ePTFE) polymer concern one of the most common alternatives for the replacement of diseased vessels. However, high failure rates arise especially due to the lack of endothelial cells (ECs). EC seeding was developed to build a monolayer on the luminal surface. Because ECs show little or no adhesion on synthetic prostheses, it is necessary to promote their retention. On ePTFE surfaces we successfully deposited polyelectrolyte multilayer films (PMFs) consisting of poly(ethylenimine) (PEI), poly(sodium 4-styrenesulfonate) (PSS), and poly(allylamine hydrochloride) (PAH) to obtain PEI-(PSS-PAH)3 films. EC adhesion and spreading on modified ePTFE were assessed by scanning electron and confocal microscopies. Cell viability was evaluated by Alamar Blue assay. After 7 days of culture, the ePTFE modified with PMF exhibited improvements of EC viability as compared to that of the controls (nonmodified ePTFE) or even ePTFE coated by a PAH monolayer (p < 0.05). Moreover, the spreading of ECs was largely enhanced compared to that of the same controls, resulting in a healthy confluent cell monolayer formation. Positive staining for the von Willebrand factor confirmed the EC phenotype. Promoting EC attachment and function on ePTFE modified with PMFs could become in the future a promising treatment for synthetic small-diameter vascular grafts.

  2. Characterization of poly(allylamine) as a polymeric ligand for ion-exchange protein chromatography.

    PubMed

    Li, Ming; Li, Yanying; Yu, Linling; Sun, Yan

    2017-02-24

    This work reports poly(allylamine) (PAA), as a polymeric ion-exchange ligand for protein chromatography. Sepharose FF was modified with PAA, and six anion exchangers with ionic capacities (ICs) from 165 to 618mmol/L were prepared. Inverse size exclusion chromatography, adsorption equilibrium, uptake kinetics and column elution were performed. It was found that both the adsorption capacity and effective diffusivity maintained low values in the IC range of 165-373mmol/L, but they started to increase beyond 373mmol/L, and increased by 80% and 23 times, respectively, when the IC reached 618mmol/L. Interestingly, a drastic decrease of pore size was observed around the IC of 373mmol/L. The results suggest that the PAA chains played an important role in protein adsorption by altering the inner pore structure of the gels. It is considered that, PAA chains turn from inextensible states with multipoint-grafting on the pore surface at low coupling densities (IC<373mmol/L) to closer, extended and flexible grafting states with less coupling points at higher coupling densities (IC>373mmol/L). These characters of the grafted chains at higher IC values benefit in protein adsorption by three-dimensional binding and encouraged the happening of "chain delivery" of bound proteins on the chains. Besides, the ion exchangers showed favorable adsorption and uptake properties in a wide ionic strength range, 0-500mmol/L NaCl, indicating much better salt tolerance feature than the so-far reported ion exchangers. Moreover, a mild condition of pH 5.0 offered effective recovery of bound proteins in elution chromatography. The results indicate that the PAA-based anion exchanger of a high IC value is promising for high-capacity protein chromatography dealing with feedstock of a wide range of ionic strengths.

  3. Fabrication and photoelectric response of poly(allylamine hydrochloride)/PM thin films by layer-by-layer deposition technique.

    PubMed

    Chu, Jinfang; Li, Xingchang; Zhang, Jianping; Tang, Ji'an

    2003-05-23

    Thin films of poly(allylamine hydrochloride) (PAH) and bacteriorhodopsin (bR) embedded in purple membrane (PM) have been prepared by layer-by-layer (LBL) self-assembly technique. The results obtained by UV-Vis spectroscopy and atomic force microscopy (AFM) analysis showed that the biological activity of bR was preserved and PM fragments could be well oriented onto the ITO substrate. A photo-electrochemical cell with the structure of ITO/(PAH/PM)(n)/electrolyte (0.5M KCl)/Pt was fabricated and studied. The photocurrent peaks of (PAH/PM)(6) corresponding to light-on and light-off were about 200 and 100 nA/cm(2), respectively, with the former enhanced 30% higher than that of the reference films made of (PDAC/PM)(6).

  4. Enhanced accumulation and visible light-assisted degradation of azo dyes in poly(allylamine hydrochloride)-modified mesoporous silica spheres

    SciTech Connect

    Tao Xia Liu Bing; Hou Qian; Xu Hui; Chen Jianfeng

    2009-02-04

    A new route for the economic and efficient treatment of azo dye pollutants is reported, in which surface-modified organic-inorganic hybrid mesoporous silica (MS) spheres were chosen as microreactors for the accumulation and subsequent photodegradation of pollutants in defined regions. The surface-modified silica materials were prepared by anchoring the polycationic species such as poly(allylamine hydrochloride) on MS spheres via a simple wet impregnation method. The as-synthesized spheres with well-defined porous structures exhibited 15 times of accumulating capacity for orange II and Congo red compared to that of the pure MS spheres. Diffuse reflectance UV-vis spectroscopy and confocal laser scanning microscopy demonstrated that the accumulated orange II and CR in defined MS spheres were rapidly degraded in the presence of Fenton reagent under visible radiation. Kinetics analysis in recycling degradation showed that the as-synthesized materials might be utilized as environment-friendly preconcentrators/microreactors for the remediation of dye wastewater.

  5. pH-sensing properties of cascaded long- and short-period fiber grating with poly acrylic acid/poly allylamine hydrochloride thin-film overlays

    NASA Astrophysics Data System (ADS)

    Yang, Ying

    2014-11-01

    Based on coupled-mode theory and transfer matrix method, the mode coupling mechanism and the reflection spectral properties of coated cascaded long- and short-period gratings (CLBG) are discussed. The effects of the thin-film parameters (film refractive index and film thickness) on the reflection spectra of the coated CLBG are simulated. By using electrostatic self-assembly method, poly acrylic acid (PAA) and poly allylamine hydrochloride (PAH) multilayer molecular pH-sensitive thin-films are assembled on the surface of the partial corroded CLBG. When the CLBG coated with PAA/PAH films are used to sense pH values, the resonant wavelengths of the CLBG have almost no shift, whereas the resonance peak reflectivities change with pH values. In addition, the sensitivities of the resonance peak reflectivities responding to pH values are improved by an order of magnitude.

  6. Preparation and characterization of magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted magnetic solid phase extraction of some metal ions.

    PubMed

    Khan, Mansoor; Yilmaz, Erkan; Sevinc, Basak; Sahmetlioglu, Ertugrul; Shah, Jasmin; Jan, Muhammad Rasul; Soylak, Mustafa

    2016-01-01

    Magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) (MGO-DVB-VA) was synthesized and used for magnetic solid phase extraction of Pb(II), Cd(II), Cu(II), Ni(II) and Co(II) prior to their determination by flame atomic absorption spectroscopy. The adsorbent surface functional group was characterized by using FT-IR and Raman spectroscopy. XRD pattern was used to determine the layers of GO. Surface morphology and elemental composition of the adsorbent were evaluated by using SEM and EDX analysis. Various parameters, effecting adsorption efficiency like initial solution pH, adsorbent dose, type and volume of eluent, volume of sample and diverse ions effects were optimized. The preconcentration factor (PF) is 40 for all the metals and the limits of detection for Pb, Cd, Cu, Ni and Co are in the range of 0.37-2.39 µg L(-1) and relative standard deviation below 3.1%. The method was validated by using the method for certified reference materials (Tobacco Leaves (INCT-OBTL-5), Tomato Leaves (1573a), Certified Water (SPS-ww2) and Certified Water (TMDA 64-2)). The method was successfully applied for natural water and food samples.

  7. Diffusion of polyphosphates into (poly(allylamine)-montmorillonite) multilayer films: flame retardant-intumescent films with improved oxygen barrier.

    PubMed

    Laachachi, Abdelghani; Ball, Vincent; Apaydin, Kadir; Toniazzo, Valérie; Ruch, David

    2011-11-15

    The present paper relies on the original idea to design multifunctional coatings, and in particular highly efficient intumescent flame retardant coatings, based on the diffusion of polyphosphates (PSPs) in exponentially growing "layer-by-layer" films made from montmorillonite (MMT) and poly(allylamine) (PAH). Here, we used polyphosphates as an acid source, polyallylamine as both a carbon source and a swelling agent, and finally clays to reinforce the intumescent char strength and also for their oxygen barrier property. The coatings made from the alternated deposition of n = 60 layer pairs of PAH and MMT reach a considerable thickness of ∼18 μm with well-defined ordering of the MMT in the direction parallel to the substrate. Structural, morphological, mechanical, gas barrier, and fire resistance properties of these films have been studied. Excellent oxygen barrier properties and extraordinary fire resistance properties are demonstrated based on the basis of a strong increase of the time to ignition and on a decrease of the heat release rate of polylactide substrates during mass loss calorimeter tests. This new and innovative intumescent flame retardant system based on (PAH-MMT)(n)-PSP coatings is a promising universal treatment for current polymeric materials.

  8. Characterization of charge properties of an ultrafiltration membrane modified by surface grafting of poly(allylamine) hydrochloride.

    PubMed

    Dejeu, J; Lakard, B; Fievet, P; Lakard, S

    2009-05-01

    A polyethersulfone ultrafiltration membrane was functionalized by a cationic polyelectrolyte, the poly(allylamine) hydrochloride (PAH). The influence of the time of adsorption of PAH on the membrane charge properties was studied. Several characterization techniques were used to investigate the membrane modification. Tangential and transmembrane streaming potential measurements were conducted to characterize the outer and inner surfaces of the membrane, respectively. Both techniques indicated that the surface modification of the membrane was efficient. The charge of the outer surface was reversed (from negative values for the unmodified membrane to positive values for the modified membrane) and the charge of the inner surface was neutralized after adsorption of the cationic polyelectrolyte onto the pore walls. The modification of both the outer surface of the membrane and the pore walls was also put in evidence with membrane potential measurements. It was found that the charge of the PAH-modified membrane is affected by the time of immersion in PAH solution. Experimental data seem to show a fast modification of the membrane for the first 15 min; nevertheless, the modification was more pronounced after 24 h of PAH adsorption. Diffusion experiments carried out with unmodified and modified membranes for four salts (KCl, NaCl, MgCl, and CaCl(2)) showed a decrease in the salt permeability after functionalization of the membrane. The permeability decrease was greater for 2:1 salts than for 1:1 salts. This decrease was explained by electrostatic interactions.

  9. Electrospun polyamide 6/poly(allylamine hydrochloride) nanofibers functionalized with carbon nanotubes for electrochemical detection of dopamine.

    PubMed

    Mercante, Luiza A; Pavinatto, Adriana; Iwaki, Leonardo E O; Scagion, Vanessa P; Zucolotto, Valtencir; Oliveira, Osvaldo N; Mattoso, Luiz H C; Correa, Daniel S

    2015-03-04

    The use of nanomaterials as an electroactive medium has improved the performance of bio/chemical sensors, particularly when synergy is reached upon combining distinct materials. In this paper, we report on a novel architecture comprising electrospun polyamide 6/poly(allylamine hydrochloride) (PA6/PAH) nanofibers functionalized with multiwalled carbon nanotubes, used to detect the neurotransmitter dopamine (DA). Miscibility of PA6 and PAH was sufficient to form a single phase material, as indicated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), leading to nanofibers with no beads onto which the nanotubes could adsorb strongly. Differential pulse voltammetry was employed with indium tin oxide (ITO) electrodes coated with the functionalized nanofibers for the selective electrochemical detection of dopamine (DA), with no interference from uric acid (UA) and ascorbic acid (AA) that are normally present in biological fluids. The response was linear for a DA concentration range from 1 to 70 μmol L(-1), with detection limit of 0.15 μmol L(-1) (S/N = 3). The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and biosensors.

  10. Non-covalent assembly of poly(allylamine hydrochloride)/triethylamine microcapsules with ionic strength-responsiveness and auto-fluorescence.

    PubMed

    Li, Huiying; Zheng, Honghao; Tong, Weijun; Gao, Changyou

    2017-06-15

    Ionic strength-responsive microcapsules with auto-fluorescence were fabricated by incubation of poly(allylamine hydrochloride) (PAH)-doped CaCO3 particles in triethylamine (Et3N), followed by core removal using HCl. Based on the combination of hydrophobic interaction and hydrogen bonding, PAH and Et3N formed a complex with a molar ratio of 3:1 (repeating unit of PAH: Et3N). The as-prepared capsules showed extraordinary stability against 1M HCl, 1M NaOH and 6M urea solutions, and could swell or shrink reversibly in response to the ionic strength. Furthermore, the capsules possessed auto-fluorescence, allowing easily tracking of capsules during applications. Such interaction may be expanded to formation of stimuli-responsive multilayer films and other colloidal particles.

  11. Formation and Structure of Calcium Carbonate Thin Films and Nanofibers Precipitated in the Presence of Poly(Allylamine Hydrochloride) and Magnesium Ions.

    PubMed

    Cantaert, Bram; Verch, Andreas; Kim, Yi-Yeoun; Ludwig, Henning; Paunov, Vesselin N; Kröger, Roland; Meldrum, Fiona C

    2013-12-23

    That the cationic polyelectrolyte poly(allylamine hydrochloride) (PAH) exerts a significant influence on CaCO3 precipitation challenges the idea that only anionic additives have this effect. Here, we show that in common with anionic polyelectrolytes such as poly(aspartic acid), PAH supports the growth of calcite thin films and abundant nanofibers. While investigating the formation of these structures, we also perform the first detailed structural analysis of the nanofibers by transmission electron microscopy (TEM) and selected area electron diffraction. The nanofibers are shown to be principally single crystal, with isolated domains of polycrystallinity, and the single crystal structure is even preserved in regions where the nanofibers dramatically change direction. The formation mechanism of the fibers, which are often hundreds of micrometers long, has been the subject of intense speculation. Our results suggest that they form by aggregation of amorphous particles, which are incorporated into the fibers uniquely at their tips, before crystallizing. Extrusion of polymer during crystallization may inhibit particle addition at the fiber walls and result in local variations in the fiber nanostructure. Finally, we investigate the influence of Mg(2+) on CaCO3 precipitation in the presence of PAH, which gives thinner and smoother films, together with fibers with more polycrystalline, granular structures.

  12. Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): structure and electron irradiation effects.

    PubMed

    Gontard, Lionel C; Fernández, Asunción; Dunin-Borkowski, Rafal E; Kasama, Takeshi; Lozano-Pérez, Sergio; Lucas, Stéphane

    2014-12-01

    Hybrid (organic shell-inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C3H5NH2. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed.

  13. Layer-by-layer self-assembled ultrathin multilayer films of lanthanide polyoxometalates and poly(allylamine hydrochloride) and their photoluminescent properties.

    PubMed

    Wang, Yonghui; Wang, Xinlong; Hu, Changwen

    2002-05-15

    Ultrathin multilayer films of two lanthanide polyoxometalates (LPOMs), K(17)[Eu(P(2)W(17)O(61))(2)] (EPW) and K(13)[Eu(SiW(11)O(39))(2)] (ESW), and poly(allylamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. UV-vis spectroscopy and ellipsometry respectively show that the absorbance values at characteristic wavelengths and the thicknesses of the multilayer films increase linearly with the number of LPOM/PAH bilayers, suggesting that the deposition process is linear and highly reproducible from layer to layer. Average thicknesses of ca. 3.4 and 2.4 nm were determined for the EPW/PAH and ESW/PAH bilayers by ellipsometry, respectively. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) images provide the surface morphology of the LPOM/PAH films, indicating that the film surface is relatively uniform and smooth. The photoluminescent properties of these films have also been investigated by fluorescence spectroscopy. The LPOM/PAH multilayer film has a good thermal stability as shown by UV-vis, X-ray photoelectron, and fluorescence spectra.

  14. Study of the Impact of Polyanions on the Formation of Lipid Bilayers on Top of Polyelectrolyte Multilayers with Poly(allylamine hydrochloride) as the Top Layer.

    PubMed

    Diamanti, Eleftheria; Andreozzi, Patrizia; Kirby, Christopher; Anguiano, Ramiro; Yate, Luis; Heinz, Hendrik; Ziolo, Ronald F; Donath, Edwin; Moya, Sergio Enrique

    2017-02-09

    The impact of polyanions on the formation of lipid bilayers on top of polyelectrolyte multilayers (PEMs) with poly(allylamine hydrochloride) (PAH) as the top layer is studied for the deposition of vesicles of mixed lipid composition, 50:50 molar ratio of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and negatively charged 1,2-dioleoyl-sn-glycero-3-phospho-l-serine (DOPS). PEMs are assembled with polystyrene sulfonate (PSS), poly(acrylic acid) (PAA), and alginic acid sodium salt (Alg) as polyanions. The assembly of the vesicles on the PEMs is followed by means of the quartz crystal microbalance with dissipation. Fluorescence recovery after photobleaching measurements are applied to evaluate bilayer formation. Whereas a bilayer is formed on top of PAH/PSS multilayers, the vesicles are adsorbed on top of PAH/Alg and PAH/PAA multilayers, remaining unruptured or only partially fused. The influence of the surface composition of the PEM and of the bulk properties of the film are analyzed. The phosphate ions present in phosphate-buffered saline (PBS) play a fundamental role in bilayer formation on top of PAH/PSS as they complex with PAH and render the surface potential close to zero. For PAH/PAA and PAH/Alg, PBS renders the surface negative. X-ray photoelectron spectroscopy shows that the dibasic phosphate ions from PBS complex preferentially with PAH in PAH/PAA and PAH/Alg multilayers, whereas monobasic phosphates complex with PAH in PAH/PSS. An explanation for the absence of bilayer formation on PAH/PAA and PAH/Alg is given on the basis of the different affinities of phosphate ions for PAH in combination with the different polyanions.

  15. Exothermic-Endothermic Transition in the Titration of Poly(allylamine chloride) with Sodium Hexametaphoshate Associated with a Change in the Proton Release Regime.

    PubMed

    Maechling, Clarisse; Ball, Vincent

    2016-05-26

    The formation of complexes (aggregates) between oppositely charged macromolecular species or between macromolecular species and multivalent ions is a fascinating fundamental research topic that allows one to understand fundamental processes in biology and in polymer science. In addition interpolyelectrolyte complexes hold by strong interactions and polyelectrolyte coacervates in which the stabilizing interactions are weaker find many applications in food and in colloidal science. The interactions between oppositely charged species are usually investigated as a function of intensive variables like the temperature, the pH, the ionic strength, and parameters related to the charged species themselves (molecular mass, charge density, charge distribution, and so forth). It appeared however in the past few years that the interaction kinetics is also of fundamental importance; a fast mixing of the interacting species can lead to the formation of frozen and out-of-equilibrium structures. The present investigation is aimed to study the interactions between a small polyphosphate (sodium hexametaphosphate) (HMP) and a linear polyamine (poly(allylamine hydrochloride)) (PAH) from both a thermodynamic and kinetic point of view as a function of the ionic strength (in NaCl solutions). It is found, unexpectedly, that the interaction is of biphasic nature with a first exothermic regime followed by an endothermic regime. The transition between both regimes is ionic strength independent between 10 and 2000 mM emphasizing the strong interactions between both species. It occurs at a charge ratio of about 0.4 between the number of negative and positive charges and is correlated with proton release in the exothermic regime and a proton uptake in the endothermic regime. When HMP solutions are titrated in PAH solutions the turbidity of the mixtures is not the same as that obtained during the reverse titration at a given charge ratio, emphasizing the difficulty to establish an "equilibrium

  16. Syntheses of sugar poly(orthoesters) through reverse anomeric effect.

    PubMed

    Li, Lingyao; Wang, Jun; Obrinske, Melissa; Milligan, Ian; O'Hara, Kylie; Bitterman, Lindsay; Du, Wenjun

    2015-04-25

    High molecular weight sugar poly(orthoesters) were synthesized through reverse anomeric effect (RAE). We demonstrated that when RAE-enabled promoters, such as 4-(dimethylamino)pyridine (DMAP), triphenylphosphine (TPP) or imidazole, were employed, efficient polymerizations were achieved, giving sugar poly(orthoesters) with molecular weights up to 18 kDa.

  17. pH- and sugar-sensitive multilayer films composed of phenylboronic acid (PBA)-modified poly(allylamine hydrochloride) (PBA-PAH) and poly(vinyl alcohol) (PVA): A significant effect of PBA content on the film stability.

    PubMed

    Seno, Masaru; Yoshida, Kentaro; Sato, Katsuhiko; Anzai, Jun-ichi

    2016-05-01

    Multilayer thin films composed of phenylboronic acid (PBA)-modified poly(allylamine hydrochloride) (PAH), PBA-PAH, with different PBA contents were prepared to study the effect of PBA content on the stability of the films. An alternate deposition of PBA-PAH and poly(vinyl alcohol) (PVA) on the surface of a quartz slide afforded multilayer films through forming boronate ester bonds between PBA-PAH and PVA. The 10-layered (PBA-PAH/PVA)10 films constructed using PBA-PAHs containing 16% and 26% PBA residues were stable in aqueous solutions over the range of pH 4.0-10.0, whereas the multilayer films composed of PBA-PAHs with 5.9% and 8.3% PBA decomposed at pH 8.0 or lower. The pH-sensitive decomposition of the films was rationalized based on the destabilization of the boronate ester bonds in neutral and acidic solutions. In addition, the (PBA-PAH/PVA)10 films decomposed in glucose and fructose solutions as a result of competitive binding of sugars to PBA-PAH in the films. The sugar response of the films depended on the PBA content in PBA-PAH. The (PBA-PAH/PVA)10 films consisting of 16% and 26% PBA-substituted PBA-PAHs are sensitive to physiological relevant level of glucose at pH7.4 while stable in glucose-free solution, suggesting a potential use of the films in constructing glucose-induced delivery systems.

  18. Indirect determination of sulfite using a polyphenol oxidase biosensor based on a glassy carbon electrode modified with multi-walled carbon nanotubes and gold nanoparticles within a poly(allylamine hydrochloride) film.

    PubMed

    Sartori, Elen Romão; Vicentini, Fernando Campanhã; Fatibello-Filho, Orlando

    2011-12-15

    The modification of a glassy carbon electrode with multi-walled carbon nanotubes and gold nanoparticles within a poly(allylamine hydrochloride) film for the development of a biosensor is proposed. This approach provides an efficient method used to immobilize polyphenol oxidase (PPO) obtained from the crude extract of sweet potato (Ipomoea batatas (L.) Lam.). The principle of the analytical method is based on the inhibitory effect of sulfite on the activity of PPO, in the reduction reaction of o-quinone to catechol and/or the reaction of o-quinone with sulfite. Under the optimum experimental conditions using the differential pulse voltammetry technique, the analytical curve obtained was linear in the concentration of sulfite in the range from 0.5 to 22 μmol L(-1) with a detection limit of 0.4 μmol L(-1). The biosensor was applied for the determination of sulfite in white and red wine samples with results in close agreement with those results obtained using a reference iodometric method (at a 95% confidence level).

  19. Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks

    DOE PAGES

    Kumarasamy, Elango; Sanders, Samuel N.; Pun, Andrew B.; ...

    2016-02-09

    Here, we describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki–Miyaura cross-coupling reactions. This synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entiremore » visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV–vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. The effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics.« less

  20. Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks

    SciTech Connect

    Kumarasamy, Elango; Sanders, Samuel N.; Pun, Andrew B.; Vaselabadi, Saeed Ahmadi; Low, Jonathan Z.; Sfeir, Matthew Y.; Steigerwald, Michael L.; Stein, Gila E.; Campos, Luis M.

    2016-02-09

    Here, we describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki–Miyaura cross-coupling reactions. This synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entire visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV–vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. The effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics.

  1. Stable biopassive insulation synthesized by initiated chemical vapor deposition of poly(1,3,5-trivinyltrimethylcyclotrisiloxane).

    PubMed

    O'Shaughnessy, W S; Murthy, S K; Edell, D J; Gleason, K K

    2007-08-01

    The permanent implantation of electronic probes capable of recording neural activity patterns requires long-term electrical insulation of these devices by biopassive coatings. In this work, the material properties and neural cell compatibility of a novel polymeric material, poly(trivinyltrimethylcyclotrisiloxane) (poly(V3D3)), are demonstrated to be suitable for application as permanently bioimplanted electrically insulating films. The poly(V3D3) polymeric films are synthesized by initiated chemical vapor deposition (iCVD), allowing for conformal and flexible encapsulation of fine wires. The poly(V3D3) also exhibits high adhesive strength to silicon substrates, a common material of manufacture for neural probes. The poly(V3D3) films were found to be insoluble in both polar and nonpolar solvents, consistent with their highly cross-linked structure. The films are pinhole-free and extremely smooth, having a root-mean-square (rms) roughness of 0.4 nm. The material possesses a bulk resistivity of 4 x 1015 Ohm-cm exceeding that of Parylene-C, the material currently used to insulate neurally implanted devices. The iCVD poly(V3D3) films are hydrolytically stable and are demonstrated to maintain their electrical properties under physiological soak conditions, and constant electrical bias, for more than 2 years. In addition, biocompatibility studies with PC12 neurons demonstrate that this material is noncytotoxic and does not influence cell proliferation.

  2. Allylamine-mediated DNA attachment to polycrystalline diamond surface

    NASA Astrophysics Data System (ADS)

    Zhuang, H.; Srikanth, Vadali. V. S. S.; Jiang, X.; Luo, J.; Ihmels, H.; Aronov, I.; Wenclawiak, B. W.; Adlung, M.; Wickleder, C.

    2009-10-01

    Allylamine, an unsaturated short carbon chain amine was used to mediate ss-DNA attachment to an H-terminated polycrystalline diamond thin film surface for biosensoric applications. At first, allylamine was photochemically tethered onto the diamond film surface; ss-DNA was then attached via the allylamine linkage. The DNA molecules are then hybridized with the complementary DNA molecules containing fluorescence labels followed by denaturing. Time-of-fight secondary ion mass spectrometry and fluorescence spectroscopy are used to confirm the allylamine bonding and the covalent DNA bonding to the diamond film surface, respectively.

  3. Preparation and structural characterization of poly-mannose synthesized by phosphoric acid catalyzation under microwave irradiation.

    PubMed

    Wang, Haisong; Cheng, Xiangrong; Shi, Yonghui; Le, Guowei

    2015-05-05

    Poly-mannose with molecular weight of 2.457 kDa was synthesized using d-mannose as substrate and phosphoric acid as catalyst under the condition of microwave irradiation for the first time. The optimum reaction conditions were microwave output power of 900 W, temperature 115°C, proton concentration 2.5 mol/L, and microwave irradiation time 5 min. The actual maximum yield was 91.46%. After purified by Sepherdex G-25 column chromatography, the structural features of poly-mannose were investigated by high-performance anion-exchange chromatography (HPAEC), high-performance gel-permeation chromatography (HPGPC), infrared (IR) spectroscopy, methylation analysis and NMR spectroscopy analysis ((1)H, (13)C, COSY, TOCSY, HMQC, and HMBC). HPAEC analysis showed that the composition of synthetic polysaccharides was d-mannose, its purity was demonstrated by HPGPC as a single symmetrical sharp peak, and additionally IR spectra demonstrated the polymerization of d-mannose. Methylation analysis and NMR spectroscopy revealed that the backbone of poly-mannose consisting of (1→3)-linked β-d-Manp, (1→3)-linked α-d-Manp, and (1→6)-linked α-d-Manp residues, and the main chain were branched at the O-2, O-3, O-4, O-6 position.

  4. Cytotoxicity and biocompatibility evaluation of a poly(magnesium acrylate) hydrogel synthesized for drug delivery.

    PubMed

    Cheddadi, Maha; López-Cabarcos, Enrique; Slowing, Karla; Barcia, Emilia; Fernández-Carballido, Ana

    2011-07-15

    We report the synthesis and characterization as well as cytotoxicity and biocompatibility studies of a poly(magnesium acrylate) hydrogel (PAMgA) developed for drug delivery applications. Two hydrogels with different mesh sizes, large and short, were synthesized (L-C PAMgA and S-C PAMgA). The hydrogels were characterized through swelling, FT-IR and DSC. Cytotoxicity in vitro was evaluated on cell line NIH-3T3 fibroblasts via direct contact and two indirect contact methods (MTT and flow citometry). Both PAMgA hydrogels exhibited low cytotoxicity with survival rates higher than 90%. To select their administration route, biocompatibility was evaluated after intraperitoneal, subcutaneous, and oral administration to mice of both hydrogels at different dose ranges. Swelling percentages obtained were 33.3 ± 4.2% and 166.7 ± 8.3% for L-C PAMgA and S-C PAMgA respectively, showing a great difference in both hydrogels. Among the administration routes assayed, the hydrogels were well tolerated after oral administration of a wide dose range (10-500 mg/kg), thereby indicating that both PAMgA hydrogels are excellent candidates for oral administration due to their in vitro biocompatibility and oral non-toxicity. These results together with the fact that their synthesis is simple and inexpensive make them good candidates for the design of oral drug delivery devices.

  5. Poly(vinyl ester) Block Copolymers Synthesized by Reversible Addition−Fragmentation Chain Transfer Polymerizations

    SciTech Connect

    Lipscomb, Corinne E.; Mahanthappa, Mahesh K.

    2009-07-31

    Homopolymerizations and block copolymerizations of vinyl acetate (VAc), vinyl pivalate (VPv), and vinyl benzoate (VBz) by reversible addition-fragmentation chain transfer (RAFT) polymerization have been studied. Polymerizations of VAc initiated with 2,2{prime}-azobis(isobutyronitrile) (AIBN) at 60 C using two different xanthate RAFT agents C{sub 2}H{sub 5}OC(=S)SR (R = -CH(CH{sub 3})CO{sub 2}C{sub 2}H{sub 5} (1) and -CH(CH{sub 3})O{sub 2}CC(CH{sub 3}){sub 3} (2)) were examined to elucidate the dependence of the polydispersities of the resulting polymers on the RAFT agent leaving group R. RAFT agent 2, in which the leaving R-group mimics a growing vinyl ester polymer chain, consistently yields poly(vinyl acetates) having broader polydispersities than those synthesized using 1 (M{sub n} = 3.6-14 kg/mol and M{sub w}/M{sub n} = 1.15-1.33). While VPv exhibits similar controlled polymerization behavior to VAc, RAFT homopolymerizations of VBz mediated by 1 indicate this electron-deficient vinyl ester requires higher temperatures to effect controlled polymerizations to yield polymers having M{sub n} = 4-14 kg/mol and M{sub w}/M{sub n} = 1.29-1.53. Chain extension reactions from xanthate-terminated vinyl ester homopolymers with VAc, VPv, and VBz proceed with variable efficiencies to furnish block copolymers that microphase separate in the melt state as determined by small-angle X-ray scattering.

  6. Antimicrobial lubricant formulations containing poly(hydroxybenzene)-trimethoprim conjugates synthesized by tyrosinase.

    PubMed

    Gonçalves, Idalina; Botelho, Cláudia M; Teixeira, Ana; Abreu, Ana S; Hilliou, Loïc; Silva, Carla; Cavaco-Paulo, Artur

    2015-05-01

    Poly(hydroxybenzene)-trimethoprim conjugates were prepared using methylparaben as substrate of the oxidative enzyme tyrosinase. MALDI-TOF MS analysis showed that the enzymatic oxidation of methylparaben alone leads to the poly(hydroxybenzene) formation. In the presence of trimethoprim, the methylparaben tyrosinase oxidation leads poly(hydroxybenzene)-trimethoprim conjugates. All of these compounds were incorporated into lubricant hydroxyethyl cellulose/glycerol mixtures. Poly(hydroxybenzene)-trimethoprim conjugates were the most effective phenolic structures against the bacterial growth reducing by 96 and 97% of Escherichia coli and Staphylococcus epidermidis suspensions, respectively (after 24 h). A novel enzymatic strategy to produce antimicrobial poly(hydroxybenzene)-antibiotic conjugates is proposed here for a wide range of applications on the biomedical field.

  7. Investigation of nonfouling polypeptides of poly(glutamic acid) with lysine side chains synthesized by EDC·HCl/HOBt chemistry.

    PubMed

    Yang, Qinghua; Li, Wenchen; Wang, Longgang; Wang, Guangzhi; Wang, Zhen; Liu, Lingyun; Chen, Shengfu

    2014-01-01

    Nonfouling polypeptides with homogenous alternating charges draw peoples' attentions for their potential capability in biodegradation. Homogenous glutamic acid (E) and lysine (K) polypeptides were proposed and synthesized before. In this work, a new polypeptide formed by poly(glutamic acid) with lysine side chains (poly(E)-K) was synthesized by facile EDC·HCl/HOBt chemistry and investigated. Results show that these polypeptides also have good nonspecific protein resistance determined by enzyme-linked immunosorbent assay. The lowest nonspecific adsorption of the model proteins, anti-IgG and fibrinogen (Fg), on the self-assembling monolayers (SAMs) surface of poly(E)-K was only 3.3 ± 1.8 and 4.4 ± 1.6%, respectively, when protein adsorption on tissue culture polystyrene surface was set as 100%. And, the relative nonspecific protein adsorption increases when the polypeptide molecular weight increases due to the repression of low density polymer brushes. Moreover, almost no obvious cytotoxicity and hemolytic activity in vitro were detected. This work suggests that polypeptides with various formats of homogenous balanced charges could achieve excellent nonspecific protein resistance, which might be the intrinsic reason for the coexistence of high concentration serum proteins in blood.

  8. Syntheses, characterization, and in vitro degradation of ethyl cellulose-graft-poly(epsilon-caprolactone)-block-poly(L-lactide) copolymers by sequential ring-opening polymerization.

    PubMed

    Yuan, Weizhong; Yuan, Jinying; Zhang, Fengbo; Xie, Xuming

    2007-04-01

    Well-defined ethyl cellulose-graft-poly(epsilon-caprolactone) (EC-g-PCL) graft copolymers were successfully synthesized via ring-opening polymerization (ROP) of epsilon-caprolactone (CL) with an ethyl cellulose (EC) initiator and a tin 2-ethylhexanoate (Sn(Oct)2) catalyst in xylene at 120 degrees C. Then, novel ethyl cellulose-graft-poly(epsilon-caprolactone)-block-poly(L-lactide) (EC-g-PCL-b-PLLA) graft-block copolymers were prepared by ROP of L-lactide (L-LA) with a hydroxyl-terminated EC-g-PCL macroinitiator and Sn(Oct)2 catalyst in bulk at 120 degrees C. Various graft and block lengths of EC-g-PCL and EC-g-PCL-b-PLLA copolymers were obtained by adjusting the molar ratios of CL monomer to EC and the L-LA monomer to CL. The thermal properties and crystalline morphologies of EC-g-PCL and EC-g-PCL-b-PLLA copolymers were different from those of linear PCL. The in vitro degradation rate of EC-g-PCL-b-PLLA was faster than those of linear PCL and EC-g-PCL due to the presence of PLLA blocks.

  9. Self-assembly of brush-like poly[poly(ethylene glycol) methyl ether methacrylate] synthesized via aqueous atom transfer radical polymerization.

    PubMed

    Hussain, Hazrat; Mya, Khine Yi; He, Chaobin

    2008-12-02

    Self-assembly of brush-like well-defined poly[poly(ethylene glycol) methyl ether methacrylate] homopolymers, abbreviated as P(PEGMA-475) and P(PEGMA-1100) is investigated in aqueous solution by employing dynamic/static light scattering (DLS/SLS) and transmission electron microscopy (TEM), whereas 475 and 1100 is molar mass of the respective PEGMA macromonomer. The mentioned brush-like homopolymers are synthesized by aqueous ATRP at room temperature. The critical association concentration (CAC) of the synthesized polymers in water depends on the length of the PEG side chains but not on the overall molar mass of the polymer. Thus, approximately the same CAC of approximately 0.35 mg/mL is estimated for various P(PEGMA-1100) samples, and approximately 0.7 mg/mL is estimated for P(PEGMA-475) series. All the investigated P(PEGMA-1100) samples form multimolecular micelles in aqueous solution, where the hydrodynamic size (Rh) and the aggregation number (Nagg) of micelles decreases as the molecular weight of P(PEGMA-1100) increases. This can be attributed to the increased steric hindrances between the PEG side chains in corona of micelles formed by higher molar mass P(PEGMA-1100). The tendency of micelle formation by samples of P(PEGMA-475) series is significantly lower than that of P(PEGMA-1100) series, as demonstrated by their significantly higher CAC and micelles of lower Nagg. The Rh of micelles does not depend strongly on polymer concentration, which suggests that these micelles are formed via the closed association model. Micelles formed by P(PEGMA-1100) series slightly shrink with increase in temperature from 25 to 60 degrees C, while those of P(PEGMA-475) series are found to be insensitive to the same temperature variation. Finally, TEM is carried out to visualize the formed micelles after transferring the aqueous solution to carbon film.

  10. Plasma polymerized allylamine coated quartz particles for humic acid removal.

    PubMed

    Jarvis, Karyn L; Majewski, Peter

    2012-08-15

    Allylamine plasma polymerization has been used to modify the surface of quartz particles for humic acid removal via an inductively coupled rotating barrel plasma reactor. Plasma polymerized allylamine (ppAA) films were deposited at a power of 25 W, allylamine flow rate of 4.4 sccm and polymerization times of 5-60 min. The influence of polymerization time on surface chemistry was investigated via X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and electrokinetic analysis. Acid orange 7 adsorption/desorption quantified the number of surface amine groups. Humic acid removal via ppAA quartz particles was examined by varying pH, removal time, humic acid concentration, and particle mass. Increasing the polymerization time increased the concentration of amine groups on the ppAA quartz surface, thus also increasing the isoelectric point. ToF-SIMS demonstrated uniform distribution of amine groups across the particle surface. Greatest humic acid removal was observed at pH 5 due to electrostatic attraction. At higher pH values, for longer polymerization times, humic acid removal was also observed due to hydrogen bonding. Increasing the initial humic acid concentration increased the mass of humic acid removed, with longer polymerization times exhibiting the greatest increases. Plasma polymerization using a rotating plasma reactor has shown to be a successful method for modifying quartz particles for the removal of humic acid. Further development of the plasma polymerization process and investigation of additional contaminants will aid in the development of a low cost water treatment system.

  11. Degree of branching in hyperbranched poly(glycerol-co-diacid)s synthesized in toluene

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hyperbranched polymers were synthesized by using a Lewis acid (dibutyltin(IV)oxide) to catalyze the polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutaric acid (n=3) or azelaic acid (n=7) in toluene. These are the first examples of diacid-glycerol hyperbranc...

  12. Gelation, swelling and water vapor permeability behavior of radiation synthesized poly(ethylene oxide) hydrogels

    NASA Astrophysics Data System (ADS)

    Savaş, Hülya; Güven, Olgun

    2002-04-01

    In this study, gamma ray induced gelation of aqueous solutions of poly(ethylene oxide), (PEO) with 73.300 Da average molecular weight has been studied. Percent of conversion of polymer into gel as well as swelling behavior were investigated gravimetrically. The effect of the dose rate on these properties was studied. Within the dose rate range studied, it is observed that low dose rate irradiation favors chain scission and although the dominant effect is still crosslinking, %gelation at a given dose decreases. Water vapor permeability (Wvp) of PEO hydrogels has been studied with regard to crosslink density changes and temperature. The water vapor permeability of hydrogels obtained at high dose rate was found to be lower than those obtained at low dose rate which was related to higher crosslink density achieved under higher dose rate irradiations.

  13. Preparation and characterization of poly(vinyl alcohol)/graphene nanofibers synthesized by electrospinning

    NASA Astrophysics Data System (ADS)

    Barzegar, Farshad; Bello, Abdulhakeem; Fabiane, Mopeli; Khamlich, Saleh; Momodu, Damilola; Taghizadeh, Fatemeh; Dangbegnon, Julien; Manyala, Ncholu

    2015-02-01

    We report on the synthesis and characterization of electrospun polyvinyl alcohol (PVA)/graphene nanofibers. The samples produced were characterized by Raman spectroscopy for structural and defect density analysis, scanning electron microscopy (SEM) for morphological analysis, and thermogravimetric (TGA) for thermal analysis. SEM measurements show uniform hollow PVA fibers formation and excellent graphene dispersion within the fibers, while TGA measurements show the improved thermal stability of PVA in the presence of graphene. The synthesized polymer reinforced nanofibers have potential to serve in many different applications such as thermal management, supercapacitor electrodes and biomedical materials for drug delivery.

  14. Calorimetrically recognized maximum yield of poly-3-hydroxybutyrate (PHB) continuously synthesized from toxic substrates.

    PubMed

    Maskow, T; Babel, W

    2000-02-17

    The broader usage of poly-beta-hydroxybutyrate (PHB), for instance as bulk plastics, calls for cheap raw materials and greater overall process efficiency. The bacterial synthesis is generally induced and promoted by the limitation of growth via nitrogen, oxygen or phosphate depletion with the simultaneous excess and higher concentration of the carbon substrate. Consequently, toxic substrates have been considered unsuitable for PHB synthesis. Nevertheless, a single-stage continuous process for producing PHB from toxic substrates using microorganisms was developed and is reported here. The maximum heat flux during continuous growth and the maximum yield of PHB versus the substrate consumption rate were found to coincide. This suggests the possibility of controlling the conversion of a growth-inhibiting substrate into PHB and maximizing the process efficiency. The observed correlation occurred irrespective of the substrates investigated (phenol or sodium benzoate), the PHB-producing strain (Ralstonia eutropha JMP 134 or Variovorax paradoxus JMP 116), or the type of limitation imposed. The maximum PHB yields obtained comprised up to 50% of cell dry mass.

  15. Modulation of phosphoinositide metabolism in aortic smooth muscle cells by allylamine

    SciTech Connect

    Cox, L.R.; Murphy, S.K.; Ramos, K. )

    1990-08-01

    Aortic smooth muscle cells (SMC) modulate from a contractile to a proliferative phenotype upon subchronic exposure to allylamine. The present studies were designed to determine if this phenotypic modulation is associated with alterations in the metabolism of membrane phosphoinositides. 32P incorporation into phosphatidylinositol 4-phosphate (PIP), phosphatidylinositol 4,5-bisphosphate (PIP2), and phosphatidic acid (PA) was lower by 31, 35, and 22%, respectively, in SMC from allylamine-treated animals relative to controls. In contrast, incorporation of (3H)myoinositol into inositol phosphates did not differ in allylamine cells relative to control cells. Exposure to dibutyryl (db) cAMP (0.2 mM) and theophylline (0.1 mM) reduced 32P incorporation into PIP and PIP2 in SMC from both experimental groups. Under these conditions, a decrease in (3H)myoinositol incorporation into inositol 1-phosphate was only observed in allylamine cells. The effects of db cAMP and theophylline in allylamine and control SMC correlated with a marked decrease in cellular proliferation. These results suggest that alterations in phosphoinositide synthesis and/or degradation contribute to the enhanced proliferation of SMC induced by allylamine. To further examine this concept, the effects of agents which modulate protein kinase C (PKC) activity were evaluated. Sphingosine (125-500 ng/ml), a PKC inhibitor, decreased SMC proliferation in allylamine, but not control cells. 12-O-Tetradecanoylphorbol-13-acetate (1-100 ng/ml), a PKC agonist, stimulated proliferation in control cells, but inhibited proliferation in cells from allylamine-treated animals. We conclude that allylamine-induced phenotypic modulation of SMC is associated with alterations in phosphoinositide metabolism.

  16. Preparation, Characterization, and Size Control of Chemically Synthesized CdS Nanoparticles Capped with Poly(ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Seoudi, R.; Allehyani, S. H. A.; Said, D. A.; Lashin, A. R.; Abouelsayed, A.

    2015-10-01

    We prepared cadmium sulfide (CdS) nanoparticles of a specific size via chemical precipitation at room temperature and characterized them using high-resolution transmission electron microscopy, x-ray powder diffraction, ultraviolet-visible spectroscopy, and Fourier-transform infrared (FTIR) measurements. The results showed that the samples were grown with a cubic phase; the particle size could be changed from 2 nm to 4 nm by varying the molar ratios of the precursors (cadmium chloride and sodium sulfide) in the presence of poly(ethylene glycol) (PEG) as an effective capping agent. The optical bandgap of the synthesized nanoparticles was calculated and ranged from 2.73 eV to 2.92 eV depending on the particle size. A large blue-shift from the bulk bandgap (2.42 eV) was observed owing to the quantum size effect. Surface passivation and adsorption of PEG on the CdS nanoparticles was explained on the basis of FTIR measurements; two bands were observed at 476 cm-1 and 622 cm-1, corresponding to cadmium and sulfide stretching vibrations. We conclude that particle size can be controlled by varying the molar ratios of the precursors. Owing to the PEG encapsulation, the as-prepared samples were extremely stable over time.

  17. The effect of poly vinyl alcohol (PVA) surfactant on phase formation and magnetic properties of hydrothermally synthesized CoFe2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Jalalian, M.; Mirkazemi, S. M.; Alamolhoda, S.

    2016-12-01

    Nanoparticles of CoFe2O4 were synthesized by hydrothermal process at 190 °C with and without poly vinyl alcohol (PVA) addition using treatment durations of 1.5-6 h. The synthesized powders were characterized with X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), Field emission scanning electron microscope (FESEM) and vibration sample magnetometer (VSM) techniques. XRD results show presence of CoFe2O4 as the main phase and Co3O4 as the lateral phase in some samples. The results show that in the samples synthesized without PVA addition considerable amount of lateral phase is present after 3 h of hydrothermal treatment while with PVA addition this phase is undetectable in the XRD patterns of the sample synthesized at the same conditions. Microstructural studies represent increasing of particle size with increasing of hydrothermal duration and formation of coarser particles with PVA addition. The highest maximum magnetization (Mmax) values in both of the samples that were synthesized with and without PVA addition are about 59 emu/g that were obtained after 4.5 h of hydrothermal treatment. Intrinsic coercive field (iHc) value of the sample without PVA addition increases from 210 to 430 Oe. While with PVA addition the iHc value changes from 83 Oe to 493 Oe. The mechanism of changes in Mmax and iHc values has been explained.

  18. Electro-optical properties of one pot synthesized polyindole in the presence of poly(vinyl acetate)

    NASA Astrophysics Data System (ADS)

    Bhagat, D. J.; Dhokane, G. R.

    2015-05-01

    Polyindole was prepared in the presence of poly(vinyl acetate) through a chemical polymerization technique. The indole monomer was polymerized using ferric chloride as an oxidant. Electrical conductivity measurements were performed through a two probe technique. The prepared composites were analyzed by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDAX), and ultraviolet-visible (UV-VIS) spectroscopy. The DC conductivity was found to be 4.46 × 10-6 S/cm at 383 K. An attempt has been made to investigate the electrooptical properties of PIN/PVAc composite films.[Figure not available: see fulltext.

  19. Syntheses and physical characterization of new aliphatic triblock poly(L-lactide-b-butylene succinate-b-L-lactide)s bearing soft and hard biodegradable building blocks.

    PubMed

    Ba, Chaoyi; Yang, Jing; Hao, Qinghui; Liu, Xiaoyun; Cao, Amin

    2003-01-01

    This study presents chemical syntheses and physical characterization of a new aliphatic poly(L-lactide-b-butylene succinate-b-L-lactide) triblock copolyester with soft and hard biodegradable building blocks. First, poly(butylene succinate) (PBS) prepolymers terminated with hydroxyl functional groups were synthesized through melt polycondensation from succinic acid and 1,4-butanediol. Further, a series of new PLLA-b-PBS-b-PLLA triblock copolyesters bearing various average PLLA block lengths were prepared via ring opening polymerization of L-lactide with the synthesized hydroxyl capped PBS prepolymer (Mn = 4.9 KDa) and stannous octanoate as the macroinitiator and catalyst, respectively. By means of GPC, NMR, FTIR, DSC, TGA, and wide-angle X-ray diffractometer (WAXD), the macromolecular structures and physical properties were intensively studied for these synthesized PBS prepolymer and PLLA-b-PBS-b-PLLA triblock copolyesters. 13C NMR and GPC experimental results confirmed the formation of sequential block structures without any detectable transesterification under the present experimental conditions, and the molecular weights of triblock copolyesters could be readily regulated by adjusting the feeding molar ratio of L-lactide monomer to the PBS macroinitiator. DSC measurements showed all single glass transitions, and their glass transition temperatures were found to be between those of PLLA and PBS, depending on the lengths of PLLA blocks. It was noteworthy that the segmental flexibilities of the hard PLLA blocks were found to be remarkably enhanced by the more flexible PBS block partner, and the PBS and PLLA building blocks were well mixed in the amorphous regions. Results of TGA analyses indicated that thermal degradation and stabilities of the PLLA blocks strongly depended on the average PLLA block lengths of triblock copolyesters. In addition, FTIR and WAXD results showed the coexistence of the assembled PLLA and PBS crystal structures when the average PLLA block

  20. Improved selective cholesterol adsorption by molecularly imprinted poly(methacrylic acid)/silica (PMAA-SiO₂) hybrid material synthesized with different molar ratios.

    PubMed

    Clausen, Débora Nobile; Pires, Igor Matheus Ruiz; Tarley, César Ricardo Teixeira

    2014-11-01

    The present paper describes the synthesis of molecularly imprinted polymer - poly(methacrylic acid)/silica and reports its performance feasibility with desired adsorption capacity and selectivity for cholesterol extraction. Two imprinted hybrid materials were synthesized at different methacrylic acid (MAA)/tetraethoxysilane (TEOS) molar ratios (6:1 and 1:5) and characterized by FT-IR, TGA, SEM and textural data. Cholesterol adsorption on hybrid materials took place preferably in apolar solvent medium, especially in chloroform. From the kinetic data, the equilibrium time was reached quickly, being 12 and 20 min for the polymers synthesized at MAA/TEOS molar ratio of 6:1 and 1:5, respectively. The pseudo-second-order model provided the best fit for cholesterol adsorption on polymers, confirming the chemical nature of the adsorption process, while the dual-site Langmuir-Freundlich equation presented the best fit to the experimental data, suggesting the existence of two kinds of adsorption sites on both polymers. The maximum adsorption capacities obtained for the polymers synthesized at MAA/TEOS molar ratios of 6:1 and 1:5 were found to be 214.8 and 166.4 mg g(-1), respectively. The results from isotherm data also indicated higher adsorption capacity for both imprinted polymers regarding to corresponding non-imprinted polymers. Nevertheless, taking into account the retention parameters and selectivity of cholesterol in the presence of structurally analogue compounds (5-α-cholestane and 7-dehydrocholesterol), it was observed that the polymer synthesized at the MAA/TEOS molar ratio of 6:1 was much more selective for cholesterol than the one prepared at the ratio of 1:5, thus suggesting that selective binding sites ascribed to the carboxyl group from MAA play a central role in the imprinting effect created on MIP.

  1. Synthese and characterization of boronic acid functionalized macroporous uniform poly(4-chloromethylstyrene-co-divinylbenzene) particles and its use in the isolation of antioxidant compounds from plant extracts.

    PubMed

    Cetinkaya, Onur; Duru, Mehmet Emin; Ciçek, Hüseyin

    2012-11-15

    Aminophenyl boronic acid (APBA) carrying uniform-macroporous poly(chloromethylstyrene-co-divinylbenzene), poly(CMS-co-DVB) particles were synthesized for selective separation of cis-diol-containing flavonoids from plant extracts. For this purpose, 2.5 μm polystyrene seed particles were first swelled by a mixture of dibutyl phthalate (DBP), toluene and dodecanol, then by a monomer mixture including CMS and DVB. The repolymerization of the monomer phase in the swollen seed particles provided macroporous and uniform particles, approximately 7 μm in size. Chlorine atoms on the surface of these particles were derivatized with APBA to gain affinity properties for flavonoids containing vicinal hydroxyl groups. Model adsorption studies showed that these particles selectively adsorbed quercetin and rutin containing cis-diol groups, but did not adsorb apigenin similar to quercetin and not carrying cis-diol groups. These particles were also tested in adsorption/desorption studies for ethanol and ethyl acetate extracts of the Hypericum perforatum (HP) stems to obtain high antioxidant mixtures. With ethanol extract, the antioxidant activity of the desorption solution was a bit higher than that of the post-adsorption solutions. However, the DPPH radical scavenging activity of the desorption solution decreased with respect to the original extract and post-adsorption solutions. A similar result was obtained for the antioxidant activity of the desorption solution using ethyl acetate extract. An interesting result was obtained that DPPH radical scavenging activity of the post-adsorption solution was higher than that of the original ethyl acetate extract and desorption solutions. These results were attributed to selective adsorption of antioxidant characterized cis-diol-containing apolar molecules much more rather than that radical scavenger characterized polar molecules.

  2. Swelling of poly(N-isopropylacrylamide) P(NIPA)-based hydrogels with bacterial-synthesized prodigiosin for localized cancer drug delivery.

    PubMed

    Danyuo, Y; Dozie-Nwachukwu, S; Obayemi, J D; Ani, C J; Odusanya, O S; Oni, Y; Anuku, N; Malatesta, K; Soboyejo, W O

    2016-02-01

    We present the results of swelling experiments on poly(N-isopropylacrylamide) P(NIPA)-based hydrogels. The swelling characteristics of P(NIPA)-based homo-polymer and P(NIPA)-based co-polymers with Acrylamide (AM) and Butyl Methacrylate (BMA), were studied using weight gain experiments. The swelling due to the uptake of biosynthesized cancer drug, prodigiosin (PG), was compared to swelling in controlled environments (distilled water (DW), paclitaxel™ (PT) and bromophenol blue (BB)). PG was synthesized with Serratia marcescens (SM) subsp. marcescens bacteria. The mechanisms of drug diffusion and swelling of P(NIPA)-based hydrogels are also elucidated along with characterizing the heterogeneous porous structure of the P(NIPA)-based hydrogels. High Performance Liquefied Chromatography (HPLC) analysis revealed the purity of the biosynthesized prodigiosin to be 92.8%. PG was then absorbed by P(NIPA)-based hydrogels at temperatures between 28-48°C. This is a temperature range that might be encountered during the implantation of biomedical devices for localized cancer treatment via drug delivery and hyperthermia. The results obtained are shown to provide insights for the design of implantable biomedical devices for the localized treatment of breast cancer.

  3. Radiation synthesized poly( n-vinyl-2-pyrrolidone)-stabilized-gold nanoparticles as LSPR-based optical sensor for mercury ions estimation

    NASA Astrophysics Data System (ADS)

    Misra, Nilanjal; Kumar, Virendra; Goel, Narender Kumar; Varshney, Lalit

    2015-07-01

    Poly( n-vinyl-2-pyrrolidone)-stabilized-gold nanoparticles (PVP-Au-NPs) have been synthesized via a green-60Co-Gamma radiolytic route and employed as a localized surface plasmon resonance (LSPR)-based optical sensor for estimation of trace quantities of Hg2+ ion in aqueous solutions. The in situ generated PVP-Au-NPs were characterized using UV-vis spectroscopy, transmission electron microscopy, and particle size analysis techniques. Reaction conditions were optimized to obtain uniformly dispersed PVP-Au-NPs with average particle size of 7.1 ± 1.6 nm (±s), which exhibited a narrow LSPR band at 527 nm. The decrease in LSPR band intensity of PVP-Au-NPs with increase in Hg2+ ion concentration was found to be linear in the Hg2+ ion concentration range of 0-100 nM. The LSPR-based PVP-Au-NPs optical sensor system was found to be selective for Hg2+ and independent of interference from other metal ions such as Ca2+, Cu2+, Cd2+, and Fe2+ up to a concentration of 500 nM.

  4. Ultrastructural alterations in allylamine cardiovascular toxicity. Late myocardial and vascular lesions.

    PubMed Central

    Boor, P. J.; Ferrans, V. J.

    1985-01-01

    The late myocardial and vascular ultrastructural changes in rat hearts following consumption of the cardiovascular toxin allylamine were studied. Rats were given 0.1% allylamine HCl in drinking water for 10-104 days. From 10 to 21 days, there was organization of acute myocardial necrosis by macrophages and scattered polymorphonuclear leukocytes with prominent interstitial-cell proliferation. Alterations at 21-104 days included extensive scarring with formation of dense mature collagen with scattered fibroblasts present, grossly evident left-ventricular aneurysm, and gross and microscopic changes similar to those observed in the secondary form of endocardial fibroelastosis. Areas of scar contained highly cellular foci of smooth-muscle cells, myofibroblasts, and abundant extracellular elastin. Cardiac myocytes frequently showed markedly disorganized myofilaments, bizarrely distorted mitochondria with condensed cristae, and other severe degenerative changes. Small vessels within and adjacent to scar showed proliferation of intimal smooth-muscle cells. Endothelial lesions or recent or organized thrombi were not seen. Focal endocardial metaplasia, consisting of both chondroid and osseous tissue, was found in areas of transmural scarring, or ventricular aneurysm. Chondrocytes had the overall nuclear and cellular morphology, abundant rough endoplasmic reticulum, and surrounding lacunae typical of mature fibrocartilage. In some areas, the collagen matrix was undergoing calcification with the typical cross-banded pattern of calcifying connective tissue. Osteocytes were located in a densely calcified bone matrix and displayed characteristic cellular extensions into surrounding canaliculi. These findings indicate a severe myocardial, small-vessel, and endocardial injury during the course of chronic allylamine intoxication. Images Figure 13 Figure 14 Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 15 Figure

  5. Infrared-induced conformer interconversion processes for allylamine in argon matrices: Wavelength dependence on the kinetics

    NASA Astrophysics Data System (ADS)

    Schriver, A.; Racine, S.; Schriver, L.

    1985-12-01

    Infrared photoisomerization of allylamine trapped in solid argon is studied by irradiation either at specific wavelengths emitted by a CO 2 laser in coincidence with bands of the three conformers (S + G +, ST and CT) or in several mid- or near-IR domains using broad band filters. Upon irradiation with broad band filters the CT → ST process is mainly observed whatever the frequency domain, with only a slight intensity increase of the S + G + bands. Upon irradiation with CO 2 lines in coincidence with CT bands the conversion CT → ST is observed; the reverse process is evidenced by irradiation at ST frequencies. Irradiation at S + G + frequency shows no effect on the conformational equilibrium. Kinetic rate constants are measured and normalized to constant light power absorbed by the sample. They are compared with those calculated by the RRKM theory of first-order processes, assuming the same torsional barrier around the CC bond as in the gas phase. The good agreement between experimental and calculated values suggests the absence of vibrational selectivity in this photoisomerization process.

  6. Glucose biosensor based on the immobilization of glucose oxidase on electrochemically synthesized polypyrrole-poly(vinyl sulphonate) composite film by cross-linking with glutaraldehyde.

    PubMed

    Colak, Ozlem; Yaşar, Ahmet; Cete, Servet; Arslan, Fatma

    2012-10-01

    In this study, a novel amperometric glucose biosensor was developed by immobilizing glucose oxidase (GOX) by cross-linking via glutaraldehyde on electrochemically polymerized polypyrrole-poly(vinyl sulphonate) (PPy-PVS) films on the surface of a platinum (Pt) electrode. Electropolymerization of pyrrole and poly(vinyl sulphonate) on the Pt surface was carried out with an electrochemical cell containing pyrrole and poly(vinyl sulphonate) by cyclic voltammetry between -1.0 and + 2.0 V (vs.Ag/AgCl) at a scan rate of 50 mV/s upon the Pt electrode. The amperometric determination was based on the electrochemical detection of H(2)O(2) generated in enzymatic reaction of glucose. Determination of glucose was carried out by the oxidation of enzymatically produced H(2)O(2) at 0.4 V vs. Ag/AgCl. The effects of pH and temperature were investigated and optimum parameters were found to be 7.5 and 65°C, respectively. The effect of working potential was investigated and optimum potential was determined to be 0.4 V. The operational stability of the enzyme electrode was also studied. The response of the PPy/PVS-GOX glucose biosensor exhibited good reproducibility with a relative standard deviation (RSD) of 2.48%. The glucose biosensor retained 63% of initial activity after 93 days when stored in 0.1 M phosphate buffer solution of pH 7.5 at 4°C. With the low operating potential, the biosensor demonstrated little interference from the possible interferants.

  7. Hyaluronic acid immobilization on the poly-allylamine coated nano-network TiO2 surface.

    PubMed

    Shim, Jae-Won; Lee, Kang; Jeong, Moon-Jin; Jung, Sang-Chul; Kim, Byung-Hoon

    2011-08-01

    Recently, biocompatibility report revealed that the TiO2 nano-network (TiO2 NT) structure has much higher cells colonization than the native TiO2 on Ti surface. In this study, we prepared the hyaluronic acid (HA) immobilized TiO2 NT layer by plasma surface modification and then evaluated biological behavior of MC3T3-E1 on the Ti, TiO2 NT and TiO2 NT/NH2/HA surface. The cell viability tests revealed slightly enhanced viability on the TiO2 NT/NH2/HA surfaces than on the untreated Ti surfaces.

  8. A poly(acrylonitrile)-functionalized porous aromatic framework synthesized by atom-transfer radical polymerization for the extraction of uranium from seawater

    SciTech Connect

    Yue, Yanfeng; Zhang, Chenxi; Tang, Qing; Mayes, Richard T.; Liao, Wei -Po; Liao, Chen; Tsouris, Costas; Stankovich, Joseph J.; Chen, Jihua; Hensley, Dale K.; Abney, Carter W.; Jiang, De-en; Brown, Suree; Dai, Sheng

    2015-10-30

    In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, which demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.

  9. A poly(acrylonitrile)-functionalized porous aromatic framework synthesized by atom-transfer radical polymerization for the extraction of uranium from seawater

    DOE PAGES

    Yue, Yanfeng; Zhang, Chenxi; Tang, Qing; ...

    2015-10-30

    In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, whichmore » demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.« less

  10. Anion recognition using newly synthesized hydrogen bonding disubstituted phenylhydrazone-based receptors: poly(vinyl chloride)-based sensor for acetate.

    PubMed

    Gupta, Vinod K; Goyal, Rajendra N; Sharma, Ram A

    2008-08-15

    A potentiometric acetate-selective sensor, based on the use of butane-2,3-dione,bis[(2,4-dinitrophenyl)hydrazone] (BDH) as a neutral carrier in poly(vinyl chloride) (PVC) matrix, is reported. Effect of various plasticizers and cation excluder, cetryaltrimethylammonium bromide (CTAB) was studied. The best performance was obtained with a membrane composition of PVC:BDH:CTAB ratio (w/w; mg) of 160:8:8. The sensor exhibits significantly enhanced selectivity toward acetate ions over a wide concentration range 5.0 x 10(-6) to 1.0 x 10(-1)M with a lower detection limit of 1.2 x 10(-6)M within pH range 6.5-7.5 with a response time of <15s and a Nernstian slope of 60.3+/-0.3 mV decade(-1) of activity. Influences of the membrane composition, and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability are demonstrated. The sensor has a response time of 15s and can be used for at least 65 days without any considerable divergence in their potential response. Selectivity coefficients determined with the separate solution method (SSM) and fixed interference method (FIM) indicate that high selectivity for acetate ion. The proposed electrode shows fairly good discrimination of acetate from several inorganic and organic anions. It was successfully applied to direct determination of acetate within food preservatives. Total concentration of acetic acid in vinegar samples were determined by direct potentiometry and the values agreed with those mentioned by the manufacturers.

  11. Synthesis and characterization of poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s

    NASA Astrophysics Data System (ADS)

    Haw, Tan Ching; Ahmad, Azizan; Anuar, Farah Hannan

    2015-09-01

    In this study, poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s was synthesized in the framework of environmental friendly products to meet the need for highly flexible polymers. Triblock copolymer with poly(ethylene glycol) as center block and poly(D,L-lactide) as side block were first synthesized by ring-opening polymerization of D,L-lactide, followed by chain extension reaction of triblocks using hexamethylene diisocyanate (HMDI). NMR and infra-red spectroscopies were used to determine the molecular composition whereas XRD analysis revealed crystallinity behavior of synthesized multiblock copolymers.

  12. Improvement in the water retention characteristics of sandy loam soil using a newly synthesized poly(acrylamide-co-acrylic acid)/AlZnFe2O4 superabsorbent hydrogel nanocomposite material.

    PubMed

    Shahid, Shaukat Ali; Qidwai, Ansar Ahmad; Anwar, Farooq; Ullah, Inam; Rashid, Umer

    2012-08-03

    The use of some novel and efficient crop nutrient-based superabsorbent hydrogel nanocomposites (SHNCs), is currently becoming increasingly important to improve the crop yield and productivity, due to their water retention properties. In the present study a poly(Acrylamide-co-acrylic acid)/AlZnFe2O4 superabsorbent hydrogel nanocomposite was synthesized and its physical properties characterized using Energy Dispersive X-ray (EDX), FE-SEM and FTIR spectroscopic techniques. The effects of different levels of SHNC were studied to evaluate the moisture retention properties of sandy loam soil (sand 59%, silt 21%, clay 19%, pH 7.4, EC 1.92 dS/m). The soil amendment with 0.1, 0.2, 0.3 and 0.4 w/w% of SHNC enhanced the moisture retention significantly at field capacity compared to the untreated soil. Besides, in a separate experiment, seed germination and seedling growth of wheat was found to be notably improved with the application of SHNC. A delay in wilting of seedlings by 5-8 days was observed for SHNC-amended soil, thereby improving wheat plant growth and establishment.

  13. Biocompatibility and enhanced osteogenic differentiation of human mesenchymal stem cells in response to surface engineered poly(D,L-lactic-co-glycolic acid) microparticles.

    PubMed

    Rogers, Catherine M; Deehan, David J; Knuth, Callie A; Rose, Felicity R A J; Shakesheff, Kevin M; Oldershaw, Rachel A

    2014-11-01

    Tissue engineering strategies can be applied to enhancing osseous integration of soft tissue grafts during ligament reconstruction. Ligament rupture results in a hemarthrosis, an acute intra-articular bleed rich in osteogenic human mesenchymal stem cells (hMSCs). With the aim of identifying an appropriate biomaterial with which to combine hemarthrosis fluid-derived hMSCs (HF-hMSCs) for therapeutic application, this work has investigated the biocompatibility of microparticles manufactured from two forms of poly(D,L-lactic-co-glycolic acid) (PLGA), one synthesized with equal monomeric ratios of lactic acid to glycolic acid (PLGA 50:50) and the other with a higher proportion of lactic acid (PLGA 85:15) which confers a longer biodegradation time. The surfaces of both types of microparticles were functionalized by plasma polymerization with allylamine to increase hydrophilicity and promote cell attachment. HF-hMSCs attached to and spread along the surface of both forms of PLGA microparticle. The osteogenic response of HF-hMSCs was enhanced when cultured with PLGA compared with control cultures differentiated on tissue culture plastic and this was independent of the type of polymer used. We have demonstrated that surface engineered PLGA microparticles are an appropriate biomaterial for combining with HF-hMSCs and the selection of PLGA is relevant only when considering the biodegradation time for each biomedical application.

  14. Synthesizing speech

    NASA Astrophysics Data System (ADS)

    Siltanen, Samuli

    2015-01-01

    Samuli Siltanen explains how solving an "inverse problem" will improve the quality of life of people who can't speak and have to use voice synthesizers - particularly women and children, whose only current option is to sound like an adult male.

  15. Waveform synthesizer

    DOEpatents

    Franks, Larry A.; Nelson, Melvin A.

    1981-01-01

    A method of producing optical and electrical pulses of desired shape. An optical pulse of arbitrary but defined shape illuminates one end of an array of optical fiber waveguides of differing lengths to time differentiate the input pulse. The optical outputs at the other end of the array are combined to form a synthesized pulse of desired shape.

  16. Partial hydrophilic modification of biaxially oriented polypropylene film by an atmospheric pressure plasma jet with the allylamine monomer

    NASA Astrophysics Data System (ADS)

    Chen, W. X.; Yu, J. S.; Hu, W.; Chen, G. L.

    2016-11-01

    In this paper, the partial modification of the biaxially oriented polypropylene (BOPP) film for potential biological and packaging applications was achieved via hydrophilic modification using atmospheric pressure plasma jet (APPJ). In the APPJ system, the allylamine (ALA) monomer was polymerized on the BOPP surface by either the Ar/O2 or the He/O2 plasma. The results showed that plasmatic modification created many micro/nano sized holes on the BOPP film, which increased the surface roughness dramatically and the increased roughness enhanced the combining intensity between the BOPP film and the ALA polymer. However, such a plasmatic modification increased the water vapor permeability. The FTIR and XPS characterizations showed that the amine groups were grafted onto the BOPP film, and the contact angle of the BOPP film decreases from 98.5° to 8°. Compared with the BOPP films treated by the Ar or He plasma, the barrier property of the modified BOPP film increased significantly when the ALA polymer was incorporated. The bio-affinity/toxicity of ALA polymer was illustrated by the attachment of the cultured SMMC-7721 hepatoma cells on the modified BOPP film. The significant enhancement in the cell density indicated that modified BOPP film was highly bio-compatible and non-toxic, especially treated with the Ar/O2/ALA plasma.

  17. Synthesizing Chaos

    NASA Astrophysics Data System (ADS)

    Blakely, Jonathan; Corron, Ned; Hayes, Scott; Pethel, Shawn

    2007-03-01

    Chaos is usually attributed only to nonlinear systems. Yet it was recently shown that chaotic waveforms can be synthesized by linear superposition of randomly polarized basis functions. The basis function contains a growing oscillation that terminates in a large pulse. We show that this function is easily realized when viewed backward in time as a pulse followed by ringing decay. Consequently, a linear filter driven by random pulses outputs a waveform that, when viewed backward in time, exhibits essential qualities of chaos, i.e. determinism and a positive Lyapunov exponent. This phenomenon suggests that chaos may be connected to physical theories whose framework is not that of a deterministic dynamical system. We demonstrate that synthesizing chaos requires a balance between the topological entropy of the random source and the dissipation in the filter. Surprisingly, using different encodings of the random source, the same filter can produce both Lorenz-like and R"ossler-like waveforms. The different encodings can be viewed as grammar restrictions on a more general encoding that produces a chaotic superset encompassing the Lorenz and R"ossler paradigms of nonlinear dynamics. Thus, the language of deterministic chaos provides a useful description for a class of signals not generated by a deterministic system.

  18. Performances of new sugar-bearing poly(acrylamide) copolymers as DNA sieving matrices and capillary coatings for electrophoresis.

    PubMed

    Chiari, M; Cretich, M; Riva, S; Casali, M

    2001-01-01

    We have synthesized two new sugar monomers, allylamine of gluconic and lactobionic acid, by opening the corresponding lactone ring with allylamine. These monomers were copolymerized with acrylamide leading to formation of copolymers with a relative molecular mass of 288000 and 180000 Da, respectively. Double-stranded DNA fragments were separated in entangled solutions of these linear polymers in capillary electrophoresis. Resolution, peak spacing and peak width were the parameters taken into account to evaluate the quality of the separation achieved with the new polymers. This work indicates that the copolymers of acrylamide and allyl gluconic acid have a high sieving capacity and provide a performance similar to that of hydroxyethylcellulose (HEC) of comparable viscosity. Unlike HEC, this copolymer selfcoats onto the capillary wall, allowing DNA fragments to be efficiently separated in an uncoated capillary.

  19. Synthesis and physicochemical properties of two analogs of poly(dA): poly(2-aminopurine-9-beta-D-deoxyribonucleotide) and poly 2-amino-deoxyadenylic acid.

    PubMed Central

    Scheit, K H; Rackwitz, H R

    1982-01-01

    Polymerization of chemically synthesized dn2h6ATP and dn2ATP by deoxynucleotidyl transferase from calf thymus furnished poly(dn2h6A) and poly(dn2A) respectively. The synthetic polynucleotides were characterized by spectroscopic, ultracentrifugation and enzymatic methods. In polynucleotide-polynucleotide interaction, poly(dn2h6A) and poly(dn2A) behaved like analogs of poly(dnA). PMID:6287431

  20. Effect of self-association of bovine serum albumin on the stability of surfactant-induced aggregates of allylamine-capped silicon quantum dots.

    PubMed

    Chatterjee, Surajit; Mukherjee, Tushar Kanti

    2013-12-19

    The concentration-dependent self-association of bovine serum albumin (BSA) and subsequent altered interaction with sodium dodecyl sulfate (SDS) has been explored by means of photoluminescence (PL) spectroscopy, dynamic light scattering (DLS), circular dichroism (CD), PL imaging, and atomic force microscopy (AFM). By using an extrinsic luminescent probe, allylamine-capped silicon quantum dots (Si-QDs), we have demonstrated the unusual concentration-dependent altered BSA-SDS interaction. Allylamine-capped Si-QDs forms ordered aggregates in the presence of 1 mM SDS due to hydrogen bonding with the surfactants head groups at pH 7.4. Although these aggregates remain stable in the presence of monomeric BSA in the concentration range 1-8 μM, they form typical ring-shaped doughnut-like structures due to "necklace and bead"-like complex formation. However, beyond 10 μM BSA, these aggregates of Si-QDs slowly dissociate and complete dissociation occurs at 150 μM BSA. These anomalous results have been explained by considering the altered hydrophilicity of self-associated BSA.

  1. Changes in permeability and in mechanical properties of layer-by-layer films made from poly(allylamine) and montmorillonite postmodified upon reaction with dopamine.

    PubMed

    Ball, Vincent; Apaydin, Kadir; Laachachi, Abdelghani; Toniazzo, Valérie; Ruch, David

    2012-12-01

    Polyelectrolyte multilayer (PEM) films present a versatile surface functionalization method allowing to address many applications. These coatings suffer; however, from weak mechanical properties this problem can be addressed by the regular incorporation of clays in the layering process. To allow for an even better control of a whole set of film properties, among them their thermal stability, their stability in water, and their impermeability to anions, we postmodify (PAH-MMT)(n) films with polydopamine, by putting the pristine PEM films in contact with an oxygenated dopamine solution. This straightforward treatment allows to totally suppress the diffusion of hexacyanoferrate anions in the films and affects significantly its mechanical properties even, if the distribution of polydopamine through the film thickness is not yet known.

  2. Fabrication and characterization of novel multilayered structures by stereocomplexion of poly(D-lactic acid)/poly(L-lactic acid) and self-assembly of polyelectrolytes

    PubMed Central

    Yang, Gesheng; Pastorino, Laura

    2016-01-01

    Summary The enantiomers poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) were alternately adsorbed directly on calcium carbonate (CaCO3) templates and on poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) multilayer precursors in order to fabricate a novel layer-by-layer (LBL) assembly. A single layer of poly(L-lysine) (PLL) was used as a linker between the (PDLA/PLLA)n stereocomplex and the cores with and without the polymeric (PSS/PAH)n/PLL multilayer precursor (PEM). Nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) were used to characterize the chemical composition and molecular weight of poly(lactic acid) polymers. Both multilayer structures, with and without polymeric precursor, were firstly fabricated and characterized on planar supports. A quartz crystal microbalance (QCM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and ellipsometry were used to evaluate the thickness and mass of the multilayers. Then, hollow, spherical microcapsules were obtained by the removal of the CaCO3 sacrificial template. The chemical composition of the obtained microcapsules was confirmed by differential scanning calorimetry (DSC) and wide X-ray diffraction (WXRD) analyses. The microcapsule morphology was evaluated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. The experimental results confirm the successful fabrication of this innovative system, and its full biocompatibility makes it worthy of further characterization as a promising drug carrier for sustained release. PMID:26925356

  3. Surface-crosslinked poly(3-mercaptopropyl)methylsiloxane-coatings on silica as new platform for low-bleed mass spectrometry-compatible functionalized stationary phases synthesized via thiol-ene click reaction.

    PubMed

    Zimmermann, Aleksandra; Horak, Jeannie; Sievers-Engler, Adrian; Sanwald, Corinna; Lindner, Wolfgang; Kramer, Markus; Lämmerhofer, Michael

    2016-03-04

    A thin functional film of poly(3-mercaptopropyl)methylsiloxane was coated onto vinyl-modified silica particles (5μm, 100Å pore size) and chemically crosslinked to the surface. Excess of thiol functionalities allow bonding of alkene containing ligands by thiol-ene click reaction in a second step (QN-VII). Besides that a single step surface modification procedure was established in which alkene functional ligands were directly added to the polysiloxane coating solution and thus, after evaporation of the solvent, crosslinking to the vinylized surface and bonding of chromatographic ligand to the thiolated polysiloxane film occur simultaneously in one step (QN-VI). Successful bonding of the polysiloxane film was confirmed for both approaches by (29)Si cross-polarization/magic angle spinning NMR spectra. The new surface functionalization concept can be utilized as a new platform for the preparation of various low-bleed, mass spectrometry-compatible stationary phases with a variety of functional ligands. The concept was demonstrated by thiol-ene click reaction with quinine carbamate and its subsequent use for enantiomer separation by HPLC-UV and HPLC-ESI-QTOF-MS of acidic chiral analytes. Chromatographic enantioselectivities were similar to a comparable brush-type CSP (QN-V0). The greatly reduced background signal in LC-MS, however, comes at expense of somewhat lower chromatographic efficiencies (C-term by factor of 2 larger compared to brush-type CSP). For quantitative analysis in single reaction monitoring (MRM(HR)) in high sensitivity mode, limit of detection and limit of quantification results are comparable for both surface-polymer modified CSPs, with only slightly higher values for the conventional brush-type CSP (QN-V0).

  4. Efficient syntheses of 17-β-amino steroids.

    PubMed

    Taylor, Scott D; Harris, Jesse

    2011-01-01

    17β-Amino steroids such as 17β-amino-1,3,5(10)-estratrien-3-ol (1), 17β-amino-5α-androstan-3β-ol (2) and, 17β-amino-3β-hydroxyandrost-5-ene (3) have been widely used as a key intermediates in the synthesis of a variety of biologically active steroid derivatives though concise, high yielding syntheses of these compounds has yet to be reported. 17β-Amino-1,3,5(10)-estratrien-3-ol (1) and 17β-amino-5α-androstan-3β-ol (2) were prepared in high yield by reductive amination of estrone and epiandrosterone using benzylamine and sodium triacetoxyborohydride followed by catalytic hydrogenolysis of the resulting 17β-benzylamino derivatives. Attempts to prepare 17β-amino-3β-hydroxyandrost-5-ene (3) from dehydroepiandosterone using a similar approach resulted in partial reduction of the double bond. 17β-Amino-3β-hydroxyandrost-5-ene (3) was ultimately obtained in high yield by reductive amination of dehydroepiandosterone using allylamine and sodium triacetoxyborohydride followed by removal of the allyl group from the resulting 17β-allylamino derivative with dimethylbarbituric acid and Pd(PPh(3))(4) as catalyst.

  5. Syntheses and studies of acetylenic polymers

    SciTech Connect

    Yiwei, Ding

    1994-03-03

    Based on new diiodo aryl compounds a series of novel soluble polymers, poly(2,5-dialkoxy-1,4-phenyleneethynylene)s (PPE polymers) were synthesized using palladium-catalysis. The molecular weights (MW) range from 8,000 to 40,000. Properties such as absorption, fluorescence, and conductivity were studied. A PPE polymer with butoxy side chain exhibits a weak electrical conductivity (σ = 10-3 S/cm) after doping with AsF5. Absorption spectra in THF solution at room temperature (RT) show a maximum at 440 nm. However, absorption spectra of PPE polymers in the film state at (RT) show a maximum at 480 nm. PPE polymer-based light emitting diode (LED) devices have been prepared; greenish light from these LED devices can be observed. Poly(ethynylene-p-arylene-ethynylene-silylene)s were synthesized through the same palladium-catalyzed polymerization; MWs are between 6,000 and 82,000. Absorption and fluorescence were studied. Some of these polymers exhibit thermotropic liquid crystalline properties. In addition, nonlinear optical properties were briefly examined. Poly(silylene-ethynylene) homopolymers as well as alternating copolymers were synthesized through a novel palladium-catalyzed polymerization; MWs range from 56 x 103 to 5.3 x 103. Thermal stability of these was also investigated; char yields range from 56 to 83%. One of these polymers exhibits thermotropic liquid crystalline properties.

  6. Gallic acid tailoring surface functionalities of plasma-polymerized allylamine-coated 316L SS to selectively direct vascular endothelial and smooth muscle cell fate for enhanced endothelialization.

    PubMed

    Yang, Zhilu; Xiong, Kaiqin; Qi, Pengkai; Yang, Ying; Tu, Qiufen; Wang, Jin; Huang, Nan

    2014-02-26

    The creation of a platform for enhanced vascular endothelia cell (VEC) growth while suppressing vascular smooth muscle cell (VSMC) proliferation offers possibility for advanced coatings of vascular stents. Gallic acid (GA), a chemically unique phenolic acid with important biological functions, presents benefits to the cardiovascular disease therapy because of its superior antioxidant effect and a selectivity to support the growth of ECs more than SMCs. In this study, GA was explored to tailor such a multifunctional stent surface combined with plasma polymerization technique. On the basis of the chemical coupling reaction, GA was bound to an amine-group-rich plasma-polymerized allylamine (PPAam) coating. The GA-functionalized PPAam (GA-PPAam) surface created a favorable microenvironment to obtain high ECs and SMCs selectivity. The GA-PPAam coating showed remarkable enhancement in the adhesion, viability, proliferation, migration, and release of nitric oxide (NO) of human umbilical vein endothelial cells (HUVECs). The GA-PPAam coating also resulted in remarkable inhibition effect on human umbilical artery smooth muscle cell (HUASMC) adhesion and proliferation. These striking findings may provide a guide for designing the new generation of multifunctional vascular devices.

  7. The covalent immobilization of heparin to pulsed-plasma polymeric allylamine films on 316L stainless steel and the resulting effects on hemocompatibility.

    PubMed

    Yang, Zhilu; Wang, Jin; Luo, Rifang; Maitz, Manfred F; Jing, Fengjuan; Sun, Hong; Huang, Nan

    2010-03-01

    For an improved hemocompatibility of 316L stainless steel (SS), we develop a facile and effective approach to fabricating a pulsed-plasma polymeric allylamine (P-PPAm) film that possesses a high cross-linking degree and a high density of amine groups, which is used for subsequent bonding of heparin. The P-PPAm film as a stent coating shows good resistance to the deformation behavior of compression and expansion of a stent. Using deionized water as an aging medium, it is demonstrated that the heparin-immobilized P-PPAm (Hep-P-PPAm) surface has a good retention of heparin. The systematic in vitro hemocompatibility evaluation reveals lower platelet adhesion, platelet activation and fibrinogen activation on the Hep-P-PPAm surface, and the activated partial thromboplastin time prolongs for about 15 s compared with 316L SS. The P-PPAm surface significantly promotes adhesion and proliferation of endothelial cells (ECs). For the Hep-P-PPAm, although EC adhesion and proliferation is slightly suppressed initially, after cultivation for 3 days, the growth behavior of ECs is remarkably improved over 316L SS. In vivo results indicate that the Hep-P-PPAm surface successfully restrain thrombus formation by growing a homogeneous and intact shuttle-like endothelium on its surface. The Hep-P-PPAm modified 316L SS shows a promising application for vascular devices.

  8. Uses of a Vinylpyridine Polymer in Undergraduate Organic Syntheses.

    ERIC Educational Resources Information Center

    Getman, Damon; And Others

    1984-01-01

    Presents a series of syntheses in which poly-4-vinylpyridine is substituted for pyridine or other tertiary amines, avoiding some of the safety problems associated with traditional reagents and providing a readily recoverable and recyclable reactant. Background information, procedures used, and results are included. (JN)

  9. Multiplexed chirp waveform synthesizer

    DOEpatents

    Dudley, Peter A.; Tise, Bert L.

    2003-09-02

    A synthesizer for generating a desired chirp signal has M parallel channels, where M is an integer greater than 1, each channel including a chirp waveform synthesizer generating at an output a portion of a digital representation of the desired chirp signal; and a multiplexer for multiplexing the M outputs to create a digital representation of the desired chirp signal. Preferably, each channel receives input information that is a function of information representing the desired chirp signal.

  10. Ideal CO2/Light Gas Separation Performance of Poly(vinylimidazolium) Membranes and Poly(vinylimidazolium)-Ionic Liquid Composite Films

    SciTech Connect

    Carlisle, TK; Wiesenauer, EF; Nicodemus, GD; Gin, DL; Noble, RD

    2013-01-23

    Six vinyl-based, imidazolium room-temperature ionic liquid (RTIL) monomers were synthesized and photopolymerized to form dense poly(RTIL) membranes. The effect of polymer backbone (i.e., poly(ethylene), poly(styrene), and poly(acrylate)) and functional cationic substituent (e.g., alkyl, fluoroalkyl, oligo(ethylene glycol), and disiloxane) on ideal CO2/N-2 and CO2/CH4 membrane separation performance was investigated. The vinyl-based poly(RTIL)s were found to be generally less CO2-selective compared to analogous styrene- and acrylate-based poly(RTIL)s. The CO2 permeability of n-hexyl-(69 barrers) and disiloxane- (130 barrers) substituted vinyl-based poly(RTIL)s were found to be exceptionally larger than that of previously studied styrene and acrylate poly(RTIL)s. The CO2 selectivity of oligo(ethylene glycol)-functionalized vinyl poly(RTIL)s was enhanced, and the CO2 permeability was reduced when compared to the n-hexyl-substituted vinyl-based poly(RTIL). Nominal improvement in CO2/CH4 selectivity was observed upon fluorination of the n-hexyl vinyl-based poly(RTIL), with no observed change in CO2 permeability. However, rather dramatic improvements in both CO2 permeability and selectivity were observed upon blending 20 mol % RTIL (emim Tf2N) into the n-hexyl- and disiloxane-functionalized vinyl poly(RTIL)s to form solid liquid composite films.

  11. PULSE SYNTHESIZING GENERATOR

    DOEpatents

    Kerns, Q.A.

    1963-08-01

    >An electronlc circuit for synthesizing electrical current pulses having very fast rise times includes several sinewave generators tuned to progressively higher harmonic frequencies with signal amplitudes and phases selectable according to the Fourier series of the waveform that is to be synthesized. Phase control is provided by periodically triggering the generators at precisely controlled times. The outputs of the generators are combined in a coaxial transmission line. Any frequency-dependent delays that occur in the transmission line can be readily compensated for so that the desired signal wave shape is obtained at the output of the line. (AEC)

  12. The Journal Synthesizing Activity.

    ERIC Educational Resources Information Center

    Garber, Zev

    The journal synthesizing activity is intended to combine aspects of the formal essay with that of a diary. Activities associated with lecture topics are written up as short journal entries of approximately five typewritten pages and are turned in during the weekly class session at which the related topic is being discussed. The journal project…

  13. Wisdom, Intelligence & Creativity Synthesized

    ERIC Educational Resources Information Center

    Sternberg, Robert J.

    2009-01-01

    How is it that smart administrators who want to do a good job often find themselves in situations that degenerate into confrontation and, ultimately, termination? In this article, the author discusses why in terms of a model of leadership--which he refers to it as WICS, an acronym for wisdom, intelligence and creativity synthesized. He describes…

  14. Synthesized night vision goggle

    NASA Astrophysics Data System (ADS)

    Zhou, Haixian

    2000-06-01

    A Synthesized Night Vision Goggle that will be described int his paper is a new type of night vision goggle with multiple functions. It consists of three parts: main observing system, picture--superimposed system (or Cathode Ray Tube system) and Charge-Coupled Device system.

  15. Structural features of carbon materials synthesized by different methods

    NASA Astrophysics Data System (ADS)

    Streletskii, O. A.; Ivanenko, I. P.; Khvostov, V. V.; Savchenko, N. F.; Nishchak, O. Yu.; Aleksandrov, A. F.

    2016-10-01

    This paper presents the results of investigations of three types of carbon structures synthesized by different methods, such as arc discharge plasma enhanced chemical vapor deposition of carbon in a magnetic field, chemical dehydrohalogenation of the poly(vinyl chloride)/poly(vinylidene chloride) precursor, and pulsed plasma ion assisted deposition. It has been found that the samples prepared by different methods have a common feature, i.e., the presence of three-dimensional clusters based on sp 2- or sp 3-bonds surrounded by quasi-one-dimensional carbon chains. It has been shown that the structure of carbon materials changes depending on the synthesis conditions.

  16. Mechanism of poly(A) synthesis by vaccinia virus.

    PubMed

    Sheldon, R; Kates, J

    1974-08-01

    Data are presented which indicate that vaccinia DNA does not contain poly(dT) sequences the size of poly(A) sequences (50 to 200 nucleotides in length) found in vaccinia RNA. A hybridization experiment and polyacrylamide gel electrophoresis and DEAE-Sephadex chromatography of pyrimidine tracts show that poly(dT) sequences can account for no more than 0.1% of vaccinia DNA. Ultraviolet irradiation (which causes thymine dimer formation) and phleomycin (which binds to thymidine) both inhibit RNA synthesis but not poly(A) synthesis by vaccinia cores. These data are consistent with a nontranscriptive mechanism for vaccinia poly(A) synthesis. Both trypsin and 50 C heat treatment inhibit RNA synthesis more than poly(A) synthesis by cores, suggesting that separate enzymes may be involved in these syntheses. When the rate of core RNA synthesis is reduced by lowering the UTP and GTP concentrations, the size of the poly(A) sequences increase. These and other data suggest that transcription is involved in the termination of poly(A) synthesis in cores. This might be due to the displacement of growing poly(A) chains by recently completed RNA 3' termini which have not yet acquired poly(A) sequences.

  17. Low cytotoxic tissue adhesive based on oxidized dextran and epsilon-poly-L-lysine.

    PubMed

    Hyon, Suong-Hyu; Nakajima, Naoki; Sugai, Hajime; Matsumura, Kazuaki

    2014-08-01

    A novel adhesive hydrogel consisting of dextran and epsilon-poly(L-lysine) (dextran-PL) with multiple biomedical applications was developed. Periodate oxidation in aqueous media almost stoichiometrically introduces aldehyde groups in dextran molecules, and aldehyde dextran can react with the primary amino groups in epsilon-PL (ɛ-PL) at neutral pH to form a hydrogel. The gelation time of the hydrogel can be easily controlled by the extent of oxidation in dextran and of the acylation in ɛ-PL by anhydrides. The shear adhesion strength of dextran-PL was 10 times higher than that of fibrin glue, when wet collagen sheets were selected as test specimens. The cytotoxicity of aldehyde dextran and ɛ-PL were 1000 times lower than that of glutaraldehyde and poly(allylamine). The considerably low cytotoxicity of aldehyde dextran could be ascribed to its low reactivity with amine species when compared with glutaraldehyde. In contrast, a high reactivity of amino groups in ɛ-PL was observed when compared with glycine, L-lysine, and gelatin, which could be explained by their poor dissociation at neutral pH, thus leading to low cytotoxicity.

  18. Explaining Synthesized Software

    NASA Technical Reports Server (NTRS)

    VanBaalen, Jeffrey; Robinson, Peter; Lowry, Michael; Pressburger, Thomas; Lau, Sonie (Technical Monitor)

    1998-01-01

    Motivated by NASA's need for high-assurance software, NASA Ames' Amphion project has developed a generic program generation system based on deductive synthesis. Amphion has a number of advantages, such as the ability to develop a new synthesis system simply by writing a declarative domain theory. However, as a practical matter, the validation of the domain theory for such a system is problematic because the link between generated programs and the domain theory is complex. As a result, when generated programs do not behave as expected, it is difficult to isolate the cause, whether it be an incorrect problem specification or an error in the domain theory. This paper describes a tool we are developing that provides formal traceability between specifications and generated code for deductive synthesis systems. It is based on extensive instrumentation of the refutation-based theorem prover used to synthesize programs. It takes augmented proof structures and abstracts them to provide explanations of the relation between a specification, a domain theory, and synthesized code. In generating these explanations, the tool exploits the structure of Amphion domain theories, so the end user is not confronted with the intricacies of raw proof traces. This tool is crucial for the validation of domain theories as well as being important in everyday use of the code synthesis system. It plays an important role in validation because when generated programs exhibit incorrect behavior, it provides the links that can be traced to identify errors in specifications or domain theory. It plays an important role in the everyday use of the synthesis system by explaining to users what parts of a specification or of the domain theory contribute to what pieces of a generated program. Comments are inserted into the synthesized code that document these explanations.

  19. SYNTH: A spectrum synthesizer

    NASA Astrophysics Data System (ADS)

    Hensley, W. K.; McKinnon, A. D.; Miley, H. S.; Panisko, M. E.; Savard, R. M.

    1993-10-01

    A computer code has been written at the Pacific Northwest Laboratory (PNL) to synthesize the results of typical gamma ray spectroscopy experiments. The code, dubbed SYNTH, allows a user to specify physical characteristics of a gamma ray source, the quantity of the nuclides producing the radiation, the source-to-detector distance and the presence of absorbers, the type and size of the detector, and the electronic set up used to gather the data. In the process of specifying the parameters needed to synthesize a spectrum, several interesting intermediate results are produced, including a photopeak transmission function versus energy, a detector efficiency curve, and a weighted list of gamma and x rays produced from a set of nuclides. All of these intermediate results are available for graphical inspection and for printing. SYNTH runs on personal computers. It is menu driven and can be customized to user specifications. SYNTH contains robust support for coaxial germanium detectors and some support for sodium iodide detectors. SYNTH is not a finished product. A number of additional developments are planned. However, the existing code has been compared carefully to spectra obtained from National Institute for Standards and Technology (NIST) certified standards with very favorable results. Examples of the use of SYNTH and several spectral results are presented.

  20. Programmable electronic synthesized capacitance

    NASA Technical Reports Server (NTRS)

    Kleinberg, Leonard L. (Inventor)

    1987-01-01

    A predetermined and variable synthesized capacitance which may be incorporated into the resonant portion of an electronic oscillator for the purpose of tuning the oscillator comprises a programmable operational amplifier circuit. The operational amplifier circuit has its output connected to its inverting input, in a follower configuration, by a network which is low impedance at the operational frequency of the circuit. The output of the operational amplifier is also connected to the noninverting input by a capacitor. The noninverting input appears as a synthesized capacitance which may be varied with a variation in gain-bandwidth product of the operational amplifier circuit. The gain-bandwidth product may, in turn, be varied with a variation in input set current with a digital to analog converter whose output is varied with a command word. The output impedance of the circuit may also be varied by the output set current. This circuit may provide very small ranges in oscillator frequency with relatively large control voltages unaffected by noise.

  1. Polynucleotides. XLVI. 1 Synthesis and properties of poly (2'-amino-2'-deoxyadenylic acid).

    PubMed

    Ikehara, M; Fukui, T; Kakiuchi, N

    1977-04-01

    Poly (2'-amino-2'-deoxyadenylic acid) [poly (Aa)] was prepared from chemically synthesized 2'-amino-2'-deoxy-ADP by the catalysis of polynucleotide phosphorylase. Poly (Aa) showed a similar UV absorption spectra to poly (A), but quite different CD spectra at pH 7.0 and 5.7. At the former pH it showed a single negative Cotton band and at the latter a curve with a large splitting of bands. Acid titration of poly (Aa) suggested protonated form below pH 7.0. Temperature absorption profiles and their dependency on sodium ion concentration suggested an ordered structure for poly (Aa) which is stabilized by stacking of bases and intrastrand interaction between 2'-amino and internucleotidic phosphate groups. Poly (Aa) forms a 1:2 complex with poly (U) at neutrality and its Tm was 45 degrees in the presence of 0.15M sodium ion.

  2. Total syntheses of Prelactone V and Prelactone B.

    PubMed

    Raghavendra, S; Tadiparthi, Krishnaji; Yadav, J S

    2017-04-10

    The total syntheses of natural products Prelactone-V and Prelactone-B have been accomplished by a novel Chiron approach starting from d-glucose. The synthesis involves isopropylidene acetal formation of d-glucose using Poly(4-vinylpyridine) supported iodine as a catalyst, Tebbe olefination, Grignard reaction, Wittig olefination, selective mono deprotection of acetal using PMA/SiO2, hydrogenation and anti-1,3-diol formation are as key steps.

  3. Method for synthesizing HMX

    DOEpatents

    McGuire, Raymond R.; Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.

    1984-01-01

    A method and apparatus for electrochemically synthesizing N.sub.2 O.sub.5 cludes oxidizing a solution of N.sub.2 O.sub.4 /HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /HNO.sub.3 solution and the anode. A potential of about 1.35 to 2.0 V vs. SCE is preferred, while a potential of about 1.80 V vs. SCE is most preferred. Thereafter, the N.sub.2 O.sub.5 is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

  4. Synthesized light transients.

    PubMed

    Wirth, A; Hassan, M Th; Grguras, I; Gagnon, J; Moulet, A; Luu, T T; Pabst, S; Santra, R; Alahmed, Z A; Azzeer, A M; Yakovlev, V S; Pervak, V; Krausz, F; Goulielmakis, E

    2011-10-14

    Manipulation of electron dynamics calls for electromagnetic forces that can be confined to and controlled over sub-femtosecond time intervals. Tailored transients of light fields can provide these forces. We report on the generation of subcycle field transients spanning the infrared, visible, and ultraviolet frequency regimes with a 1.5-octave three-channel optical field synthesizer and their attosecond sampling. To demonstrate applicability, we field-ionized krypton atoms within a single wave crest and launched a valence-shell electron wavepacket with a well-defined initial phase. Half-cycle field excitation and attosecond probing revealed fine details of atomic-scale electron motion, such as the instantaneous rate of tunneling, the initial charge distribution of a valence-shell wavepacket, the attosecond dynamic shift (instantaneous ac Stark shift) of its energy levels, and its few-femtosecond coherent oscillations.

  5. Doclet To Synthesize UML

    NASA Technical Reports Server (NTRS)

    Barry, Matthew R.; Osborne, Richard N.

    2005-01-01

    The RoseDoclet computer program extends the capability of Java doclet software to automatically synthesize Unified Modeling Language (UML) content from Java language source code. [Doclets are Java-language programs that use the doclet application programming interface (API) to specify the content and format of the output of Javadoc. Javadoc is a program, originally designed to generate API documentation from Java source code, now also useful as an extensible engine for processing Java source code.] RoseDoclet takes advantage of Javadoc comments and tags already in the source code to produce a UML model of that code. RoseDoclet applies the doclet API to create a doclet passed to Javadoc. The Javadoc engine applies the doclet to the source code, emitting the output format specified by the doclet. RoseDoclet emits a Rose model file and populates it with fully documented packages, classes, methods, variables, and class diagrams identified in the source code. The way in which UML models are generated can be controlled by use of new Javadoc comment tags that RoseDoclet provides. The advantage of using RoseDoclet is that Javadoc documentation becomes leveraged for two purposes: documenting the as-built API and keeping the design documentation up to date.

  6. Controlled Degradation of Poly(Ethyl Cyanoacrylate-Co-Methyl Methacrylate)(PECA-Co-PMMA) Copolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper describes a method for modifying poly(ethyl cyanoacrylate) in order to control the degradation and the stability as well as the glass transition temperatures. Copolymers of poly(ethyl cyanoacrylate-co-methyl methacrylate) (PECA-co-PMMA) with various compositions were synthesized by free ...

  7. Synthesis, characterization and nanocomposite formation of poly(glycerol succinate-co-maleate) with cellulose nanowhiskers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with cellulose nanowhiskers. This glycerol-based polymer is thermally stable as...

  8. Solid-state synthesis of poly(3',4'-dimethoxy-2,2':5',2"- terthiophene): comparison with poly(terthiophene) and poly(3',4'-ethylenedioxy-2,2':5',2"- terthiophene).

    PubMed

    Abdiryim, Tursun; Jamal, Ruxangul; Ubul, Aminam; Nurulla, Ismayil

    2012-07-23

    A new terthiophene monomer: 3',4'-dimethoxy-2,2':5',2"-terthiophene (TMT) was synthesized and characterized by ¹H-NMR, ¹³C-NMR and FTIR. The solid-state oxidative polymerizations of TMT were performed in various ratios of oxidant (FeCl₃) to monomer (TMT). The resulting polymers were characterized by ¹H-NMR, FTIR, UV-vis-NIR, GPC, X-ray diffraction, CV, as well as TGA and conductivity measurements. The structure and properties of poly (TMT) were compared with those of polyterthiophene [poly(TT)] and poly (3',4'-ethylenedioxy-2,2':5',2"-terthiophene) [poly(TET)] prepared under the same polymerization conditions. After comparative analysis with poly(TT) and poly(TET), the effects of the dimethoxy substituent and FeCl₃ on the structural and physicochemical properties of the poly(TMT)s were discussed in depth. The comparison suggested that the dimethoxy-substituted polymer did not display higher crystallinity, thermal stability, conductivity and electrochemical activity than ethylenedioxy substituted one. The results also showed that the effect of FeCl₃ on poly(TMT) was similar that seen with the poly(TT), in which the oxidation degree, electrochemical activity and conductivity increased steadily with increasing [FeCl₃/[TT] ratio. Furthermore, the poly(TMT) and poly(TT) are mostly made up of dimers with a small amount of higher molecular weight components.

  9. Synthesis of poly(aminoamides)via enzymatic means

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Poly(aminoamides) constitute a subclass of polyamides that are water-soluble and useful for several applications. Commercially they are made via chemical reaction pathways. A review is made in this work of the enzymatic approaches towards their syntheses. Lipases and esterases have been found to ...

  10. Structure Confirmation and Properties of Poly(Dimethylsiloxaneco-diethylsiloxane) Copolymer

    NASA Astrophysics Data System (ADS)

    Gao, Li-Juan; Ma, De-Peng; Feng, Sheng-Yu

    2016-05-01

    High molecular weight poly (dimethylsiloxane-co-diethylsiloxane) (PMES) copolymer was synthesized by anionic ring opening polymerization. Its composition and structures was determined by 29Si NMR spectroscopy. A random microstructure of copolymer was observed in the 29Si NMR spectrum. Further, PMES was characterized by GPC and DSC. The results show that PMES is crystallization-free copolymer with low glass transition temperatures.

  11. Synthesis and surface immobilization of antibacterial hybrid silver-poly(l-lactide) nanoparticles

    NASA Astrophysics Data System (ADS)

    Taheri, Shima; Baier, Grit; Majewski, Peter; Barton, Mary; Förch, Renate; Landfester, Katharina; Vasilev, Krasimir

    2014-08-01

    Infections associated with medical devices are a substantial healthcare problem. Consequently, there has been increasing research and technological efforts directed toward the development of coatings that are capable of preventing bacterial colonization of the device surface. Herein, we report on novel hybrid silver loaded poly(L-lactic acid) nanoparticles (PLLA-AgNPs) with narrowly distributed sizes (17 ± 3 nm) prepared using a combination of solvent evaporation and mini-emulsion technology. These particles were then immobilized onto solid surfaces premodified with a thin layer of allylamine plasma polymer (AApp). The antibacterial efficacy of the PLLA-AgNPs nanoparticles was studied in vitro against both gram-positive (Staphylococcus epidermidis) and gram-negative (Escherichia coli) bacteria. The minimal inhibitory concentration values against Staphylococcus epidermidis and Escherichia coli were 0.610 and 1.156 μg · mL-1, respectively. The capacity of the prepared coatings to prevent bacterial surface colonization was assessed in the presence of Staphylococcus epidermidis, which is a strong biofilm former that causes substantial problems with medical device associated infections. The level of inhibition of bacterial growth was 98%. The substrate independent nature and the high antibacterial efficacy of coatings presented in this study may offer new alternatives for antibacterial coatings for medical devices.

  12. Poly(lactic acid) and poly(lactic-co-glycolic acid) particles as versatile carrier platforms for vaccine delivery.

    PubMed

    Pavot, Vincent; Berthet, Morgane; Rességuier, Julien; Legaz, Sophie; Handké, Nadège; Gilbert, Sarah C; Paul, Stéphane; Verrier, Bernard

    2014-12-01

    The development of safe and effective vaccines for cancer and infectious diseases remains a major goal in public health. Over the last two decades, controlled release of vaccine antigens and immunostimulant molecules has been achieved using nanometer or micron-sized delivery vehicles synthesized using biodegradable polymers. In addition to achieving a depot effect, enhanced vaccine efficacy using such delivery vehicles has been attributed to efficient targeting of antigen presenting cells such as dendritic cells. Biodegradable and biocompatible poly(lactic acid) and poly(lactic-co-glycolic acid) polymers belong to one such family of polymers that have been a popular choice of material used in the design of these delivery vehicles. This review summarizes research findings from ourselves and others highlighting the promise of poly(lactic acid)- and poly(lactic-co-glycolic acid)-based vaccine carriers in enhancing immune responses.

  13. Phenylethynyl-Terminated Poly(Arylene Ethers)

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Bryant, Robert G.; Hergenrother, Paul M.

    1994-01-01

    Phenylethynyl-terminated poly(arylene ethers) synthesized in wide range of molecular weights by adjusting monomer ratios and adding appropriate amounts of 4-phenylethynyl-4'-fluorobenzophenone to monomers to end-cap oligomers during polymerization. Have low molecular weights and low melt viscosities, and are easily processed as adhesives, composites, and moldings. Thermally cured to provide materials that are crosslinked and insoluble in common organic solvents. Exhibit increased resistance to solvents, greater tensile moduli, and better high-temperature properties. Useful as adhesives, composite matrices, and moldings, especially in applications in which combination of toughness and resistance to solvents needed.

  14. Copper nanocoils synthesized through solvothermal method.

    PubMed

    Liu, Yanjuan; Liu, Xiaowei; Zhan, Yongjie; Fan, Haiming; Lu, Yang

    2015-11-26

    Recently helical nanostructures such as nanosprings and nanocoils have drawn great interests in nanotechnology, due to their unique morphologies and physical properties, and they may be potential building blocks in sorts of electromechanical, magnetic, photoelectronic and plasmonic devices at micro/nanoscales. In this report, multi-turns copper nanocoils were synthesized through a modified solvothermal method, in which the mixture of water and N-methyl-2-pyrrolidone (NMP) were selected as reaction medium and copolymer poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA 64E) as reductant. In the liquid solution, nanosprings could be formed from relaxed nanocoils and demonstrated high elasticity. These nanocoils and nanosprings are of single crystalline structure, with the characteristics wire diameters ranging from tens to a few hundreds of nanometers and the ring/coil diameters mostly ~10-35 microns. Their growth and deformation mechanisms were then investigated and discussed along with that of previously reported single-turn copper nanorings. This work could be of importance for researchers working on synthesis and applications of novel 1-D helical nanomaterials and their functional devices.

  15. Copper nanocoils synthesized through solvothermal method

    NASA Astrophysics Data System (ADS)

    Liu, Yanjuan; Liu, Xiaowei; Zhan, Yongjie; Fan, Haiming; Lu, Yang

    2015-11-01

    Recently helical nanostructures such as nanosprings and nanocoils have drawn great interests in nanotechnology, due to their unique morphologies and physical properties, and they may be potential building blocks in sorts of electromechanical, magnetic, photoelectronic and plasmonic devices at micro/nanoscales. In this report, multi-turns copper nanocoils were synthesized through a modified solvothermal method, in which the mixture of water and N-methyl-2-pyrrolidone (NMP) were selected as reaction medium and copolymer poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA 64E) as reductant. In the liquid solution, nanosprings could be formed from relaxed nanocoils and demonstrated high elasticity. These nanocoils and nanosprings are of single crystalline structure, with the characteristics wire diameters ranging from tens to a few hundreds of nanometers and the ring/coil diameters mostly ~10-35 microns. Their growth and deformation mechanisms were then investigated and discussed along with that of previously reported single-turn copper nanorings. This work could be of importance for researchers working on synthesis and applications of novel 1-D helical nanomaterials and their functional devices.

  16. Copper nanocoils synthesized through solvothermal method

    PubMed Central

    Liu, Yanjuan; Liu, Xiaowei; Zhan, Yongjie; Fan, Haiming; Lu, Yang

    2015-01-01

    Recently helical nanostructures such as nanosprings and nanocoils have drawn great interests in nanotechnology, due to their unique morphologies and physical properties, and they may be potential building blocks in sorts of electromechanical, magnetic, photoelectronic and plasmonic devices at micro/nanoscales. In this report, multi-turns copper nanocoils were synthesized through a modified solvothermal method, in which the mixture of water and N-methyl-2-pyrrolidone (NMP) were selected as reaction medium and copolymer poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA 64E) as reductant. In the liquid solution, nanosprings could be formed from relaxed nanocoils and demonstrated high elasticity. These nanocoils and nanosprings are of single crystalline structure, with the characteristics wire diameters ranging from tens to a few hundreds of nanometers and the ring/coil diameters mostly ~10–35 microns. Their growth and deformation mechanisms were then investigated and discussed along with that of previously reported single-turn copper nanorings. This work could be of importance for researchers working on synthesis and applications of novel 1-D helical nanomaterials and their functional devices. PMID:26607386

  17. Immobilization of poly(acrylamide) brushes onto poly(caprolactone) surface by combining ATRP and "click" chemistry: Synthesis, characterization and evaluation of protein adhesion

    NASA Astrophysics Data System (ADS)

    Ma, Yuhao; Bian, Xinxiu; He, Liu; Cai, Mengtan; Xie, Xiaoxiong; Luo, Xianglin

    2015-02-01

    Developments of poly(caprolactone) in blood-contacting applications are often restricted due to its intrinsic hydrophobicity. One common way to improve its hemocompatibility is to attach hydrophilic polymers. Here we developed a non-destructive method to graft hydrophilic poly(acrylamide) (PAAm) onto poly(caprolactone) (PCL) surface. In this strategy, azido-ended PCL with low molecular weights was synthesized and blended with PCL to create a surface with "clickable" property. Alkyne-ended poly(acrylamide)s with controlled chain lengths were then synthesized by atom transfer radical polymerization (ATRP), and finally were immobilized onto PCL surface by "click" reaction. The occurrence of immobilization was verified qualitatively by water contact angle measurement and quantitatively by X-ray photoelectron spectroscopy (XPS). The PAAm grafted surface exhibited fouling resistant properties, as demonstrated by reduced bovine serum albumin (BSA) and fibrinogen (Fg) adhesion.

  18. Strong nonlinear photonic responses from microbiologically synthesized tellurium nanocomposites

    USGS Publications Warehouse

    Liao, K.-S.; Wang, Jingyuan; Dias, S.; Dewald, J.; Alley, N.J.; Baesman, S.M.; Oremland, R.S.; Blau, W.J.; Curran, S.A.

    2010-01-01

    A new class of nanomaterials, namely microbiologically-formed nanorods composed of elemental tellurium [Te(0)] that forms unusual nanocomposites when combined with poly(m-phenylenevinylene-co-2,5-dioctoxy-phenylenevinylene) (PmPV) is described. These bio-nanocomposites exhibit excellent broadband optical limiting at 532 and 1064 nm. Nonlinear scattering, originating from the laser induced solvent bubbles and microplasmas, is responsible for this nonlinear behavior. The use of bacterially-formed Te(0) when combined with an organic chemical host (e.g., PmPV) is a new green method of nanoparticle syntheses. This opens the possibilities of using unique, biologically synthesized materials to advance future nanoelectronic and nanophotonic applications. ?? 2009 Elsevier B.V. All rights reserved.

  19. Preparation of magnetic microspheres based on poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone) copolymers by modified solvent diffusion method.

    PubMed

    Men, Ke; Zeng, Shi; Gou, MaLing; Guo, Gang; Gu, Ying Chun; Luo, Feng; Zhao, Xia; Wei, YuQuan; Qian, ZhiYong

    2010-06-01

    Magnetic microspheres have promising application in biomedical field. In this paper, biodegradable poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCEC) triblock copolymers were synthesized by ring-opening polymerization method. Through adjusting the epsilon-CL/PEG weight ratio in feed, PCEC copolymers with different block ratio were obtained. A novel modified solvent diffusion method was described to prepare magnetic PCEC composite microspheres containing magnetite nanoparticles. The particle size of microsphere decreased with increase in the PEG/PCL block ratio. The obtained microspheres could response to external magnetic field. This study described a novel method to prepare magnetic microspheres. The obtained magnetic polymeric microspheres might have potential application in drug delivery system or disease diagnosis field.

  20. A Family of Bioreducible Poly(disulfide amine)s for Gene Delivery

    PubMed Central

    Ou, Mei; Xu, Rongzuo; Kim, Sun Hwa; Bull, David A.; Kim, Sung Wan

    2009-01-01

    A family of bioreducible poly(disulfide amine)s, which differ in the length of polymethylene spacer [–(CH2)n–] in the main chain and the side chain, has been synthesized. These bioreducible poly(disulfide amine)s exhibit local environment specific degradability and are associated with lower cytotoxicity than branched poly(ethylenimine) (bPEI, 25kDa). These cationic polymers also show higher buffering capacity and protonation degree than bPEI, facilitating the endosomal escape of carried genetic materials. The transfection efficiency of these agents is polymethylene length dependent. Poly(cystaminebisacrylamide-spermine) [poly(CBA-SP);], poly(cystaminebisacrylamide-bis(3-aminopropyl)-1,3-propanediamine) [poly(CBA-APPD);], and poly(cyxtaminebisacrylamide-bis(3-aminopropyl)-ethylenediamine) [ploy(CBA-APED);] with longer propylene [–(CH2)3–] side spacer, demonstrate higher transfection efficacy than the counterpart poly(cystaminebisacrylamide-bis(2-aminoethyl)-1,3-propanediamine) [poly(CBA-AEPD);] and poly(cystaminebisacrylamide-triethylenetetramine) [poly(CBA-TETA);], which have shorter ethylene [–(CH2)2–] side spacer. The poly(CBA-SP), poly(CBA-APPD), poly(CBA-APED) with the main chain spacer of –(CH2)4–, –(CH2)3–, –(CH2)2– demonstrate similar transfection efficiency, indicating the length of polymer main chain spacer has less influence on transfection efficiency. However, with the same short ethylene [–(CH2)2–] side spacer, poly(CBA-AEPD), with the longer main chain oligomethylene units [–(CH2)3–], showed relatively higher transfection efficiency than poly(CBA-TETA), having shorter main chain oligomethylene units [–(CH2)2–]. Of these polymeric carriers, poly(CBA-SP) demonstrated the highest transfection in the C2C12 cell line, while poly(CBA-APED) showed the highest transfection in the Hela cell line. All of these agents showed greater transfection activity than commercialized bPEI 25kDa. The poly(disulfide amine)s are promising

  1. Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC.

    PubMed

    Maeda, Katsuhiro; Maruta, Miyuki; Sakai, Yuki; Ikai, Tomoyuki; Kanoh, Shigeyoshi

    2016-11-07

    A series of optically active poly(diphenylacetylene) derivatives bearing a chiral substituent (poly-2S) or chiral and achiral substituents (poly-(2Sx-co-31-x)) on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenyl)acetylene) with (S)-1-phenylethylamine ((S)-2) or benzylamine (3) in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) were investigated. Poly-2S and poly-(2Sx-co-31-x) (0.06 < x < 0.71) formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2S and h-poly-(2Sx-co-31-x)). Furthermore, h-poly-2S and h-poly-(2S0.36-co-30.64) emitted circularly polarized luminescence with opposite signs. h-Poly-2S showed higher chiral recognition abilities toward a larger number of racemates than poly-2S without a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene) derivative bearing the same chiral substituent on half of its pendant phenyl rings. h-Poly-(2S0.36-co-30.64) also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared with h-poly-2S.

  2. Reactanceless synthesized impedance bandpass amplifier

    NASA Technical Reports Server (NTRS)

    Kleinberg, L. L. (Inventor)

    1985-01-01

    An active R bandpass filter network is formed by four operational amplifier stages interconnected by discrete resistances. One pair of stages synthesize an equivalent input impedance of an inductance (L sub eq) in parallel with a discrete resistance (R sub o) while the second pair of stages synthesizes an equivalent input impedance of a capacitance (C sub eq) serially coupled to another discrete resistance (R sub i) coupled in parallel with the first two stages. The equivalent input impedances aggregately define a tuned resonant bandpass filter in the roll-off regions of the operational amplifiers.

  3. Poly(cyclohexylethylene)-block-poly(ethylene oxide) block polymers for metal oxide templating

    SciTech Connect

    Schulze, Morgan W.; Sinturel, Christophe

    2015-09-01

    A series of poly(cyclohexylethylene)-block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation produces an ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.

  4. Synthesis and Properties of Poly(l-lactide)-b-poly (l-phenylalanine) Hybrid Copolymers

    PubMed Central

    Planellas, Marc; Puiggalí, Jordi

    2014-01-01

    Hybrid materials constituted by peptides and synthetic polymers have nowadays a great interest since they can combine the properties and functions of each constitutive block, being also possible to modify the final characteristics by using different topologies. Poly(l-lactide-b-l-phenylalanine) copolymers with various block lengths were synthesized by sequential ring-opening polymerization of l-lactide and the N-carboxyanhydride of l-phenylalanine. The resulting block copolymers were characterized by NMR spectrometry, IR spectroscopy, gel permeation chromatography, MALDI-TOF and UV-vis, revealing the successful incorporation of the polyphenylalanine (PPhe) peptide into the previously formed poly(l-lactide) (PLLA) polymer chain. X-ray diffraction and DSC data also suggested that the copolymers were phase-separated in domains containing either crystalline PLLA or PPhe phases. A peculiar thermal behavior was also found by thermogravimetric analysis when polyphenylalanine blocks were incorporated into polylactide. PMID:25075980

  5. Poly(cyclohexylethylene)-block-poly(ethylene oxide) block polymers for metal oxide templating

    DOE PAGES

    Schulze, Morgan W.; Sinturel, Christophe; Hillmyer, Marc A.

    2015-09-01

    A series of poly(cyclohexylethylene)-block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation produces anmore » ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.« less

  6. Information Retrieval for Ecological Syntheses

    ERIC Educational Resources Information Center

    Bayliss, Helen R.; Beyer, Fiona R.

    2015-01-01

    Research syntheses are increasingly being conducted within the fields of ecology and environmental management. Information retrieval is crucial in any synthesis in identifying data for inclusion whilst potentially reducing biases in the dataset gathered, yet the nature of ecological information provides several challenges when compared with…

  7. Method of synthesizing pyrite nanocrystals

    DOEpatents

    Wadia, Cyrus; Wu, Yue

    2013-04-23

    A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

  8. Laboratory Syntheses of Insect Pheromones.

    ERIC Educational Resources Information Center

    Cormier, Russell A.; Hoban, James N.

    1984-01-01

    Provides background information and procedures for the multi-step synthesis of tiger moth and boll weevil pheromones (sex attractants). These syntheses require several laboratory periods. The tiger moth pheromone synthesis is suitable for introductory organic chemistry while the boll weevil pheromone is recommended for an advanced laboratory…

  9. Confined Flocculation of Ionic Pollutants by Poly(L-dopa)-Based Polyelectrolyte Complexes in Hydrogel Beads for Three-Dimensional, Quantitative, Efficient Water Decontamination.

    PubMed

    Yu, Li; Liu, Xiaokong; Yuan, Weichang; Brown, Lauren Joan; Wang, Dayang

    2015-06-16

    The development of simple and recyclable adsorbents with high adsorption capacity is a technical imperative for water treatment. In this work, we have successfully developed new adsorbents for the removal of ionic pollutants from water via encapsulation of polyelectrolyte complexes (PECs) made from positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(l-3,4-dihydroxyphenylalanine) (PDopa), obtained via the self-polymerization of l-3,4-dihydroxyphenylalanine (l-Dopa). Given the outstanding mass transport through the hydrogel host matrixes, the PDopa-PAH PEC guests loaded inside can effectively and efficiently remove various ionic pollutants, including heavy metal ions and ionic organic dyes, from water. The adsorption efficiency of the PDopa-PAH PECs can be quantitatively correlated to and tailored by the PDopa-to-PAH molar ratio. Because PDopa embodies one catechol group, one carboxyl group, and one amino group in each repeating unit, the resulting PDopa-PAH PECs exhibit the largest capacity of adsorption of heavy metal ions compared to available adsorbents. Because both PDopa and PAH are pH-sensitive, the PDopa-PAH PEC-loaded agarose hydrogel beads can be easily and completely recovered after the adsorption of ionic pollutants by adjusting the pH of the surrounding media. The present strategy is similar to the conventional process of using PECs to flocculate ionic pollutants from water, while in our system flocculation is confined to the agarose hydrogel beads, thus allowing easy separation of the resulting adsorbents from water.

  10. Preparation of poly(butyl methacrylate-co-ethyleneglyceldimethacrylate) monolithic column modified with β-cyclodextrin and nano-cuprous oxide and its application in polymer monolithic microextraction of polychlorinated biphenyls.

    PubMed

    Zheng, Haijiao; Liu, Qingwen; Jia, Qiong

    2014-05-23

    A poly(butyl methacrylate-co-ethyleneglyceldimethacrylate) (poly(BMA-EDMA)) monolithic column was prepared with in situ polymerization method and modified with allylamine-β-cyclodextrin (ALA-β-CD) and nano-cuprous oxide (Cu2O). A polymer monolith microextraction method was developed with the modified monolithic column for the preconcentration of polychlorinated biphenyls combined with gas chromatography-electron capture detector. Various parameters affecting the extraction efficiency were investigated and optimized. Under the optimum experimental conditions, we obtained acceptable linearities, low limits of detection, and good intra-day/inter-day relative standard deviations. Because of the hydrophobic properties of β-CD and the porous nano structure of Cu2O, the enrichment capacity of the poly(BMA-EDMA) monolithic column was significantly improved. The extraction efficiency followed the order: poly(BMA-EDMA-ALA-β-CD-Cu2O)>poly(BMA-EDMA-ALA-β-CD)>poly(BMA-EDMA)>direct GC analysis. When applied to the determination of polychlorinated biphenyls in wine samples, low limits of detection (0.09ngmL(-1)) were obtained under the preoptimized conditions (sample volume 1.0mL, sample flow rate 0.1mLmin(-1), eluent volume 0.1mL, and eluent flow rate 0.05mLmin(-1)). In addition, the present method was employed to determine polychlorinated biphenyls in red wine samples and the accuracy was assessed through recovery experiments. The obtained recovery values were in the range of 78.8-104.1% with relative standard deviations less than 9.0%.

  11. Tunneling conduction in graphene/(poly)vinyl alcohol composite

    NASA Astrophysics Data System (ADS)

    Mitra, Sreemanta; Banerjee, Sourish; Chakravorty, Dipankar

    2013-04-01

    Graphene/(Poly)vinyl alcohol (PVA) composite film with thickness 60μm was synthesized by solidification of a PVA solution comprising of dispersed graphene nanosheets. The close proximity of the graphene sheets enables the fluctuation induced tunneling of electrons to occur from one sheet to another. The dielectric data show that the present system can be simulated to a parallel resistance-capacitor network. The high frequency exponent of the frequency variation of the ac conductivity indicates that the charge carriers move in a two-dimensional space. The sample preparation technique will be helpful for synthesizing flexible conductors.

  12. TSS-Thermal Synthesizer System

    NASA Technical Reports Server (NTRS)

    Chimenti, Edward; Rickman, Steven; Vogt, Robert; Longo, Carlos R. Ortiz; Bauman, Noel; Lepore, Joseph; Mackey, Phil; Pavlovsky, James, II; Welch, Mark; Fogerson, Peter; Dawber, Mark; Fong, Cynthia Jone; Hecke, Peter; Morrison, Susan; Castillo, Ernie; Chou, ZU; Fried, Lawrence; Howard, Jerry; Lombardi, Mike; Middleton, Jack

    1996-01-01

    Thermal Synthesizer System (TSS) is integrated set of thermal-analysis application programs designed to solve problems encountered by thermal engineers. Combines functionality of Systems Improved Numerical Differencing Analyzer/Fluid Integrator (SINDA/FLUINT) and radiation analysis with friendly and easily understood user-interface environment coupled with powerful interactive color graphics and geometric modeling capability. Enables thermal engineers to spend more time solving engineering problems instead of laboriously constructing and verifying math models. Written in FORTRAN and C language.

  13. Catalytic method for synthesizing hydrocarbons

    DOEpatents

    Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

    A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

  14. Catalytic method for synthesizing hydrocarbons

    DOEpatents

    Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

    1984-01-01

    A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

  15. Stereoselective Syntheses of Soman Analog

    DTIC Science & Technology

    1993-04-28

    AD-A283 855 AD_ _ _ _ CONTRACT NO: DAMDl7-88-C-8021 0 / TITLE: STEREOSELECTIVE SYNTHESES OF SOMAN ANALOG SUBTITLE: Synthesis of Pentacoordinate...SUPPLEMENTARY NOTES SUBTITLE: Synthesis of Pentacoordinate Phosphorus Compounds, "Bait and Switch" Compounds, and Soman Simulants as Hapten. for Production of...simulant. We reporit a detailed study on the synthesis , isolation and characterization of the four pure enantiomners; of [(S or R)-4 -amino-2,2-diniethyl-2

  16. Method for synthesizing powder materials

    DOEpatents

    Buss, R.J.; Ho, P.

    1988-01-21

    A method for synthesizing ultrafine powder materials, for example, ceramic and metal powders, comprises admitting gaseous reactants from which the powder material is to be formed into a vacuum reaction chamber maintained at a pressure less than atmospheric and at a temperature less than about 400/degree/K (127/degree/C). The gaseous reactants are directed through a glow discharge provided in the vacuum reaction chamber to form the ultrafine powder material. 1 fig.

  17. Electroconductive Hydrogel Based on Functional Poly(Ethylenedioxy Thiophene)

    PubMed Central

    2016-01-01

    Poly(ethylene dioxythiophene) with functional pendant groups bearing double bonds is synthesized and employed for the fabrication of electroactive hydrogels with advantageous characteristics: covalently cross-linked porous 3D scaffolds with notable swelling ratio, appropriate mechanical properties, electroactivity in physiological conditions, and suitability for proliferation and differentiation of C2C12 cells. This is a new approach for the fabrication of conductive engineered constructs. PMID:27656042

  18. Synthesis and characterization of triblock copolymers of methoxy poly(ethylene glycol) and poly(propylene fumarate).

    PubMed

    Behravesh, Esfandiar; Shung, Albert K; Jo, Seongbong; Mikos, Antonios G

    2002-01-01

    Amphiphilic block copolymers were synthesized by transesterification of hydrophilic methoxy poly(ethylene glycol) (mPEG) and hydrophobic poly(propylene fumarate) (PPF) and characterized. Four block copolymers were synthesized with a 2:1 mPEG:PPF molar ratio and mPEGs of molecular weights 570, 800, 1960, and 5190 and PPF of molecular weight 1570 as determined by NMR. The copolymers synthesized with mPEG of molecular weights 570 and 800 had 1.9 and 1.8 mPEG blocks per copolymer, respectively, as measured by NMR, representing an ABA-type block copolymer. The number of mPEG blocks of the copolymer decreased with increasing mPEG block length to as low as 1.5 mPEG blocks for copolymer synthesized with mPEG of molecular weight 5190. At a concentration range of 5-25 wt % in phosphate-buffered saline, copolymers synthesized with mPEG molecular weights of 570 and 800 possessed lower critical solution temperatures (LCST) between 40 and 45 degrees C and between 55 and 60 degrees C, respectively. Aqueous solutions of copolymer synthesized with mPEG 570 and 800 also experienced thermoreversible gelation. The sol-gel transition temperature was dependent on the sodium chloride concentration as well as the mPEG block length. The copolymer synthesized from mPEG 570 had a transition temperature between 40 and 20 degrees C with salt concentrations between 1 and 10 wt %, while the sol-gel transition temperatures of the copolymer synthesized from mPEG molecular weight 800 were higher in the range 75-30 degrees C with salt concentrations between 1 and 15 wt %. These novel thermoreversible copolymers are the first biodegradable copolymers with unsaturated double bonds along their macromolecular chain that can undergo both physical and chemical gelation and hold great promise for drug delivery and tissue engineering applications.

  19. Chromatographic enantioseparation by poly(biphenylylacetylene) derivatives with memory of both axial chirality and macromolecular helicity.

    PubMed

    Ishidate, Ryoma; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji; Maeda, Katsuhiro

    2017-03-29

    Novel poly(biphenylylacetylene) derivatives bearing two acetyloxy groups at the 2- and 2'-positions and an alkoxycarbonyl group at the 4'-position of the biphenyl pendants (poly-Ac's) were synthesized by the polymerization of the corresponding biphenylylacetylenes using a rhodium catalyst. The obtained stereoregular (cis-transoidal) poly-Ac's folded into a predominantly one-handed helical conformation accompanied by a preferred-handed axially twisted conformation of the biphenyl pendants through noncovalent interactions with a chiral alcohol and both the induced main-chain helicity and the pendant axial chirality were maintained, that is, memorized, after complete removal of the chiral alcohol. The stability of the helicity memory of the poly-Ac's in a solution was lower than that of the analogous poly(biphenylylacetylene)s bearing two methoxymethoxy groups at the 2- and 2'-positions of the biphenyl pendants (poly-MOM's). In the solid state, however, the helicity memory of the poly-Ac's was much more stable and showed a better chiral recognition ability toward several racemates than that of the previously reported poly-MOM when used as a chiral stationary phase for high-performance liquid chromatography. In particular, the poly-Ac-based CSP with a helicity memory efficiently separated racemic benzoin derivatives into enantiomers.

  20. Cholic acid functionalized star poly(DL-lactide) for promoting cell adhesion and proliferation.

    PubMed

    Fu, Hui-Li; Zou, Tao; Cheng, Si-Xue; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2007-01-01

    Cholic acid functionalized star poly(DL-lactide) was synthesized through the ring-opening polymerization of DL-lactide initiated by cholic acid. The properties and cell behaviour of the cholic acid functionalized star poly(DL-lactide) were investigated as compared with linear poly(DL-lactide)s with different molecular weights and a star poly(DL-lactide) initiated by glycerol. In comparison to linear poly(DL-lactide)s, the cholic acid functionalized star poly(DL-lactide) had better wettability and slightly higher surface energy. The cell adhesion and proliferation on different materials were evaluated using two types of cells, 3T3 mouse fibroblasts and ECV304 human endothelial cells. Compared with the linear poly(DL-lactide)s, the cholic acid functionalized star poly(DL-lactide) showed obviously improved property for cell adhesion. The cell proliferation on the cholic acid functionalized star poly(DL-lactide) was also enhanced. The improvement in cell proliferation was not so significant as compared with the improvement in cell adhesion. This modification strategy provides an effective and simple way to promote cell attachment and growth in tissue engineering.

  1. Poly(citric acid)-block-poly(ethylene glycol) copolymers--new biocompatible hybrid materials for nanomedicine.

    PubMed

    Naeini, Ashkan Tavakoli; Adeli, Mohsen; Vossoughi, Manouchehr

    2010-08-01

    Linear-dendritic ABA triblock copolymers containing poly(ethylene glycol) (PEG) as B block and hyperbranched poly(citric acid) (PCA) as A blocks were synthesized through polycondensation. The molecular self-assembly of synthesized PCA-PEG-PCA copolymers in water led to formation of nanoparticles and fibers in different sizes and shapes depending on the time and size of PCA blocks. Ten days after dissolving PCA-PEG-PCA copolymers in water, the size of fibers had reached several millimeters. Mixing a water solution of fluorescein as a small guest molecule and PCA-PEG-PCA copolymers led to the encapsulation of fluorescein by products of molecular self-assembly. To investigate their potential application in nanomedicine and to understand the limitations and capabilities of these materials as nanoexcipients in biological systems, different types of short-term in vitro cytotoxicity experiments on the HT1080 cell line (human fibrosarcoma) and hemocompatibility tests were performed. From the clinical editor: This manuscript investigates the potentials of linear-dendritic ABA triblock copolymers containing poly(ethylene glycol) (PEG) as B block and hyperbranched poly(citric acid) (PCA) as A blocks for future applications in nanomedicine.

  2. Synthesis and Characterization of Multiwalled Carbon Nanotubes/Poly(HEMA-co-MMA) by Utilizing Click Chemistry.

    PubMed

    Bach, Long Giang; Cao, Xuan Thang; Islam, Md Rafiqul; Jeong, Yeon Tae; Kim, Jong Su; Lim, Kwon Taek

    2016-03-01

    The hybrid material consisting of multi walled carbon nanotubes (MWNTs) and poly(2-hydroxyethylmethacrylate-co-methylmethacrylate) [poly(HEMA-co-MMA)] was synthesized by a combination of RAFT and Click chemistry. In the primary stage, the copolymer poly(HEMA-co-MMA) was prepared by applying RAFT technique. Alkynyl side groups were incorporated onto the poly(HEMA-co-MMA) backbone by esterification reaction. Then, MWNTs-N3 was prepared by treating MWNTs with 4-azidobutylamine. The click coupling reaction between azide-functionalized MWNTs (MWNTs-N3) and the alkyne-functionalized random copolymer ((HEMA-co-MMA)-Alkyne) with the Cu(I)-catalyzed [3+2] Huisgen cycloaddition afforded the hybrid compound. The structure and properties of poly(MMA-co-HEMA)-g-MWNTs were investigated by FT-IR, EDX and TGA measurements. The copolymer brushes were observed to be immobilized onto the functionalized MWNTs by SEM and TEM analysis.

  3. PolyMorphine: an innovative biodegradable polymer drug for extended pain relief

    PubMed Central

    Rosario-Meléndez, Roselin; Harris, Carolyn L.; Delgado-Rivera, Roberto; Yu, Lei; Uhrich, Kathryn E.

    2012-01-01

    Morphine, a potent narcotic analgesic used for the treatment of acute and chronic pain, was chemically incorporated into a poly(anhydride-ester) backbone. The polymer termed “PolyMorphine”, was designed to degrade hydrolytically releasing morphine in a controlled manner to ultimately provide analgesia for an extended time period. PolyMorphine was synthesized via melt-condensation polymerization and its structure was characterized using proton and carbon nuclear magnetic resonance spectroscopies, and infrared spectroscopy. The weight-average molecular weight and the thermal properties were determined. The hydrolytic degradation pathway of the polymer was determined by in vitro studies, showing that free morphine is released. In vitro cytocompatibility studies demonstrated that PolyMorphine is non-cytotoxic towards fibroblasts. In vivo studies using mice showed that PolyMorphine provides analgesia for 3 days, 20 times the analgesic window of free morphine. The animals retained full responsiveness to morphine after being subjected to an acute morphine challenge. PMID:22877734

  4. New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

    NASA Technical Reports Server (NTRS)

    Wolfe, James F.

    1993-01-01

    The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

  5. Poly(3-Hydroxypropionate): a Promising Alternative to Fossil Fuel-Based Materials

    PubMed Central

    Andreeßen, Björn; Taylor, Nicolas

    2014-01-01

    Polyhydroxyalkanoates (PHAs) are storage compounds synthesized by numerous microorganisms and have attracted the interest of industry since they are biobased and biodegradable alternatives to fossil fuel-derived plastics. Among PHAs, poly(3-hydroxypropionate) [poly(3HP)] has outstanding material characteristics and exhibits a large variety of applications. As it is not brittle like, e.g., the best-studied PHA, poly(3-hydroxybutyrate) [poly(3HB)], it can be used as a plasticizer in blends to improve their properties. Furthermore, 3-hydroxypropionic acid (3HP) is considered likely to become one of the new industrial building blocks, and it can be obtained from poly(3HP) by simple hydrolysis. Unfortunately, no natural organism is known to accumulate poly(3HP) so far. Thus, several efforts have been made to engineer genetically modified organisms capable of synthesizing the homopolymer or copolymers containing 3HP. In this review, the achievements made so far in efforts to obtain biomass which has accumulated poly(3HP) or 3HP-containing copolymers, as well as the properties of these polyesters and their applications, are compiled and evaluated. PMID:25149521

  6. Poly(3-hydroxypropionate): a promising alternative to fossil fuel-based materials.

    PubMed

    Andreessen, Björn; Taylor, Nicolas; Steinbüchel, Alexander

    2014-11-01

    Polyhydroxyalkanoates (PHAs) are storage compounds synthesized by numerous microorganisms and have attracted the interest of industry since they are biobased and biodegradable alternatives to fossil fuel-derived plastics. Among PHAs, poly(3-hydroxypropionate) [poly(3HP)] has outstanding material characteristics and exhibits a large variety of applications. As it is not brittle like, e.g., the best-studied PHA, poly(3-hydroxybutyrate) [poly(3HB)], it can be used as a plasticizer in blends to improve their properties. Furthermore, 3-hydroxypropionic acid (3HP) is considered likely to become one of the new industrial building blocks, and it can be obtained from poly(3HP) by simple hydrolysis. Unfortunately, no natural organism is known to accumulate poly(3HP) so far. Thus, several efforts have been made to engineer genetically modified organisms capable of synthesizing the homopolymer or copolymers containing 3HP. In this review, the achievements made so far in efforts to obtain biomass which has accumulated poly(3HP) or 3HP-containing copolymers, as well as the properties of these polyesters and their applications, are compiled and evaluated.

  7. Synthesis, characterization and antimicrobial applications of zinc oxide nanoparticles loaded gum acacia/poly(SA) hydrogels.

    PubMed

    Bajpai, S K; Jadaun, Mamta; Tiwari, Seema

    2016-11-20

    In this work, zinc oxide nanoparticles were synthesized in-situ within the gum acacia/poly (acrylate) hydrogel network using hydrothermal approach. The synthesized zinc oxide nanoparticles were characterized by Surface plasmon resonance (SPR), X-Ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM). The water absorption behavior of ZnO/GA/poly(SA) hydrogels was investigated in the phosphate buffer saline (PBS) of pH 7.4 at 37°C. The water uptake data were analyzed with the help of various kinetic models. Finally, the antimicrobial action of nanocomposites was studied using E. coli as model bacteria.

  8. Physiologically driven avian vocal synthesizer

    NASA Astrophysics Data System (ADS)

    Sitt, Jacobo D.; Arneodo, Ezequiel M.; Goller, Franz; Mindlin, Gabriel B.

    2010-03-01

    In this work, we build an electronic syrinx, i.e., a programmable electronic device capable of integrating biomechanical model equations for the avian vocal organ in order to synthesize song. This vocal prosthesis is controlled by the bird’s neural instructions to respiratory and the syringeal motor systems, thus opening great potential for studying motor control and its modification by sensory feedback mechanisms. Furthermore, a well-functioning subject-controlled vocal prosthesis can lay the foundation for similar devices in humans and thus provide directly health-related data and procedures.

  9. Method of synthesizing tungsten nanoparticles

    SciTech Connect

    Thoma, Steven G; Anderson, Travis M

    2013-02-12

    A method to synthesize tungsten nanoparticles has been developed that enables synthesis of nanometer-scale, monodisperse particles that can be stabilized only by tetrahydrofuran. The method can be used at room temperature, is scalable, and the product concentrated by standard means. Since no additives or stabilizing surfactants are required, this method is particularly well suited for producing tungsten nanoparticles for dispersion in polymers. If complete dispersion is achieved due to the size of the nanoparticles, then the optical properties of the polymer can be largely maintained.

  10. PREPARATION OF BLOCK COPOLYMERS OF POLY(STYRENE) AND POLY(T-BUTYL ACRYLATE) OF VARIOUS MOLECULAR WEIGHTS AND ARCHITECTURES BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    EPA Science Inventory

    Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NA novel PLED architecture containing biologically synthesized gold nanoparticles and ultra thin silver layer

    NASA Astrophysics Data System (ADS)

    Pıravadılı Mucur, Selin; Tekin, Emine; San, Sait Eren; Duygulu, Özgür; Öztürk, Hasan Ümit; Utkan, Güldem; Denizci, Aziz Akın

    2015-09-01

    The influences of biologically synthesized gold nanoparticles (bio-GNPs) and ultra thin silver layer (UTSL) on the polymer light emitting diodes (PLEDs) are investigated for the first time. The performance of the fabricated PLEDs is enhanced by embedding of bio-GNPs into the hole transport layer (HTL). Furthermore, the tailored device architecture containing UTSL increases the electron transport through lightning rod effect. Bio-GNPs are successfully produced as spherical shape with size of circa 10.4 nm. Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene (MEH-PPV) and [poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate); (PEDOT:PSS)/bio-GNPs blends are used as an active layer and HTL, respectively. Novel PLEDs fabricated with 0.125 wt% bio-GNPs/PEDOT:PSS and 0.5 nm UTSL exhibit nearly 2.5-fold enhancement in the device efficiency.

  11. Block poly(ester-urethane)s based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and poly(3-hydroxyhexanoate-co-3-hydroxyoctanoate).

    PubMed

    Chen, Zhifei; Cheng, Shaoting; Xu, Kaitian

    2009-04-01

    A series of block poly(ester-urethane) poly(3/4HB-HHxHO) urethanes (abbreviated as PUHO) based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB-diol) and poly(3-hydroxyhexanoate-co-3-hydroxyoctanoate) (PHHxHO-diol) segments were synthesized by a facile way of melting polymerization using 1,6-hexamethylene diisocyanate (HDI) as the coupling agent, with different 3HB, 4HB, HHxHO compositions and segment lengths. The chemical structure, molecular weight and distribution were systematically characterized by (1)H, (13)C nuclear magnetic resonance spectrum (NMR), two-dimensional correlation spectroscopy (COSY ((1)H, (13)C) NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The thermal property was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hydrophilicity was investigated by static contact angle of water and CH(2)I(2). DSC revealed that the poly(3/4HB-HHxHO) urethanes are almost amorphous with a little crystallinity (less than 6%) and T(g) from -23 degrees C to -3 degrees C. The polyurethanes are more hydrophobic (water contact angle 88 degrees -117 degrees ) than the P3/4HB and PHHxHO raw materials. The lactate dehydrogenase (LDH) assay and platelet adhesion determination showed that the obtained polyurethanes have much higher platelet adhesion property than raw materials and common biodegradable polymers polylactic acid (PLA) and poly(3-hydroxybutyrate) (PHB). Hydrophobicity and crystallinity degree are important factors to affect the platelet adhesion. All the properties can be tailored by changing the composition and segment length of prepolymers P3/4HB-diol and PHHxHO-diol.

  12. Poly(Lactic Acid) Hemodialysis Membranes with Poly(Lactic Acid)-block-Poly(2-Hydroxyethyl Methacrylate) Copolymer As Additive: Preparation, Characterization, and Performance.

    PubMed

    Zhu, Lijing; Liu, Fu; Yu, Xuemin; Xue, Lixin

    2015-08-19

    Poly(lactic acid) (PLA) hemodialysis membranes with enhanced antifouling capability and hemocompatibility were developed using poly(lactic acid)-block-poly(2-hydroxyethyl methacrylate) (PLA-PHEMA) copolymers as the blending additive. PLA-PHEMA block copolymers were synthesized via reversible addition-fragmentation (RAFT) polymerization from aminolyzed PLA. Gel permeation chromatography (GPC) and (1)H-nuclear magnetic resonance ((1)H NMR) were applied to characterize the synthesized products. By blending PLA with the amphiphilic block copolymer, PLA/PLA-PHEMA membranes were prepared by nonsolvent induced phase separation (NIPS) method. Their chemistry and structure were characterized with X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy (AFM). The results revealed that PLA/PLA-PHEMA membranes with high PLA-PHEMA contents exhibited enhanced hydrophilicity, water permeability, antifouling and hemocompatibility. Especially, when the PLA-PHEMA concentration was 15 wt %, the water flux of the modified membrane was about 236 L m(-2) h(-1). Its urea and creatinine clearance was more than 0.70 mL/min, lysozyme clearance was about 0.50 mL/min, BSA clearance was as less as 0.31 mL/min. All the results suggest that PLA-PHEMA copolymers had served as effective agents for optimizing the property of PLA-based membrane for hemodialysis applications.

  13. Synthetic evaluation of disulphide-bonded sarafotoxin on a poly(oxy ether) grafted dendrimeric poly(alkyl amine) support for polymer assisted organic synthesis.

    PubMed

    Siyad, M A; Kumar, G S Vinod

    2013-08-07

    The present paper describes the synthesis, characterization and assessment of a novel class of insoluble polymeric polystyrene supports which combines polar poly(ethylene glycol)dimethacrylate as a cross-linker and poly(ethylene glycol) grafted poly(N,N-bisethylamine) as a dendritic template. Poly(N,N-bisethylamine) dendrimers were generated by a series of reactions such as Schiff base integration, acidolysis, diazotization and thionyl chloride treatment. The same successive sequences of reactions have been followed for second generation dendrimers also and subjected to PEGylation (PEG 600) to achieve the desirable physico-chemical properties. The applicability of the novel PEGylated dendrimer support was demonstrated by synthesizing linear as well as disulfide bonded peptides in high yields and purities.

  14. Hydrophilic polymer composites synthesized by electrospinning under dense carbon dioxide

    NASA Astrophysics Data System (ADS)

    Wahyudiono, Okamoto, Koichi; Machmudah, Siti; Kanda, Hideki; Goto, Motonobu

    2015-12-01

    Electrospinning technique is feasible in some applications, it has attracted more attention in recent years. Various polymers have been successfully electrospun into ultrafine fibers in solvent solution and some in melt form. In this work, polyvinylpyrrolidone (PVP) as a hydrophilic polymer would be synthesized by electrospinning under dense carbon dioxide (CO2). The experiments were performed at 40 °C and ˜ 5 MPa. During the electrospinning process, the applied voltage was 10-17 kV and the distance of nozzle and collector was 8 cm. The concentration of PVP solution as a major component was 4 wt%. The results showed that the fibers surface morphology from PVP which blended with poly L-lactide acid (PLLA) were smooth with hollow core fibers at 5 MPa. At the same conditions, PVP-carbon nanotube was also successfully generated into electrospun fiber products with diameter ˜ 2 μm.

  15. Molecular Syntheses of Extended Materials

    NASA Astrophysics Data System (ADS)

    Paley, Daniel W.

    Bottom-up molecular synthesis is a route to chemically and crystallographically uniform polymers and solid-state materials. Through the use of molecular precursors, we gain atomic-level control of functionality and fine-tuning of the collective properties of materials. This dissertation presents two studies that demonstrate this approach. Ring-opening alkyne metathesis polymerization is a possible approach to monodisperse conjugated polymers, but its applications have been limited by difficult syntheses and high air sensitivity of known organometallic ROAMP initiators. We designed a dimeric, air-stable molybdenum alkylidyne with a tris(phenolate) supporting ligand. The precatalyst is activated by addition of methanol and polymerizes cyclooctynes with excellent chemical selectivity and functional group tolerance. The Nuckolls and Roy groups have introduced a new family of solid-state compounds synthesized from cobalt chalcogenide clusters Co6Q 8(PR3)6 and fullerenes. The first examples of these materials crystallized in superatom lattices with the symmetry of simple inorganic solids CdI2 (P-3m1) and NaCl (Fm-3m). This dissertation reveals that further members of the family feature extraordinary diversity of structure, including a pseudo-trigonal array of fulleride dimers in [Co 6Te8(PEt3)6]2[C140 ][C70]2 and a heterolayered van der Waals cocrystal [Co6Se8(PEt2phen)6][C 60]5. In addition to these unusual crystal structures, this dissertation presents a method for assigning redox states from crystallographic data in Co6Q8 clusters. Finally, a detailed guide to the collection and solution of single-crystal X-ray data is presented. The guide is intended for independent study by new crystallographers.

  16. Synthesis and Structure-Property Relationships of Poly(sulfone)s for Anion Exchange Membranes

    SciTech Connect

    Yan, JL; Moore, HD; Hibbs, MR; Hickner, MA

    2013-10-05

    Membranes based on cationic polymers that conduct anions are important for enabling alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. Anion exchange membranes with poly(arylene ether sulfone) backbones are demonstrated by two routes: chloromethylation of commercially available poly(sulfone)s or radical bromination of benzylmethyl moieties in poly(sulfone)s containing tetramethylbisphenol A monomer residues. Polymers with tethered trimethylbenzyl ammonium moieties resulted from conversion of the halomethyl groups by quaternization with trimethyl amine. The water uptake of the chloromethylated polymers was dependent on the type of poly(sulfone) backbone for a given IEC. Bisphenol A-based Udel (R) poly(sulfone) membranes swelled in water to a large extent while membranes from biphenol-based Radel (R) poly(sulfone), a stiffer backbone than Udel, only showed moderate water uptake. The water uptake of cationic poly(sulfone)s was further reduced by synthesizing tetramethylbisphenol A and 4,4-biphenol-containing poly(sulfone) copolymers where the ionic groups were clustered on the tetramethylbisphenol A residues. The conductivity of all samples scaled with the bulk water uptake. The hydration number of the membranes could be increased by casting membranes from the ionic form polymers versus converting the halomethyl form cast polymers to ionic form in the solid state. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1790-1798, 2013

  17. Solar CalPoly

    SciTech Connect

    Stannard, Sandra

    2016-06-15

    The target budget of INhouse was about $650,000 for all materials and student expenses of the Solar Decathlon competition. In order to reach our goal, Cal Poly students and faculty worked with the College of Architecture and Environmental Design’s External Relations office to actively fundraise for INhouse. Students connected with Cal Poly alumni through phone calls, postal mail, email, and live presentations to reach as many alumni in the state of California as possible. Before construction begun, students and faculty met on a weekly basis to determine what brands of materials for the home to use and who would be responsible for reaching out to the company to seek a donation. Our College of Architecture and Environmental Design’s administration was essential in helping us fundraise. For some time, the college was hoping to depend on about half of our fundraising expenses to be covered through the sale of INhouse. However, plans to sell the home fell through during the design development phase; the college turned to the sale of a different asset in to help us meet our goal. If we were to do this project again, completing the design concept and securing a future location of our home sooner would have enhanced our fundraising activities.

  18. Synthese de champs sonores adaptative

    NASA Astrophysics Data System (ADS)

    Gauthier, Philippe-Aubert

    La reproduction de champs acoustiques est une approche physique au probleme technologique de la spatialisation sonore. Cette these concerne l'aspect physique de la reproduction de champs acoustiques. L'objectif principal est l'amelioration de la reproduction de champs acoustiques par "synthese de champs acoustiques" ("Wave Field Synthesis", WFS), une approche connue, basee sur des hypotheses de champ libre, a l'aide du controle actif par l'ajout de capteurs de l'erreur de reproduction et d'une boucle fermee. Un premier chapitre technique (chapitre 4) expose les resultats d'appreciation objective de la WFS par simulations et mesures experimentales. L'effet indesirable de la salle de reproduction sur les qualites objectives de la WFS fut illustre. Une premiere question de recherche fut ensuite abordee (chapitre 5), a savoir s'il est possible de reproduire des champs progressifs en salle dans un paradigme physique de controle actif: cette possibilite fut prouvee. L'approche technique privilegiee, "synthese de champs adaptative" ("Adaptive Wave Field Synthesis" [AWFS]), fut definie, puis simulee (chapitre 6). Cette approche d'AWFS comporte une originalite en controle actif et en reproduction de champs acoustiques: la fonction cout quadratique representant la minimisation des erreurs de reproduction inclut une regularisation de Tikhonov avec solution a priori qui vient de la WFS. L'etude de l'AWFS a l'aide de la decomposition en valeurs singulieres (chapitre 7) a permis de comprendre les mecanismes propres a l'AWFS. C'est la deuxieme principale originalite de la these. L'algorithme FXLMS (LMS et reference filtree) est modifie pour l'AWFS (chapitre 8). Le decouplage du systeme par decomposition en valeurs singulieres est illustre dans le domaine du traitement de signal et l'AWFS basee sur le controle independant des modes de rayonnement est simulee (chapitre 8). Ce qui constitue la troisieme originalite principale de cette these. Ces simulations du traitement de signal

  19. Synthesis and characterization of poly(sodium acrylate)/ bentonite superabsorbent composite

    NASA Astrophysics Data System (ADS)

    Xie, Yiming; Wei, Yuelin; Huang, Yunfang; Lin, Jianming; Wu, Jihuai

    2012-01-01

    Poly(sodium acrylate)/bentonite superabsorbent composite with water absorbency 1562 g·g-1 was synthesized by inverse suspension polymerization. The introduction of bentonite improves the water absorbency and facilitates the particle size even distribution of the composite. The network structure in the superabsorbent hydrogel is confirmed.

  1. Synthesis and structural dependence of the functional properties of new green fluorescent poly(propyleneamine) dendrimers

    NASA Astrophysics Data System (ADS)

    Grabchev, Ivo; Mokreva, Pavlina; Gancheva, Valeria; Terlemezyan, Levon

    2013-04-01

    Two new green fluorescence poly(propyleneamine) dendrimers from second generation, comprising eight 1,8-naphthalimide signaling units in their periphery have been synthesized and investigated. Тheir photophysical characteristics have been determined in organic solvents of different polarity. Particular attention has been paid to the spectral characteristics of the solid dendrimer films. The photostability of the dendrimers has also been studied.

  2. Sophorolipid-derived unsaturated and epoxy fatty acid estolides as plasticizers for poly(3-hydroxybutyrate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Unsaturated and epoxy fatty acid estolides were synthesized from the omega and omega-1 hydroxy fatty acids derived from sophorolipids (SLs) prepared by fermentation from glucose:soybean oil and glucose:oleic acid, respectively. These estolides were utilized as additives in solution-cast poly(3-hydro...

  3. Thermo- and electro-dual responsive poly(ionic liquid) electrolyte based smart windows.

    PubMed

    Chen, Fei; Ren, Yongyuan; Guo, Jiangna; Yan, Feng

    2017-01-31

    Thermo- and electro-dual responsive poly(ionic liquid) (PIL) based electrolytes were synthesized by co-polymerization of N-isopropylacrylamide (NIPAM) with (or without) 3-butyl-1-vinyl-imidazolium bromide ([BVIm][Br]) using diallyl-viologen (DAV) as both the cross-linking agent and electrochromic material.

  4. Diblock copolymers containing compositionally-uniform poly(HEMA-co-DMAEMA)

    NASA Astrophysics Data System (ADS)

    Guice, Kyle; Teoh, Raymond; Loo, Yueh-Lin

    2007-03-01

    Hydroxyethyl methacrylate (HEMA) and dimethylaminoethyl methacrylate (DMAEMA) have been investigated as precursors for pH-responsive hydrogels. DMAEMA contains tertiary amine functionality that is reversibly protonated below its pKa. The swelling characteristics of poly(HEMA-co-DMAEMA) hydrogels are dependent on the distribution of DMAEMA, which in turn depends on the monomer composition and the monomer reactivity ratios. We find that the reactivity ratios are highly solvent dependent. Gradient copolymers are favored in most solvents at all monomer compositions. In dimethylsulfoxide, however, the reactivity ratios are near unity; compositionally-uniform poly(HEMA-co-DMAEMA) copolymers can therefore be synthesized at any composition. We have synthesized diblock copolymers containing poly(HEMA-co-DMAEMA) by a combination of atom transfer radical polymerization and click chemistry. The resulting diblock copolymers have controlled molecular weights, molecular weight distributions, and comonomer distributions, and they form well-defined periodic nanoscale structures consistent with their molecular characteristics.

  5. Poly(carbonate–amide)s Derived from Bio-Based Resources: Poly(ferulic acid-co-tyrosine)

    PubMed Central

    2015-01-01

    Ferulic acid (FA), a bio-based resource found in fruits and vegetables, was coupled with a hydroxyl-amino acid to generate a new class of monomers to afford poly(carbonate–amide)s with potential to degrade into natural products. l-Serine was first selected as the hydroxyl-amino partner for FA, from which the activated p-nitrophenyl carbonate monomer was synthesized. Unfortunately, polymerizations were unsuccessful, and the elimination product was systematically obtained. To avoid elimination, we revised our strategy and used l-tyrosine ethyl ester, which lacks an acidic proton on the α position of the ethyl ester. Four new monomers were synthesized and converted into the corresponding poly(carbonate–amide)s with specific regioselectivities. The polymers were fully characterized through thermal and spectroscopic analyses. Preliminary fluorescent studies revealed interesting photophysical properties for the monomers and their corresponding poly(carbonate–amide)s, beyond the fluorescence characteristics of l-tyrosine and FA, making these materials potentially viable for sensing and/or imaging applications, in addition to their attractiveness as engineering materials derived from renewable resources. PMID:24839309

  6. Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles.

    PubMed

    Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

    2011-01-01

    Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers.

  7. Switching the Biointerface of Displaceable Poly-p-xylylene Coatings.

    PubMed

    Guan, Zhen-Yu; Wu, Chih-Yu; Li, Yi-Jye; Chen, Hsien-Yeh

    2015-07-08

    A new class of functionalized poly-p-xylyene coating has been synthesized to provide switchable and displaceable surface properties for biomaterials. The switchability is achieved through a mechanism for detaching/attaching biomolecules and/or a mechanism through which the programmed restoration of functions or their replacement by other functions can be carried out. This advanced version of poly-p-xylylene comprises an integrated disulfide moiety within the functional side group, and the switching phenomenon between the immobilized functional molecules is triggered by the redox thiol-disulfide interchange reaction. These dynamically well-defined molecules on the surfaces respond simultaneously to altered biological properties and controlled biointerfacial functions, for example, switching wettability or reversibly altered cell adhesion activity. Poly-p-xylylenes are a key player in controlling surface properties for many important applications, such as medical implants, biosensors, bioMEMS devices, and microfluidics. The introduction of this new facet of poly-p-xylylenes enables the dynamic mimicry of biological functions relevant to the design of new biomaterials.

  8. Synthesis and water-swelling of thermo-responsive poly(ester urethane)s containing poly(epsilon-caprolactone), poly(ethylene glycol) and poly(propylene glycol).

    PubMed

    Loh, Xian Jun; Colin Sng, Kian Boon; Li, Jun

    2008-08-01

    Thermo-responsive multiblock poly(ester urethane)s comprising poly(epsilon-caprolactone) (PCL), poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. The copolymers were characterized by GPC, NMR, FTIR, XRD, DSC and TGA. Water-swelling analysis carried out at different temperatures revealed that the bulk hydrophilicity of the copolymers could be controlled either by adjusting the composition of the copolymer or by changing the temperature of the environment. These thermo-responsive copolymer films formed highly swollen hydrogel-like materials when soaked in cold water and shrank when soaked in warm water. The changes are reversible. The mechanical properties of the copolymer films were assessed by tensile strength measurement. These copolymers were ductile when compared to PCL homopolymers. Young's modulus and the stress at break increased with increasing PCL content, whereas the strain at break increased with increasing PEG content. The results of the cytotoxicity tests based on the ISO 10993-5 protocol demonstrated that the copolymers were non-cytotoxic and could be potentially used in biomedical applications.

  9. Synthesizing Diamond from Liquid Feedstock

    NASA Technical Reports Server (NTRS)

    Tzeng, Yonhua

    2005-01-01

    A relatively economical method of chemical vapor deposition (CVD) has been developed for synthesizing diamond crystals and films. Unlike prior CVD methods for synthesizing diamond, this method does not require precisely proportioned flows of compressed gas feedstocks or the use of electrical discharges to decompose the feedstocks to obtain free radicals needed for deposition chemical reactions. Instead, the feedstocks used in this method are mixtures of common organic liquids that can be prepared in advance, and decomposition of feedstock vapors is effected simply by heating. The feedstock used in this method is a solution comprising between 90 and 99 weight percent of methanol and the balance of one or more other oxyhydrocarbons that could include ethanol, isopropanol, and/or acetone. This mixture of compounds is chosen so that dissociation of molecules results in the desired proportions of carbon-containing radicals (principally, CH3) and of OH, H, and O radicals. Undesirably, the CVD temperature and pressure conditions thermodynamically favor the growth of graphite over the growth of diamond. The H radicals are desirable because they help to stabilize the growing surface of diamond by shifting the thermodynamic balance toward favoring the growth of diamond. The OH and O radicals are desirable because they preferentially etch graphite and other non-diamond carbon, thereby helping to ensure the net deposition of pure diamond. The non-methanol compounds are included in the solution because (1) methanol contains equal numbers of C and O atoms; (2) an excess of C over O is needed to obtain net deposition of diamond; and (3) the non-methanol molecules contain multiple carbon atoms for each oxygen atom and thus supply the needed excess carbon A typical apparatus used in this method includes a reservoir containing the feedstock liquid and a partially evacuated stainless-steel reaction chamber. The reservoir is connected to the chamber via tubing and a needle valve or

  10. Engineering and Design of Polymeric Shells: Inwards Interweaving Polymers as Multilayer Nanofilm, Immobilization Matrix, or Chromatography Resins.

    PubMed

    Pan, Houwen Matthew; Yu, Han; Guigas, Gernot; Fery, Andreas; Weiss, Matthias; Patzel, Volker; Trau, Dieter

    2017-02-15

    Hydrogels with complex internal structures are required for advanced drug delivery systems and tissue engineering or used as inks for 3D printing. However, hydrogels lack the tunability and diversity of polymeric shells and require complicated postsynthesis steps to alter its structure or properties. We report on the first integrated approach to assemble and design polymeric shells to take on various complex structures and functions such as multilayer nanofilms, multidensity immobilization matrix, or multiadhesive chromatography resins via the tuning of four assembly parameters: (a) poly(allylamine) (PA) concentration, (b) number of poly(allylamine)/poly(styrenesulfonic acid) (PA/PSSA) incubations, (c) poly(allylamine) (PA) to poly(ethylene glycol) (PEG) grafting ratio, and (d) % H2O present during assembly. Our approach combines the complex 3D structures of hydrogels with the versatility of self-assembled polymeric layers. Polymeric shells produced from our method have a highly uniform material distribution and well-defined shell boundaries. Shell thickness, density, and adhesive properties are easily tunable. By virtue of such unique material features, we demonstrate that polymeric shells can be designed to expand beyond its conventional function as thin films and serve as immobilization matrix, chromatography resins, or even reaction compartments. This technique could also uncover interesting perspectives in the development of novel multimaterials for 3D printing to synthesize scaffolds at a higher order of complexity.

  11. Polycaprolactone-poly(ethylene glycol) multiblock copolymers as potential substitutes for di(ethylhexyl) phthalate in flexible poly(vinyl chloride) formulations.

    PubMed

    Ferruti, Paolo; Mancin, Ivan; Ranucci, Elisabetta; De Felice, Claudio; Latini, Giuseppe; Laus, Michele

    2003-01-01

    New high-molecular-weight hydrophobic/hydrophilic segmented copolymers of poly(ester ether carbonate) structure, containing poly(epsilon-caprolactone) (PCL) and poly(ethylene glycol) (PEG) segments in their main chain, were synthesized and characterized. These copolymers were obtained by a two-step chain-extension reaction carried out in the presence of alpha,omega-dihydroxy-oligoPCL of molecular weight 1250 and PEG samples of molecular weight 150, 400, 600, 1000, and 2000. The molecular structures of all synthesized materials were characterized by means of (1)H NMR and (13)C NMR spectroscopy, their molecular weights were determined by means of size exclusion chromatography, and their thermal properties were obtained by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The poly(ester ether carbonate)s of this study are partly or totally miscible at least up to 50 wt % with poly(vinyl chloride) (PVC) and could be used to produce flexible PVC formulations. The miscibility between PVC and the poly(ester ether carbonate)s reported in this paper was investigated by means of DSC and DMA analysis. PVC blends were also analyzed by determining their swellability and the amount of extractables in aqueous media. By comparison purposes, the chain-extension product of PCL1250, that is, PCL polycarbonate, was also synthesized and characterized. The results obtained demonstrated that the copolymers with shortest PEG segment length, i.e. PEG150, 400, and 600, give the best results in terms of miscibility with PVC and lead to blends with maximum resistance to extraction by water. Therefore, they represent, in principle, good substitutes for low-molecular-weight, leachable PVC plasticizers, such as di(ethylhexyl) phthalate.

  12. POLY-1,2,4-TRIAZOLES AND POLY-1,3,4-OXADIAZOLES FROM PRECURSOR POLY-N-ACYLHYDRAZIDINES,

    DTIC Science & Technology

    oxadiazole . Whereas, conversion of the precursor poly-N-acylhydrazidine predominantly to poly-1,2,4-triazole was affected by refluxing in solvents such... oxadiazole depending upon the heating rate. Poly-N-acylhydrazidine was of sufficient molecular weight to cast a clear yellow film which exhibited good...flexibility. The film, upon thermal treatment to temperatures as high as 300C, became brittle. The poly-1,3,4- oxadiazole and poly-1,2,4-triazole

  13. The mouse immune response to the double stranded polyribonucleotide complex poly(G) . poly(C).

    PubMed Central

    Gaffiero, G V; Robin, P; Nahon, E

    1984-01-01

    Ten inbred strains of mice were immunized with the double stranded polyribonucleotide complex polyguanylic . polycytidylic acid [poly(G) . poly(C)]. While some immunogenic properties of this duplex were comparable to those of other nucleic acids antigens, differences were also noted. High (SJL/J, BALB/c), low (DBA/2, AKR) and intermediate responders were observed; these differences were not abolished by adsorption of the duplex to MBSA. This pattern of immune response is distinct both from that observed with two other synthetic polyribonucleotide double helices [poly(A) . poly(U) and poly(I) . poly(C)] and with single stranded DNA. The anti-poly(G) . poly(C) activity was localized in the 7S region, whether the sera came from high or low responders, from mice immunized with or without a carrier, after one or several injections. In contrast with anti-poly(A) . poly(U) sera which do not react with poly(G) . poly(C), anti-poly(G) . poly(C) exhibited poly(A) . poly(U) binding activity; no clear relationship between the two activities, however, could be demonstrated. Thus a series of immunological properties differentiates poly(G) . poly(C) not only from the natural polydeoxyribonucleotide single stranded DNA, but also, and more unexpectedly, from two other double stranded polyribonucleotide complexes. These observations suggest that the mechanism controlling the antibody response to poly(G) . poly(C) differs from that regulating poly(A) . poly(U) and/or poly(I) . poly(C), and are to be connected with the fact that the anti-poly(G) . poly(C) antibodies occurring in the sera of patients with systemic lupus erythematosus did not correlate with the antibody activities directed toward the other duplexes. PMID:6697564

  14. Cellular behaviour of hepatocyte-like cells from nude mouse bone marrow-derived mesenchymal stem cells on galactosylated poly(D,L-lactic-co-glycolic acid).

    PubMed

    Roh, Hyun; Yang, Dae Hyeok; Chun, Heung Jae; Khang, Gilson

    2015-07-01

    Previously, the galactosylation of poly(d,l-lactic-co-glycolic acid) (PLGA) surface was accomplished by grafting allylamine (AA), using inductively coupled plasma-assisted chemical vapour deposition (ICP-CVD) and conjugating lactobionic acid (LA) with AA via 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide (EDC/NHS) activation for hepatic tissue-engineering purposes. As a continuation study, the cellular behaviour of hepatocyte-like cells (HLCs) on the surface of the galactosylated PLGA were investigated. Nude mouse bone marrow-derived mesenchymal stem cells (MSCs) were cultured under hepatogenic conditions and the differentiated cells were characterized by reverse-transcription polymerase chain reaction (RT-PCR), immunofluorescence and periodic acid-Schiff (PAS) staining. Galactosylated PLGA enhanced the proliferation rate of HLCs compared to the control; HLCs on the surface of the sample became aggregated and formed spheroids after 3 days of culture. A large number of cells on the surface of the sample exhibited increased liver-specific functional activities, such as albumin and urea secretions. In addition, multicellular spheroids in the sample strongly expressed phospholyated focal adhesion kinase (pFAK) (cell-matrix interactions), E-cadherin (cell-cell interactions) and connexin 32 (Cox32; gap junction).

  15. Balanced Ambipolar Poly(diketopyrrolopyrrole-alt-tetrafluorobenzene) Semiconducting Polymers Synthesized via Direct Arylation Polymerization.

    PubMed

    Wang, Kai; Wang, Guojie; Wang, Mingfeng

    2015-12-01

    The synthesis of an ambipolar π-conjugated copolymer consisting of alternating diketopyrrolopyrrole and tetrafluorobenzene via direct arylation polymerization (DAP) is reported. Two different combinations of monomers are investigated under various catalytic conditions for DAP. The target polymer obtained under an optimized catalytic condition shows minimal structural defects, a number-average molecular weight of 33.2 kDa, and balanced electron and hole mobility of 1 × 10(-2) cm(2) V(-1) S(-1) in the organic field-effect transistors fabricated and tested under ambient conditions.

  16. Structure and properties of poly(benzyl acrylate) synthesized under microwave energy

    NASA Astrophysics Data System (ADS)

    Oberti, Tamara G.; Schiavoni, M. Mercedes; Cortizo, M. Susana

    2008-05-01

    Benzyl acrylate was polymerized under microwave irradiation using radical initiation (benzoyl peroxide, BP). The effect of the concentration of BP and power irradiation on the conversion, average molecular weights and the polydispersity index ( Mw/ Mn) were investigated. The 1H NMR and 13C NMR spectra analysis showed tendency to syndiotacticity and branched polymers were obtained at high conversion of reactions. A significant enhancement of the rates of polymerization and similar thermodynamic behavior, as compared with those obtained under thermal conditions was found.

  17. PolyMetformin combines carrier and anticancer activities for in vivo siRNA delivery

    PubMed Central

    Zhao, Yi; Wang, Wei; Guo, Shutao; Wang, Yuhua; Miao, Lei; Xiong, Yang; Huang, Leaf

    2016-01-01

    Metformin, a widely implemented anti-diabetic drug, exhibits potent anticancer efficacies. Herein a polymeric construction of Metformin, PolyMetformin (PolyMet) is successfully synthesized through conjugation of linear polyethylenimine (PEI) with dicyandiamide. The delocalization of cationic charges in the biguanide groups of PolyMet reduces the toxicity of PEI both in vitro and in vivo. Furthermore, the polycationic properties of PolyMet permits capture of siRNA into a core-membrane structured lipid-polycation-hyaluronic acid (LPH) nanoparticle for systemic gene delivery. Advances herein permit LPH-PolyMet nanoparticles to facilitate VEGF siRNA delivery for VEGF knockdown in a human lung cancer xenograft, leading to enhanced tumour suppressive efficacy. Even in the absence of RNAi, LPH-PolyMet nanoparticles act similarly to Metformin and induce antitumour efficacy through activation of the AMPK and inhibition of the mTOR. In essence, PolyMet successfully combines the intrinsic anticancer efficacy of Metformin with the capacity to carry siRNA to enhance the therapeutic activity of an anticancer gene therapy. PMID:27264609

  18. Maleimide Functionalized Poly(ε-caprolactone)-b-poly(ethylene glycol) (PCL-PEG-MAL): Synthesis, Nanoparticle Formation, and Thiol Conjugation

    PubMed Central

    Ji, Shengxiang; Zhu, Zhengxi; Hoye, Thomas R.; Macosko, Christopher W.

    2010-01-01

    Summary Carboxylic acid terminated poly(ε-caprolactone)s (PCL-COOHs) with narrow polydispersity were synthesized and coupled with poly(ethylene glycol) (HO-PEG-OH) to afford PCL-PEG-OH copolymers. The hydroxyl groups in the PCL-PEG-OHs were then converted to maleimide groups to afford maleimide terminated PCL-PEG-MALs that contained 70–90% maleimide functionality. Nanoparticles with maleimide functionality on their surfaces were prepared by impingement mixing. Particle sizes and size distributions were determined by dynamic light scattering. Conjugation of reduced glutathione with model maleimides and two MAL-functional nanoparticles was also demonstrated. The amount of accessible maleimide on the particle surface was measured using Ellman’s reagent to range between ~51–67%. PMID:21731402

  19. Preparation and evaluation of poly(ethylene glycol)-poly(lactide) micelles as nanocarriers for oral delivery of cyclosporine a.

    PubMed

    Zhang, Yanhui; Li, Xinru; Zhou, Yanxia; Wang, Xiaoning; Fan, Yating; Huang, Yanqing; Liu, Yan

    2010-03-27

    A series of monomethoxy poly(ethylene glycol)-poly(lactide) (mPEG-PLA) diblock copolymers were designed according to polymer-drug compatibility and synthesized, and mPEG-PLA micelle was fabricated and used as a nanocarrier for solubilization and oral delivery of Cyclosporine A (CyA). CyA was efficiently encapsulated into the micelles with nanoscaled diameter ranged from 60 to 96 nm with a narrow size distribution. The favorable stabilities of CyA-loaded polymeric micelles were observed in simulated gastric and intestinal fluids. The in vitro drug release investigation demonstrated that drug release was retarded by polymeric micelles. The enhanced intestinal absorption of CyA-loaded polymeric micelles, which was comparable to the commercial formulation of CyA (Sandimmun Neoral®), was found. These suggested that polymeric micelles might be an effective nanocarrier for solubilization of poorly soluble CyA and further improving oral absorption of the drug.

  20. Surface modification by grafting of poly(SBMA-co-AEMA)-g-PDA coating and its application in CE.

    PubMed

    Chen, Lijuan; Tan, Lin; Liu, Songtao; Bai, Longchao; Wang, Yanmei

    2014-01-01

    In this paper, a novel copolymer consisting of sulfobetaine methacrylate (SBMA) and 2-aminoethyl methacrylate (AEMA) named as poly(SBMA-co-AEMA) was synthesized by conventional free-radical polymerization, the poly(SBMA-co-AEMA) zwitterionic copolymer was immobilized onto glass slides surface through polydopamine (PDA)-anchored coating and formed poly(SBMA-co-AEMA)-g-PDA coating. The defined copolymer was characterized by nuclear magnetic resonance hydrogen spectroscopy ((1)H NMR) and gel permeation chromatography. The surface morphology, thickness, and chemical component of poly(SBMA-co-AEMA)-g-PDA coating were studied by atom force microscope, ellipsometry, and X-ray photoelectron spectroscopy, respectively. The hydrophilicity and stability of these coatings were investigated by static water contact angles. And finally, the poly(SBMA-co-AEMA)-g-PDA coating was successfully applied into capillary inner surface for suppression electro-osmotic flow and protein separation by capillary electrophoresis.

  1. Poly-instanton inflation

    SciTech Connect

    Cicoli, Michele; Pedro, Francisco G.; Tasinato, Gianmassimo E-mail: f.pedro1@physics.ox.ac.uk

    2011-12-01

    We propose a new inflationary scenario in type IIB Calabi-Yau compactifications, where the inflaton is a Kähler modulus parameterising the volume of an internal four-cycle. The inflaton potential is generated via poly-instanton corrections to the superpotential which give rise to a naturally flat direction due to their double exponential suppression. Given that the volume mode is kept stable during inflation, all the inflaton-dependent higher dimensional operators are suppressed. Moreover, string loop effects can be shown to be negligible throughout all the inflationary dynamics for natural values of the underlying parameters. The model is characterised by a reheating temperature of the order T{sub rh} ≅ 10{sup 6} GeV which requires N{sub e} ≅ 54 e-foldings of inflation. All the inflationary observables are compatible with current observations since the spectral index is n{sub s} ≅ 0.96, while the tensor-to-scalar ratio is r ≅ 10{sup −5}. The volume of the Calabi-Yau is of order 10{sup 3} in string units, corresponding to an inflationary scale around 10{sup 15} GeV.

  2. Biologic activities of poly (2-azaadenylic acid) and poly (2-azainosinic acid).

    PubMed Central

    De Clercq, E; Huang, G F; Torrence, P F; Fukui, T; Kakiuchi, N; Ikehara, M

    1977-01-01

    Poly (2-azaadenylic acid) [(aza2A)n] and poly(2-azainosinic acid [(aza2I)n], two newly synthesized analogues of (A)n and (I)n, in which CH-2 of the purine ring is replaced by a nitrogen atom, have been evaluated in various biological assay systems. (Aza2A) n formed a complex with (U)n and (br5U)n, and (aza2I)n formed a complex with (C)n and (br5C)n, but these complexes were markedly destabilized relative to the corresponding (A)n or (I)n complexes. The (aza2A)n-and (aza2I)n-derived complexes failed to stimulate the production of interferon in primary rabbit kidney cells and human diploid fibroblasts, under conditions (A)n. (U)n, (I)n. (C)n and (I)n. (br5C)n induced high amounts of interferon. both (aza2A)n and (aza2I)n exerted a marked inhibitory effect on the endogenous RNA directed DNA polymerase (reverse transcriptase) activity associated with murine leukemia virus. They caused a relatively mild inhibition of complement activity in an hemolytic assay system. PMID:73166

  3. 21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber... purposes of this section, poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) are...

  4. 21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber... purposes of this section, poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) are...

  5. 21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber... purposes of this section, poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) are...

  6. 21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly(p-methylstyrene) and rubber-modified poly(p... Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber... purposes of this section, poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene) are...

  7. Injectable biodegradable thermosensitive hydrogel composite for orthopedic tissue engineering. 1. Preparation and characterization of nanohydroxyapatite/poly(ethylene glycol)-poly(epsilon-caprolactone)-poly(ethylene glycol) hydrogel nanocomposites.

    PubMed

    Fu, Shaozhi; Guo, Gang; Gong, Changyang; Zeng, Shi; Liang, Hang; Luo, Feng; Zhang, Xiaoning; Zhao, Xia; Wei, Yuquan; Qian, Zhiyong

    2009-12-31

    In this study, we synthesized a biodegradable triblock copolymer poly(ethylene glycol)-poly(epsilon-caprolactone)-poly(ethylene glycol) (PEG-PCL-PEG, PECE) by ring-opening copolymerization, and nanohydroxyapatite (n-HA) powder was prepared by a hydrothermal precipitation method. The obtained n-HA was incorporated into the PECE matrix to prepare injectable thermosensitive hydrogel nanocomposites. (1)H NMR, FT-IR, XRD, DSC, and TEM were used to investigate the properties of PECE copolymer and n-HA/PECE nanocomposites. The rheological measurements for n-HA/PECE nanocomposites revealed that the gelation temperature was approximately 36 degrees C. The sol-gel-sol transition behavior and phase transition diagrams were recorded through a test tube inverting method. The results showed that n-HA/PECE nanocomposites still had thermoresponsivity like that of PECE thermosensitive hydrogel. The morphology of the nanocomposites was observed by SEM; the results showed that the nanocomposites had a 3D network structure. In addition, the effects of n-HA contents on the properties of n-HA/PECE nanocomposites are also discussed in the paper. From the results, n-HA/PECE hydrogel is believed to be promising for injectable orthopedic tissue engineering due to its good thermosensitivity and injectability.

  8. Preparation and characterization of tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) nanogels for controlled release of naltrexone.

    PubMed

    Asadi, H; Rostamizadeh, K; Salari, D; Hamidi, M

    2011-09-15

    Tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) copolymers and related acrylated derivative were synthesized and used to prepare micelles and nanogels for controlled release of naltrexone. The resulting copolymers, micelles and nanogels were characterized by various techniques such as proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, fluorescence spectrometry, differential scanning calorimetry, photon correlation spectroscopy and scanning electron microscopy. The nanogels exhibited high encapsulation efficiency around 60% and excellent stability for long periods of time. The drug release profiles of micelles and nanogels were compared and it was found that the naltrexone loaded nanogels offered a steady and long-term release pattern for different periods of time up to 35 days, depending on the crosslinker concentration, compared to the micelles. The size of nanogels could be manipulated easily in the range of 128-200nm by variations in polymer concentration used in the nanogels preparation step. From the results obtained it can be concluded that PLA-PEG-PLA nanogels can be considered as a promising carrier for drug delivery purpose.

  9. Synthesis and self-assembly of brush-type poly[poly(ethylene glycol)methyl ether methacrylate]-block-poly(pentafluorostyrene) amphiphilic diblock copolymers in aqueous solution.

    PubMed

    Tan, B H; Hussain, H; Liu, Y; He, C B; Davis, T P

    2010-02-16

    Well-defined fluorinated brush-like amphiphilic diblock copolymers of poly[poly(ethylene glycol)methyl ether methacrylate] (P(PEGMA)) and poly(pentafluorostyrene) (PPFS) have been successfully synthesized via atom transfer radical polymerization (ATRP). The self-assembly behavior of these polymers in aqueous solutions was studied using (1)H NMR, fluorescence spectrometry, static and dynamic light scattering and transmission electron microscopy techniques. The micellar structure comprised of PPFS as the core and brush-like (hydrophobic main chain and hydrophilic branches) polymers as the coronas. The hydrodynamic radius (R(h)) of the micelles in aqueous solution was in the nanometer range, independent of the polymer concentration, consistent with a closed association model. Diblock copolymers with a longer P(PEGMA) block formed micelles with smaller R(h) and lower aggregation numbers consistent with an improved solubilization of the core. The micelles possessed a thick hydration layer as verified by the ratio of the radius of gyration, R(g) to the hydrodynamic radius, R(h). The aggregation number and ratio of R(g) to R(h) were observed to increase with temperature (20-50 degrees C), while the R(h) of the micelle decreased slightly over the same temperature range. An increase in temperature induced the brush-like PEG segments in the corona to dehydrate and shrink while forming micelles with larger aggregation numbers.

  10. Delivery of phytochemical thymoquinone using molecular micelle modified poly(D, L lactide-co-glycolide) (PLGA) nanoparticles

    NASA Astrophysics Data System (ADS)

    Ganea, Gabriela M.; Fakayode, Sayo O.; Losso, Jack N.; van Nostrum, Cornelus F.; Sabliov, Cristina M.; Warner, Isiah M.

    2010-07-01

    Continuous efforts have been made in the development of potent benzoquinone-based anticancer drugs aiming for improved water solubility and reduced adverse reactions. Thymoquinone is a liposoluble benzoquinone-based phytochemical that has been shown to have remarkable antioxidant and anticancer activities. In the study reported here, thymoquinone-loaded PLGA nanoparticles were synthesized and evaluated for physico-chemical, antioxidant and anticancer properties. The nanoparticles were synthesized by an emulsion solvent evaporation method using anionic molecular micelles as emulsifiers. The system was optimized for maximum entrapment efficiency using a Box-Behnken experimental design. Optimum conditions were found for 100 mg PLGA, 15 mg TQ and 0.5% w/v poly(sodium N-undecylenyl-glycinate) (poly-SUG). In addition, other structurally related molecular micelles such as poly(sodium N-heptenyl-glycinate) (poly-SHG), poly(sodium N-undecylenyl-leucinate) (poly-SUL), and poly(sodium N-undecylenyl-valinate) (poly-SUV) were also examined as emulsifiers. All investigated molecular micelles provided excellent emulsifier properties, leading to maximum optimized TQ entrapment efficiency, and monodispersed particle sizes below 200 nm. The release of TQ from molecular micelle modified nanoparticles was investigated by dialysis and reached lower levels than the free drug. The antioxidant activity of TQ-loaded nanoparticles, indicated by IC50 (mg ml - 1 TQ for 50% 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity), was highest for poly-SUV emulsified nanoparticles (0.030 ± 0.002 mg ml - 1) as compared to free TQ. In addition, it was observed that TQ-loaded nanoparticles emulsified with poly-SUV were more effective than free TQ against MDA-MB-231 cancer cell growth inhibition, presenting a cell viability of 16.0 ± 5.6% after 96 h.

  11. Vault-poly-ADP-ribose polymerase in the Octopus vulgaris brain: a regulatory factor of actin polymerization dynamic.

    PubMed

    De Maio, Anna; Natale, Emiliana; Rotondo, Sergio; Di Cosmo, Anna; Faraone-Mennella, Maria Rosaria

    2013-09-01

    Our previous behavioural, biochemical and immunohistochemical analyses conducted in selected regions (supra/sub oesophageal masses) of the Octopus vulgaris brain detected a cytoplasmic poly-ADP-ribose polymerase (more than 90% of total enzyme activity). The protein was identified as the vault-free form of vault-poly-ADP-ribose polymerase. The present research extends and integrates the biochemical characterization of poly-ADP-ribosylation system, namely, reaction product, i.e., poly-ADP-ribose, and acceptor proteins, in the O. vulgaris brain. Immunochemical analyses evidenced that the sole poly-ADP-ribose acceptor was the octopus cytoskeleton 50-kDa actin. It was present in both free, endogenously poly-ADP-ribosylated form (70kDa) and in complex with V-poly-ADP-ribose polymerase and poly-ADP-ribose (260kDa). The components of this complex, alkali and high salt sensitive, were purified and characterized. The kind and the length of poly-ADP-ribose corresponded to linear chains of 30-35 ADP-ribose units, in accordance with the features of the polymer synthesized by the known vault-poly-ADP-ribose polymerase. In vitro experiments showed that V-poly-ADP-ribose polymerase activity of brain cytoplasmic fraction containing endogenous actin increased upon the addition of commercial actin and was highly reduced by ATP. Anti-actin immunoblot of the mixture in the presence and absence of ATP showed that the poly-ADP-ribosylation of octopus actin is a dynamic process balanced by the ATP-dependent polymerization of the cytoskeleton protein, a fundamental mechanism for synaptic plasticity.

  12. Development of biomimetic nano-hydroxyapatite/poly(hexamethylene adipamide) composites.

    PubMed

    Wang, Xuejiang; Li, Yubao; Wei, Jie; de Groot, Klass

    2002-12-01

    In this study, acicular nano-hydroxyapatite (n-HA) was used to make a new biomimetic composite with polyamide (poly hexamethylene adipamide) by a unique technique. The physical and chemical characteristics of the composites were tested. It was found that these synthesized n-HA crystals were similar to bone apatite in size, phase composition and crystal structure. The biomimetic n-HA crystals were uniformly distributed in the polymer matrix and its content can reach 65%, close to that in natural bone. Chemical binding between inorganic n-HA and polyamide was investigated and discussed. The mechanical properties of the composites were found to match well with those of natural bone.

  13. Patterned Poly(dopamine) Films for Enhanced Cell Adhesion.

    PubMed

    Chen, Xi; Cortez-Jugo, Christina; Choi, Gwan H; Björnmalm, Mattias; Dai, Yunlu; Yoo, Pil J; Caruso, Frank

    2017-01-18

    Engineered materials that promote cell adhesion and cell growth are important in tissue engineering and regenerative medicine. In this work, we produced poly(dopamine) (PDA) films with engineered patterns for improved cell adhesion. The patterned films were synthesized via the polymerization of dopamine at the air-water interface of a floating bed of spherical particles. Subsequent dissolution of the particles yielded free-standing PDA films with tunable geometrical patterns. Our results show that these patterned PDA films significantly enhance the adhesion of both cancer cells and stem cells, thus showing promise as substrates for cell attachment for various biomedical applications.

  14. Composites comprising biologically-synthesized nanomaterials

    DOEpatents

    Curran, Seamus; Dias, Sampath; Blau, Werner; Wang, Jun; Oremland, Ronald S; Baesman, Shaun

    2013-04-30

    The present disclosure describes composite materials containing a polymer material and a nanoscale material dispersed in the polymer material. The nanoscale materials may be biologically synthesized, such as tellurium nanorods synthesized by Bacillus selenitireducens. Composite materials of the present disclosure may have optical limiting properties and find use in optical limiting devices.

  15. "Comments on Slavin": Synthesizing Causal Inferences

    ERIC Educational Resources Information Center

    Briggs, Derek C.

    2008-01-01

    When causal inferences are to be synthesized across multiple studies, efforts to establish the magnitude of a causal effect should be balanced by an effort to evaluate the generalizability of the effect. The evaluation of generalizability depends on two factors that are given little attention in current syntheses: construct validity and external…

  16. Synthesizing Regression Results: A Factored Likelihood Method

    ERIC Educational Resources Information Center

    Wu, Meng-Jia; Becker, Betsy Jane

    2013-01-01

    Regression methods are widely used by researchers in many fields, yet methods for synthesizing regression results are scarce. This study proposes using a factored likelihood method, originally developed to handle missing data, to appropriately synthesize regression models involving different predictors. This method uses the correlations reported…

  17. Synthesizing Smart Polymeric and Composite Materials

    NASA Astrophysics Data System (ADS)

    Gong, Chaokun

    Smart materials have been widely investigated to explore new functionalities unavailable to traditional materials or to mimic the multifunctionality of biological systems. Synthetic polymers are particularly attractive as they already possess some of the attributes required for smart materials, and there are vast room to further enhance the existing properties or impart new properties by polymer synthesis or composite formulation. In this work, three types of smart polymer and composites have been investigated with important new applications: (1) healable polymer composites for structural application and healable composite conductor for electronic device application; (2) conducting polymer polypyrrole actuator for implantable medical device application; and (3) ferroelectric polymer and ceramic nanoparticles composites for electrocaloric effect based solid state refrigeration application. These application entail highly challenging materials innovation, and my work has led to significant progress in all three areas. For the healable polymer composites, well known intrinsically healable polymer 2MEP4F (a Diels-Alder crosslinked polymer formed from a monomer with four furan groups and another monomer with two maleimide groups) was first chosen as the matrix reinforced with fiber. Glass fibers were successfully functionalized with maleimide functional groups on their surface. Composites from functionalized glass fibers and 2MEP4F healable polymer were made to compare with composites made from commercial carbon fibers and 2MEP4F polymer. Dramatically improved short beam shear strength was obtained from composite of functionalized glass fibers and 2MEP4F polymer. The high cost of 2MEP4F polymer can potentially limit the large-scale application of the developed healable composite, we further developed a new healable polymer with much lower cost. This new polymer was formed through the Diels-Alder crosslinking of poly(furfuryl alcohol) (PFA) and 1,1'-(Methylenedi-4

  18. Reversible adsorption of catalase onto Fe(3+) chelated poly(AAm-GMA)-IDA cryogels.

    PubMed

    Aktaş Uygun, Deniz; Uygun, Murat; Akgöl, Sinan; Denizli, Adil

    2015-05-01

    In this presented study, poly(acrylamide-glycidyl methacrylate) [poly(AAm-GMA)] cryogels were synthesized by cryopolymerization technique at sub-zero temperature. Prepared cryogels were then functionalized with iminodiacetic acid (IDA) and chelated with Fe(3+) ions in order produce the metal chelate affinity matrix. Synthesized cryogels were characterized with FTIR, ESEM and EDX analysis, and it was found that the cryogel had sponge like structure with interconnected pores and their pore diameter was about 200 μm. Fe(3+) chelated poly(AAm-GMA)-IDA cryogels were used for the adsorption of catalase and optimum adsorption conditions were determined by varying the medium pH, initial catalase concentration, temperature and ionic strength. Maximum catalase adsorption onto Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was found to be 12.99 mg/g cryogel at 25 °C, by using pH 5.0 acetate buffer. Adsorbed catalase was removed from the cryogel by using 1.0M of NaCl solution and desorption yield was found to be 96%. Additionally, reusability profile of the Fe(3+) chelated poly(AAm-GMA)-IDA cryogel was also investigated and it was found that, adsorption capacity of the cryogels didn't decrease significantly at the end of the 40 reuses. Catalase activity studies were also tested and it was demonstrated that desorbed catalase retained 70% of its initial activity.

  19. Efficient gene transfection using novel cationic polymers poly(hydroxyalkylene imines).

    PubMed

    Zaliauskiene, Lolita; Bernadisiute, Ula; Vareikis, Ausvydas; Makuska, Ricardas; Volungeviciene, Ieva; Petuskaite, Agne; Riauba, Laurynas; Lagunavicius, Arunas; Zigmantas, Sarunas

    2010-09-15

    A series of novel cationic polymers poly(hydroxyalkylene imines) were synthesized and tested for their ability to transfect cells in vitro and in vivo. Poly(hydroxyalkylene imines), in particular, poly(2-hydroxypropylene imine) (pHP), poly(2-hydroxypropylene imine ethylene imine) (pHPE), and poly(hydroxypropylene imine propylene imine) (pHPP) were synthesized by polycondensation reaction from 1,3-diamino-2-propanol and the appropriate dibromide. Electron microscopic examination demonstrated that the resulting polymers condensed DNA into toroid shape complexes of 100-150 nm in size. Transfection studies showed that all three polymers were able to deliver genetic material into the cell, with pHP being superior to pHPP and pHPE. pHP acted as an efficient gene delivery agent in a variety of different cell lines and outcompeted most of the widely used polymer or lipid based transfection reagents. Intravenous administration of pHP-DNA polyplexes in mice followed by the reporter gene analysis showed that the reagent was suitable for in vivo applications. In summary, the results indicate that pHP is a new efficient reagent for gene delivery in vitro and in vivo.

  20. High-molecular-weight poly(Gly-Val-Gly-Val-Pro) synthesis through microwave irradiation.

    PubMed

    Goto, Mitsuaki; Endo, Takeshi

    2016-07-01

    In this study, we synthesized a polypeptide from its pentapeptide unit using microwave irradiation. Effective methods for polypeptide synthesis from unit peptides have not been reported. Here, we used a key elastin peptide, H-GlyValGlyValPro-OH (GVGVP), as the monomer peptide. It is difficult to obtain poly(Gly-Val-Gly-Val-Pro) (poly(GVGVP)) from the pentapeptide unit of elastin, GVGVP, via polycondensation. Poly(GVGVP) prepared from genetically recombinant Escherichia coli is a well-known temperature-sensitive polypeptide, and this temperature sensitivity is known as the lower critical solution temperature. When microwave irradiation was performed in the presence of various additives, the pentapeptide (GVGVP) polycondensation reaction proceeded smoothly, resulting in a product with a high molecular weight in a relatively good yield. The reaction conditions, like microwave irradiation, coupling agents, and solvents, were optimized to increase the reaction efficiency. The product exhibited a molecular weight greater than Mr 7000. Further, the product could be synthesized on a gram scale. The synthesized polypeptide exhibited a temperature sensitivity that was similar to that of poly(GVGVP) prepared from genetically recombinant E. coli. Therefore, this technique offers a facile and quick approach to prepare polypeptides in large amounts. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

  1. Overview on poly(ADP-ribose) immuno-biomedicine and future prospects

    PubMed Central

    KANAI, Yoshiyuki

    2016-01-01

    Poly(ADP-ribose), identified in 1966 independently by three groups Strassbourg, Kyoto and Tokyo, is synthesized by poly(ADP-ribose) polymerases (PARP) from NAD+ as a substrate in the presence of Mg2+. The structure was unique in that it has ribose-ribose linkage. In the early-1970s, however, its function in vivo/in vitro was still controversial and the antibody against it was desired to help clear its significance. Thereupon, the author tried to produce antibody against poly(ADP-ribose) in rabbits and succeeded in it for the first time in the world. Eventually, this success has led to the following two groundbreaking papers in Nature: “Naturally-occurring antibody against poly(ADP-ribose) in patients with autoimmune disease SLE”, and “Induction of anti-poly(ADP-ribose) antibody by immunization with synthetic double-stranded RNA, poly(A)·poly(U)”. On the way to the publication of the first paper, a reviewer gave me a friendly comment that there is “heteroclitic” fashion as a mechanism of the production of natural antibody. This comment was really a God-send for me, and became a train of power for publication of another paper, as described above. Accordingly, I thought this, I would say, episode is worth describing herein. Because of its importance in biomedical phenomena, a certain number of articles related to “heteroclitic” have become to be introduced in this review, although they were not always directly related to immuno-biological works on poly(ADP-ribose). Also, I tried to speculate on the future prospects of poly(ADP-ribose), product of PARP, as an immuno-regulatory molecule, including either induced or naturally-occurring antibodies, in view of “heteroclitic”. PMID:27477457

  2. Poly(lactic acid) microparticles coated with insulin-containing layer-by-layer films and their pH-dependent insulin release.

    PubMed

    Hashide, Ryosuke; Yoshida, Kentaro; Hasebe, Yasushi; Seno, Masaru; Takahashi, Shigehiro; Sato, Katsuhiko; Anzai, Jun-Ichi

    2014-04-01

    Poly(lactic acid) (PLA) microparticles were coated with layer-by-layer (LbL) films containing insulin and the pH-dependent release of insulin was studied. The LbL films were prepared on the surface of PLA microparticles by the alternate deposition of insulin and poly(allylamine hydrochloride) (PAH) through the electrostatic attraction between insulin and PAH. The insulin loading on the PLA microparticles depended on the film thickness, which corresponded to the number of insulin layers, and on the pH of the solution used to deposit insulin. The insulin loading increased with the film thickness and when the film was prepared at pH 7.4. The LbL films decomposed upon exposure to acidic solutions because the electrostatic attraction between the insulin and the PAH in the films disappeared when the charge on insulin changed from negative to positive at an acidic pH, which resulted in the release of insulin. The temperature and salt concentration did not affect the pH stability of the LbL films. The pH threshold for insulin release was pH 5.0-6.0, which corresponds to isoelectric point of insulin, 5.4. The release of insulin from the microparticles was rapid, and was almost complete within a few minutes. The circular dichroism spectra showed that the released insulin retained its original secondary structure. Our insulin-loaded PLA microparticles may be useful for the controlled release of insulin.

  3. A new combinatorial method for synthesizing, screening, and discovering antifouling surface chemistries.

    PubMed

    Imbrogno, Joseph; Williams, Matthew D; Belfort, Georges

    2015-02-04

    A set of diverse monomers were synthesized using combinatorial chemistry and tested using our unique high-throughput screening platform. The versatility of our platform is exemplified by possible applications in reducing biological fouling on ship hulls, filtration membranes, and surgical instruments, to name a few. To demonstrate its efficacy, the novel monomers were graft-polymerized onto light sensitive poly(ether sulfone) (PES) membranes via atmospheric-pressure plasma polymerization. A diverse library was synthesized by reacting a common vinyl ester linker with a library of maleimides containing various different functional groups. This allowed us to produce a library of many different surfaces and graft them all using the same linker chemistry. The modified surfaces were then tested and screened for the best antiprotein adsorption (nonfouling) properties. Membranes, functionalized with carboxylic acid, zwitterionic, and ester groups, had the lowest protein adhesion compared with that of an unmodified control PES membrane after a static fouling test. After dynamic fouling, these same functionalities as well as a hydroxyl group exhibited the highest permeability. These monomers performed better than our best previously synthesized amide monomers as well as our best poly(ethylene glycol) monomers, which are known to have very high protein resistance. Hansen solubility parameters qualitatively predicted which monomers performed best, indicating favorable interactions with water molecules.

  4. Synthesis of Well-Defined Miktoarm Star Copolymer composed of Poly(3-hexylthiophene) and Poly(methyl methacrylate) via combining anionic polymerization and click reaction

    NASA Astrophysics Data System (ADS)

    Park, Jicheol; Moon, Hong Chul; Kim, Jin Kon

    2013-03-01

    We synthesized well-defined miktoarm star copolymer composed of regioregular poly(3-hexylthiophene) and poly(methyl methacrylate) ((P3HT)2- b-PMMA) by combining anionic polymerization and click reaction. First, we synthesized PMMA terminated with 1,3,5-tris(bromomethy)lbenzene (PMMA-(br)2) by anionic polymerization. Then, the bromide end groups transformed to azide group (PMMA-(N3)2) . For the synthesis (P3HT)2- b-PMMA, click reaction between ethynyl-capped P3HT and PMMA-(N3)2 was performed. The optical property and thin film morphology of (P3HT)2- b-PMMA were investigated by using UV-Vis spectra and atomic force microscopy, respectively.

  5. Star-shaped poly(L-lactide)-b-poly(lactobionamidoethyl methacrylate) with porphyrin core: synthesis, self-assembly, singlet oxygen research and recognition properties.

    PubMed

    Dai, Xiao-Hui; Wang, Zhi-Ming; Pan, Jian-Ming; Yuan, Si-Song; Yan, Yong-sheng; Liu, Dong-Ming; Sun, Lin

    2014-01-01

    Star-shaped porphyrin-cored poly(L-lactide)-b-poly(lactobionamidoethyl methacrylate) block copolymers (SPPLA-b-PLAMA) were synthesized via RAFT of unprotected Lactobionamidoethyl methacrylate (LAMA) in 1-methyl-2-pyrrolidinone (NMP) solution at 70 °C. The structure of this as-synthesized SPPLA-b-PLAMA block copolymer was thoroughly studied by nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC), and Fourier transforms infrared. Moreover, under the irradiation, such SPPLA-b-PGAMA copolymer exhibits efficient singlet oxygen generation (0.17) and indicates high fluorescence quantum yields (0.20). Notably, with UV-vis investigation, SPPLA-b-PLAMA showed a very specific recognition with RCA120 lectin. This will not only provide potentially prophyrin-cored star-shaped SPPLA-b-PLAMA block copolymers for targeted photodynamic therapy, but also improve the physical, biodegradation, biocompatibility properties of PLA-based biomaterials.

  6. Syntheses of Novel Nitrogen and Phosphorus Heterocycles.

    DTIC Science & Technology

    2014-09-26

    Chemicals and Materials Research Department, Ultrasystems, Inc. under Contract F49620-82-C-0021, "Syntheses of Novel Nitrogen and Phosphorus Hetero- * cycles ...ADl-NISS9 449 SYNTHESES OF NOVEL NITROGEN AND PHOSPHORUS HETEROCYCLES In (U) ULTRRSYSTENS INC IRVINE CR K L PRCIOREK ET RL. 26 RPR 85 SN-209?-F RFOSR...MICROCOPY RESOLUTION TEST CHART NATIONAL BURE&U OF STAOACS-963-A SR-I"I" s, -Ŕ 500 4 SYNTHESES OF NOVEL NITROGEN AND PHOSPHORUS HETEROCYCLES Contract No

  7. Aggregation Behavior of Chemically Synthesized, Full-Length Huntingtin Exon1

    PubMed Central

    2015-01-01

    Repeat length disease thresholds vary among the 10 expanded polyglutamine (polyQ) repeat diseases, from about 20 to about 50 glutamine residues. The unique amino acid sequences flanking the polyQ segment are thought to contribute to these repeat length thresholds. The specific portions of the flanking sequences that modulate polyQ properties are not always clear, however. This ambiguity may be important in Huntington’s disease (HD), for example, where in vitro studies of aggregation mechanisms have led to distinctly different mechanistic models. Most in vitro studies of the aggregation of the huntingtin (HTT) exon1 fragment implicated in the HD mechanism have been conducted on inexact molecules that are imprecise either on the N-terminus (recombinantly produced peptides) or on the C-terminus (chemically synthesized peptides). In this paper, we investigate the aggregation properties of chemically synthesized HTT exon1 peptides that are full-length and complete, containing both normal and expanded polyQ repeat lengths, and compare the results directly to previously investigated molecules containing truncated C-termini. The results on the full-length peptides are consistent with a two-step aggregation mechanism originally developed based on studies of the C-terminally truncated analogues. Thus, we observe relatively rapid formation of spherical oligomers containing from 100 to 600 HTT exon1 molecules and intermediate formation of short protofibril-like structures containing from 500 to 2600 molecules. In contrast to this relatively rapid assembly, mature HTT exon1 amyloid requires about one month to dissociate in vitro, which is similar to the time required for neuronal HTT exon1 aggregates to disappear in vivo after HTT production is discontinued. PMID:24921664

  8. Mesoporous CeO2 nanoparticles synthesized by an inverse miniemulsion technique and their catalytic properties in methane oxidation

    NASA Astrophysics Data System (ADS)

    Nabih, Nermeen; Schiller, Renate; Lieberwirth, Ingo; Kockrick, Emanuel; Frind, Robert; Kaskel, Stefan; Weiss, Clemens K.; Landfester, Katharina

    2011-04-01

    Cerium(IV) oxide nanoparticles were synthesized using an inverse miniemulsion technique with cerium nitrate hexahydrate as precursor. The resulting nanocrystallites are as small as 5 nm with a specific surface area of 158 m2 g - 1 after calcination at 400 °C. With the addition of cetyltrimethylammonium bromide (CTAB) or (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)) triblock copolymers (PEO-PPO-PEO) as template in the miniemulsion droplets, the specific surface area can be increased up to 255 m2 g - 1. The miniemulsions were characterized by dynamic light scattering (DLS) and the obtained oxides were examined by x-ray diffraction (XRD), nitrogen sorption (BET and BJH), and transmission electron microscopy (TEM). The catalytic activity of the resulting ceria was investigated for the temperature-programmed oxidation (TPO) of methane.

  9. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

    SciTech Connect

    Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.; Hillmyer, Marc A.

    2015-08-28

    Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.

  10. Active targeting co-delivery system based on pH-sensitive methoxy-poly(ethylene glycol)2K-poly(ε-caprolactone)4K-poly(glutamic acid)1K for enhanced cancer therapy.

    PubMed

    Li, Nuannuan; Huang, Chunzhi; Luan, Yuxia; Song, Aixin; Song, Yunmei; Garg, Sanjay

    2016-06-15

    In this paper, we successfully synthesized folate-modified pH-sensitive copolymer methoxy-poly(ethylene glycol)2K-poly(ε-caprolactone)4K-poly(glutamic acid)1K (mPEG2K-PCL4K-PGA1K-FA), which could form the polymeric assembly in an aqueous solution, for co-delivering hydrophilic drugs doxorubicin hydrochloride (DOX) and verapamil hydrochloride (VER) (FA-poly(DOX+VER)). Since VER was an effective P-glycoprotein inhibitor, the combination of DOX and VER could reverse the multidrug resistance efficiently and enhance the therapeutic effect. Therefore, the inhibition ratios of MCF-7/ADR resistant cancer cell treated by FA-poly (DOX+VER) were almost more than 30% higher than those of FA-polyDOX after 48h and 72h. Furthermore, the conjugation of FA could lead the co-delivery systems actively targeting into the FA receptor over-expressing cancer cells in addition to the passive accumulation of the assembly in tumor tissues. Importantly, the prepared mPEG2K-PCL4K-PGA1K-FA assembly showed high pH-sensitive property, which made the drugs mostly released in tumor tissue (acid environment) than in physiological environment (neutral environment). In summary, the as-prepared co-delivery system FA-poly(DOX+VER) demonstrated a high efficiency in reversing the multidrug resistance and targeting FA receptor to improve the anticancer effect of DOX in MCF-7/ADR resistant cells.

  11. Preparation of albumin preferential surfaces on poly(vinyl chloride) membranes via surface self-segregation.

    PubMed

    Ji, Jian; Feng, Linxian; Shen, Jiacong; Barbosa, M A

    2002-08-01

    Poly(vinyl chlorides)-graft-[omega-stearyl-poly(ethylene oxide)] (PVC-g-SPEO), which has a poly(vinyl chloride) (PVC) backbone, poly(ethylene oxide) (PEO) side chain, and stearyl end groups, has been synthesized. Self-organizing blends of the amphiphilic comb polymer in poly(vinyl chlorides) have been examined as a means to create albumin preferential surfaces on polymer films. X-ray photoelectron spectroscopy (XPS) analysis indicates substantial surface segregation of the PVC-g-SPEO. A surface concentration of 59.9 EO wt % is achieved by the solution casting and heat treatment of a film with a bulk concentration of only 3.78 EO wt %. In the aqueous environment, the surface rearrangement of PVC-g-SPEO/PVC blend film is limited and presents a high interfacial energy and high depolar component of interfacial energy due to the "tail-like" SPEO side chain. Protein adsorption tests confirm that PVC-g-SPEO/PVC blend films absorb high levels of albumin and dramatically resist fibrinogen adsorption. Surfaces to attract and reversibly bind albumin, which might diminish the occurrence of thrombosis, inflammation, and infection, are developed by self-organizing blends of the amphiphilic comb polymer in poly(vinyl chlorides).

  12. Biodegradable Poly(aminoester)-Mediated p53 Gene Delivery for Cancer Therapy.

    PubMed

    Shen, He; Liu, Min; Zhang, Zhijun

    2016-03-01

    Gene therapy is a promising strategy in cancer treatment. However, efficient gene translation still remains challenging. In the previous work, a hydrolytically degradable poly(aminoester) with good biocompatibility was synthesized. Herein, the poly(aminoester) was explored as a vector for gene delivery and cancer therapy. The experiments revealed that the poly(aminoester) condensed plasmid DNA into nanosized particles via electrostatic interaction. The pEGFP-N1 and pGL-3 were first used as two reporter genes to study intracellular transfection. The poly(aminoester) showed higher GFP expression (33%) than PEI 25 kDa (21%). Intracellular trafficking of Cy3-labelled pGL-3 also indicated that the poly(aminoester) showed superior DNA delivery ability to nucleus compared to PEI 25 kDa. Furthermore, the therapeutic gene (p53) was translated into the breast cancer cell line (MCF-7), and then induced cell apoptosis. These results suggested that the degradable poly(aminoester) is a promising and efficient gene delivery vector for gene therapeutic applications.

  13. Selective Ion Pair Adsorption of Cobalt and Copper Salts on Cationically Produced Poly(1,3-divinylimidazolid-2-one)/Silica Hybrid Particles.

    PubMed

    Meyer, Torsten; Prause, Silvio; Spange, Stefan; Friedrich, Manfred

    2001-04-15

    For quantitative metal salt adsorption, poly(1,3-divinylimidazolid-2-one)/silica [poly BVU(cat.)/silica] particles with different polymer contents have been synthesized by a cationic surface polymerization of 1,3-divinylimidazolid-2-one onto silica. Preliminary experiments with the metal ion salts CoCl(2), CoI(2), CuCl(2), and FeCl(3) on poly-BVU(cat.)/silica particles, a radically produced poly-BVU(rad.) resin, and a cationically produced poly-BVU(cat.) resin have been carried in acetone solution to check the suitability of the adsorbents. The adsorption mechanism for Co(2+) and Cu(2+) on poly-BVU(cat.)/silica is in accordance with the Langmuir model for monolayer adsorption as shown by quantitative adsorption measurements by means of UV/vis spectroscopy. An ion pair adsorption mechanism is suggested for CoCl(2), CoI(2), and CuCl(2) on poly-BVU(cat.)/silica because both environments cationically produced poly-BVU and residual silanol groups are required for linking the cation and anion. ESR spectroscopic results of CoCl(2)-, CuCl(2)-, and FeCl(3)-poly-BVU(cat.)/silica hybrid adsorbates show selective adsorption for Co(2+) and Cu(2+). However, two different adsorption sites are indicated for Fe(3+) on poly-BVU(cat.)/silica. Copyright 2001 Academic Press.

  14. Thermoelectric Properties of Solution Synthesized Nanostructured Materials.

    PubMed

    Finefrock, Scott W; Yang, Haoran; Fang, Haiyu; Wu, Yue

    2015-01-01

    Thermoelectric nanocomposites made by solution synthesis and compression of nanostructured chalcogenides could potentially be low-cost, scalable alternatives to traditional solid-state synthesized materials. We review the progress in this field by comparing the power factor and/or the thermoelectric figure of merit, ZT, of four classes of materials: (Bi,Sb)2(Te,Se)3, PbTe, ternary and quaternary copper chalcogenides, and silver chalcogenides. We also discuss the thermal conductivity reduction associated with multiphased nanocomposites. The ZT of the best solution synthesized materials are, in several cases, shown to be equal to or greater than the corresponding bulk materials despite the generally reduced mobility associated with solution synthesized nanocomposites. For the solution synthesized materials with the highest performance, the synthesis and processing conditions are summarized to provide guidance for future work.

  15. ORGANIC SYNTHESES USING MICROWAVES AND SUPPORTED REAGENTS

    EPA Science Inventory

    Microwave-accelerated chemical syntheses under solvent-free conditions have witnessed an explosive growth. The technique has found widespread application predominantly exploiting the inexpensive unmodified household microwave (MW) ovens although the use of dedicated MW equipment...

  16. The Trajectory Synthesizer Generalized Profile Interface

    NASA Technical Reports Server (NTRS)

    Lee, Alan G.; Bouyssounouse, Xavier; Murphy, James R.

    2010-01-01

    The Trajectory Synthesizer is a software program that generates aircraft predictions for Air Traffic Management decision support tools. The Trajectory Synthesizer being used by researchers at NASA Ames Research Center was restricted in the number of trajectory types that could be generated. This limitation was not sufficient to support the rapidly changing Air Traffic Management research requirements. The Generalized Profile Interface was developed to address this issue. It provides a flexible approach to describe the constraints applied to trajectory generation and may provide a method for interoperability between trajectory generators. It also supports the request and generation of new types of trajectory profiles not possible with the previous interface to the Trajectory Synthesizer. Other enhancements allow the Trajectory Synthesizer to meet the current and future needs of Air Traffic Management research.

  17. Method to synthesize metal chalcogenide monolayer nanomaterials

    SciTech Connect

    Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

    2016-12-13

    Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

  18. Antimicrobial activity of poly(acrylic acid) block copolymers.

    PubMed

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P; Lackner, Maximilian

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid-base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure.

  19. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers

    PubMed Central

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O.; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B.; Ebenso, Eno E.

    2016-01-01

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results. PMID:27515383

  20. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers.

    PubMed

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B; Ebenso, Eno E

    2016-08-12

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results.

  1. Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers

    NASA Astrophysics Data System (ADS)

    Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O.; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B.; Ebenso, Eno E.

    2016-08-01

    Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results.

  2. Psychoacoustic Analysis of Synthesized Jet Noise

    NASA Technical Reports Server (NTRS)

    Okcu, Selen; Rathsam, Jonathan; Rizzi, Stephen A.

    2013-01-01

    An aircraft noise synthesis capability is being developed so the annoyance caused by proposed aircraft can be assessed during the design stage. To make synthesized signals as realistic as possible, high fidelity simulation is required for source (e.g., engine noise, airframe noise), propagation and receiver effects. This psychoacoustic study tests whether the jet noise component of synthesized aircraft engine noise can be made more realistic using a low frequency oscillator (LFO) technique to simulate fluctuations in level observed in recordings. Jet noise predictions are commonly made in the frequency domain based on models of time-averaged empirical data. The synthesis process involves conversion of the frequency domain prediction into an audible pressure time history. However, because the predictions are time-invariant, the synthesized sound lacks fluctuations observed in recordings. Such fluctuations are hypothesized to be perceptually important. To introduce time-varying characteristics into jet noise synthesis, a method has been developed that modulates measured or predicted 1/3-octave band levels with a (<20Hz) LFO. The LFO characteristics are determined through analysis of laboratory jet noise recordings. For the aft emission angle, results indicate that signals synthesized using a generic LFO are perceived as more similar to recordings than those using no LFO, and signals synthesized with an angle-specific LFO are more similar to recordings than those synthesized with a generic LFO.

  3. Degradation behavior of poly(glycerol sebacate).

    PubMed

    Pomerantseva, Irina; Krebs, Nicholas; Hart, Alison; Neville, Craig M; Huang, Albert Y; Sundback, Cathryn A

    2009-12-15

    Poly(glycerol sebacate) (PGS), a promising scaffold material for soft tissue engineering applications, is a soft, tough elastomer with excellent biocompatibility. However, the rapid in vivo degradation rate of PGS limits its use as a scaffold material. To determine the impact of crosslink density on degradation rate, a family of PGS materials was synthesized by incrementally increasing the curing time from 42 to 144 h, at 120 degrees C and 10 mTorr vacuum. As expected, PGS became a stiffer, tougher, and stronger elastomer with increasing curing time. PGS disks were subcutaneously implanted into rats and periodically harvested; only mild tissue responses were observed and the biocompatibility remained excellent. Regardless of crosslink density, surface erosion degradation was observed. The sample dimensions linearly decreased with implantation time, and the mass loss rates were constant after 1-week implantation. As surface erosion degradation frequently correlates with enzymatic digestion, parallel in vitro digestion studies were conducted in lipase solutions which hydrolyze ester bonds. Enzymatic digestion played a significant role in degrading PGS, and the mass loss rates were not a function of curing time. Alternative chemistry approaches will be required to decrease the enzymatic hydrolysis rate of the ester bonds in PGS polymers.

  4. Poly(vinyl alcohol)/poly(acrylic acid) hydrogel coatings for improving electrode-neural tissue interface.

    PubMed

    Lu, Yi; Wang, Dingfang; Li, Tao; Zhao, Xueqing; Cao, Yuliang; Yang, Hanxi; Duan, Yanwen Y

    2009-09-01

    A major problem which hinders the applications of neural prostheses is the inconsistent performance caused by tissue responses during long-term implantation. The study investigated a new approach for improving the electrode-neural tissue interface. Hydrogel poly(vinyl alcohol)/poly(acrylic acid) interpenetrating polymer networks (PVA/PAA IPNs) were synthesized and tailored as coatings for poly(dimethylsiloxane) (PDMS) based neural electrodes with the aid of plasma pretreatment. Changes in the electrochemical impedance and maximum charge injection (Q(inj)) limits of the coated iridium oxide microelectrodes were negligible. Protein adsorption on PDMS was reduced by approximately 85% after coating. In the presence of nerve growth factor (NGF), neurite extension of rat pheochromocytoma (PC12) cells was clearly greater on PVA/PAA IPN films than on PDMS substrates. Furthermore, the tissue responses of PDMS implants coated with PVA/PAA IPN films were studied by 6-week implantation in the cortex of rats, which found that the glial fibrillary acidic protein (GFAP) immunoreactivity in animals (n=8) receiving coated implants was significantly lower (p<0.05) compared to that of uncoated implants (n=7) along the entire distance of 150 microm from the outer skirt to the implant interface. The coated film remained on the surface of the explanted implants, confirmed by scanning electron microscopy (SEM). All of these suggest the hydrogel coating is feasible and favorable to neural electrode applications.

  5. Properties of radiation-synthesized polyvinylpyrrolidone/chitosan hydrogel blends

    SciTech Connect

    Mahmud, Maznah; Daik, Rusli; Adam, Zainah

    2015-09-25

    Poly(vinylpyrrolidone) (PVP)-crosslinked chitosan hydrogels were prepared by gamma radiation at various doses; 1, 3 5, 7, 10, 15, 20, 25 and 30kGy. Gamma radiation was used as a crosslinking tool which requires no chemical initiator, no heating process and need no purification step on the end products obtained. The hydrogel formulations were composed of 6% chitosan with average molecular weight (Mw) = 48 800 g/mol and 14% PVP with Mw = 10 000 g/mol in 2% lactic acid. Physical properties of hydrogels such as gel fraction and swelling property at pH 5.5 and pH 7.0 as well as syneresis activity were determined. It was found that different radiation dose induces different effect on hydrogels’ network formed. Morphological study of hydrogels has been carried out by scanning electron microscope (SEM). From these preliminary evaluations, it can be concluded that gamma radiation is an effective tool for network development of hydrogels and it also induces enhancement on characteristics of hydrogels synthesized.

  6. Properties of radiation-synthesized polyvinylpyrrolidone/chitosan hydrogel blends

    NASA Astrophysics Data System (ADS)

    Mahmud, Maznah; Daik, Rusli; Adam, Zainah

    2015-09-01

    Poly(vinylpyrrolidone) (PVP)-crosslinked chitosan hydrogels were prepared by gamma radiation at various doses; 1, 3 5, 7, 10, 15, 20, 25 and 30kGy. Gamma radiation was used as a crosslinking tool which requires no chemical initiator, no heating process and need no purification step on the end products obtained. The hydrogel formulations were composed of 6% chitosan with average molecular weight (Mw) = 48 800 g/mol and 14% PVP with Mw = 10 000 g/mol in 2% lactic acid. Physical properties of hydrogels such as gel fraction and swelling property at pH 5.5 and pH 7.0 as well as syneresis activity were determined. It was found that different radiation dose induces different effect on hydrogels' network formed. Morphological study of hydrogels has been carried out by scanning electron microscope (SEM). From these preliminary evaluations, it can be concluded that gamma radiation is an effective tool for network development of hydrogels and it also induces enhancement on characteristics of hydrogels synthesized.

  7. Massachusetts Special Olympics Poly Hockey.

    ERIC Educational Resources Information Center

    Morrissey, Jim

    Poly Hockey is featured in this manual of instructions for coaches and teachers to use with mentally retarded boys and girls of all ages and ability levels. It is noted that the sport has been supported by the Board of Directors of the Special Olympics and has been used in Massachusetts for over 7 years. Explained is use of the game indoors, and…

  8. Hydrophilic poly (ethylene glycol) capped poly (lactic-co-glycolic) acid nanoparticles for subcutaneous delivery of insulin in diabetic rats.

    PubMed

    S, Saravanan; S, Malathi; P S L, Sesh; S, Selvasubramanian; S, Balasubramanian; V, Pandiyan

    2017-02-01

    The aim of the present study is to evaluate the effect of insulin loaded poly(ethylene glycol) capped poly(lactic-co-glycolic)acid nanoparticles (ISPPLG NPs) by subcutaneous administration in diabetic rats. A series of biodegradable low molecular weight PLGA [90/10 (PLG2) and 80/20 (PLG4)] copolymers were synthesized by melt polycondensation and their ISPPLG NPs were synthesized by water-oil-water (W/O/W) emulsion solvent evaporation method. The PLGA copolymers and their nanoparticles were characterized. The maximum encapsulation efficiency of ISPPLG4 NPs is 66% and the diameter of the nanoparticles is about 140nm. The in-vivo studies of ISPPLG NPs carried out in diabetic rats by subcutaneous administration show considerable reduction in serum glucose level along with partial restoration of tissue defense systems. Histopathological studies reveal that ISPPLG NPs could restore the damages caused by oxidants during hyperglycaemia. The subcutaneous administration of ISPPLG4 NPs is thus an effective method of reducing hyperglycaemia associated complications.

  9. Stereo matching image processing by synthesized color and the characteristic area by the synthesized color

    NASA Astrophysics Data System (ADS)

    Akiyama, Akira; Mutoh, Eiichiro; Kumagai, Hideo

    2014-09-01

    We have developed the stereo matching image processing by synthesized color and the corresponding area by the synthesized color for ranging the object and image recognition. The typical images from a pair of the stereo imagers may have some image disagreement each other due to the size change, missed place, appearance change and deformation of characteristic area. We constructed the synthesized color and corresponding color area with the same synthesized color to make the distinct stereo matching. We constructed the synthesized color and corresponding color area with the same synthesized color by the 3 steps. The first step is making binary edge image by differentiating the focused image from each imager and verifying that differentiated image has normal density of frequency distribution to find the threshold level of binary procedure. We used Daubechies wavelet transformation for the procedures of differentiating in this study. The second step is deriving the synthesized color by averaging color brightness between binary edge points with respect to horizontal direction and vertical direction alternatively. The averaging color procedure was done many times until the fluctuation of averaged color become negligible with respect to 256 levels in brightness. The third step is extracting area with same synthesized color by collecting the pixel of same synthesized color and grouping these pixel points by 4 directional connectivity relations. The matching areas for the stereo matching are determined by using synthesized color areas. The matching point is the center of gravity of each synthesized color area. The parallax between a pair of images is derived by the center of gravity of synthesized color area easily. The experiment of this stereo matching was done for the object of the soccer ball toy. From this experiment we showed that stereo matching by the synthesized color technique are simple and effective.

  10. 21 CFR 177.1635 - Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Poly(p-methylstyrene) and rubber-modified poly(p... Components of Single and Repeated Use Food Contact Surfaces § 177.1635 Poly(p-methylstyrene) and rubber-modified poly(p-methyl-styrene). Poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene)...

  11. MICROWAVE-ASSISTED SHAPE CONTROLLED BULK SYNTHESIS OF AG AND FE NANORODS IN POLY (ETHYLENE GLYCOL) SOLUTIONS

    EPA Science Inventory

    Bulk syntheses of silver (Ag) and iron (Fe) nanorods using poly (ethylene glycol), PEG, under microwave irradiation (MW) conditions are reported. Favorable conditions to make Ag nanorods were established and can be extended to make Fe nanorods with uniform size and shape. The nan...

  12. The directing effect of linking units on building microporous architecture in tetraphenyladmantane-based poly(Schiff base) networks.

    PubMed

    Li, Guiyang; Zhang, Biao; Yan, Jun; Wang, Zhonggang

    2014-02-21

    Tetraphenyladamantane-based porous poly(Schiff base)s with BET surface area (>1000 m(2) g(-1)), CO2 uptake (15 wt%, 273 K/1 bar) and H2 uptake (1.26 wt%, 77 K/1 bar) were synthesized. The structure-directing effect of isomers of phenyl diamines on building porous architecture was investigated.

  13. A novel biobased plasticizer of epoxidized cardanol glycidylether: Synthesis and application in soft poly(vinyl chloride) films

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel plasticizer derived from cardanol, epoxied cardanol glycidyl ether (ECGE), was synthesized and characterized by 1H-NMR and 13C-NMR. Effects of the ECGE combined with dioctyl phthalate (DOP), a commercial plasticizer, in soft poly(vinyl chloride) (PVC) films were studied. Dynamic mechanical a...

  14. Stereoregularity of poly (lactic acid) and their model compounds as studied by NMR and quantum chemical calculations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order to understand the origin of the tacticity splitting in the NMR spectrum of poly(lactic acid), monomer model compound and dimer model compounds (both isotactic and syndiotactic) were synthesized and their 1H and 13C NMR chemical shifts observed. Two energetically stable conformations were o...

  15. Synthesize of barium ferrite nanowire array by self-fabricated porous silicon template

    NASA Astrophysics Data System (ADS)

    Zheng, Hui; Han, Mangui; Deng, Jiangxia; Zheng, Liang; Wu, Jun; Deng, Longjiang; Qin, Huibin

    2014-08-01

    In this work, we synthesize barium ferrite (BaFe12O19) nanowire array in porous silicon template. The porous silicon templates are prepared via gold-assisted chemical etching method. The gold (Au) nanoparticles with mean diameter of 30 nm and distance of 100 nm were ordered on the surface of Si substrate through the Polystyrene (510000)-block-poly (2-vinylpyridine) (31000) (PS510000-b-P2VP31000) diblock copolymer. Porous silicon templates with mean diameter of 500 nm and distance between the pores of 500 nm were fabricated by two etching steps. BaFe12O19 nanowires with mean diameter of 200 nm were synthesized into a porous silicon template by a sol-gel method. Magnetic hysteresis loops show an isotropic feature of the BaFe12O19 nanowires array. The coercivity (Hc) and squareness ratio (Mr/Ms) of nanowire arrays are 2560 Oe and 0.6, respectively.

  16. Electrical properties of bilayer graphene synthesized using surface wave microwave plasma techniques at low temperature

    NASA Astrophysics Data System (ADS)

    Yamada, Takatoshi; Kato, Hiromitsu; Okigawa, Yuki; Ishihara, Masatou; Hasegawa, Masataka

    2017-01-01

    Bilayer graphene was synthesized at low temperature using surface wave microwave plasma techniques where poly(methyl metacrylate) (PMMA) and methane (CH4) were used as carbon sources. Temperature-dependent Hall effect measurements were carried out in a helium atmosphere. Sheet resistance, sheet carrier density and mobility showed weak temperature dependence for graphene from PMMA, and the highest carrier mobility is 740 cm2 V-1 s-1. For graphene from CH4, tunneling of the domain boundary limited carrier transport. The difference in average domain size was determined by Raman signal maps. In addition, residuals of PMMA were detected on graphene from PMMA. The low sheet resistances of graphene synthesized at a temperature of 280 °C using plasma techniques were explained by the PMMA related residuals rather than the domain sizes.

  17. Menthols as Chiral Auxiliaries for Asymmetric Cycloadditive Oligomerization: Syntheses and Studies of β-Proline Hexamers.

    PubMed

    Kudryavtsev, Konstantin V; Ivantcova, Polina M; Muhle-Goll, Claudia; Churakov, Andrei V; Sokolov, Mikhail N; Dyuba, Artem V; Arutyunyan, Alexander M; Howard, Judith A K; Yu, Chia-Chun; Guh, Jih-Hwa; Zefirov, Nikolay S; Bräse, Stefan

    2015-12-18

    To produce a novel class of structurally ordered poly-β-prolines, an emergent method for synthesizing chiral β-peptide molecular frameworks was developed based on 1,3-dipolar cycloaddition chemistry of azomethine ylides. Functionalized short β-peptides with up to six monomeric residues were efficiently synthesized in homochiral forms using a cycloadditive oligomerization approach. X-ray, NMR, and CD structural analyses of the novel β-peptides revealed secondary structure features that were generated primarily by Z/E-β-peptide bond isomerism. Anticancer in cellulo activity of the new β-peptides toward hormone-refractory prostate cancer cells was observed and was dependent on the absolute configuration of the stereogenic centers and the chain length of the β-proline oligomers.

  18. Poly(ethylene glycol) analogs grafted with low molecular weight poly(ethylene imine) as non-viral gene vectors.

    PubMed

    Zhang, Zhenfang; Yang, Cuihong; Duan, Yajun; Wang, Yanming; Liu, Jianfeng; Wang, Lianyong; Kong, Deling

    2010-07-01

    A novel class of non-viral gene vectors consisting of low molecular weight poly(ethylene imine) (PEI) (molecular weight 800 Da) grafted onto degradable linear poly(ethylene glycol) (PEG) analogs was synthesized. First, a Michael addition reaction between poly(ethylene glycol) diacrylates (PEGDA) (molecular weight 258 Da) and d,l-dithiothreitol (DTT) was carried out to generate a linear polymer (PEG-DTT) having a terminal thiol, methacrylate and pendant hydroxyl functional groups. Five PEG-DTT analogs were synthesized by varying the molar ratio of diacrylates to thiols from 1.2:1 to 1:1.2. Then PEI (800 Da) was grafted onto the main chain of the PEG-DTTs using 1,1'-carbonyldiimidazole as the linker. The above reaction gave rise to a new class of non-viral gene vectors, (PEG-DTT)-g-PEI copolymers, which can effectively complex DNA to form nanoparticles. The molecular weights and structures of the copolymers were characterized by gel permeation chromatography, (1)H nuclear magnetic resonance and Fourier transform infrared spectroscopy. The size of the nanoparticles was<200 nm and the surface charge of the nanoparticles, expressed as the zeta potential, was between+20 and+40 mV. Cytotoxicity assays showed that the copolymers exhibited much lower cytotoxicities than high molecular weight PEI (25 kDa). Transfection was performed in cultured HeLa, HepG2, MCF-7 and COS-7 cells. The copolymers showed higher transfection efficiencies than PEI (25 kDa) tested in four cell lines. The presence of serum (up to 30%) had no inhibitory effect on the transfection efficiency. These results indicate that this new class of non-viral gene vectors may be a promising gene carrier that is worth further investigation.

  19. Hyperbranched poly(epsilon-caprolactone) as a nonmigrating alternative plasticizer for phthalates in flexible PVC.

    PubMed

    Choi, Jeongsoo; Kwak, Seung-Yeop

    2007-05-15

    Hyperbranched (dendritic) poly(epsilon-caprolactone)s (HPCLs) were synthesized to have architectural variations, which are the different lengths of linear segments and different numbers of branches, and were used as plasticizers for flexible poly(vinyl chloride) (PVC). The plasticization efficiency estimated by the lowering of glass transition temperature and the enhancement in ultimate elongation indicated that the HPCLs with the shorter linear segments and the larger number of branches imparted as high flexibility as di(ethylhexyl) phthalate (DEHP) and much higher flexibility than their linear analogue, linear poly(epsilon-caprolactone), which is one of currently used polymer plasticizers. Volatility, extractability, and exudation tests for PVC/HPCL samples showed that there was no plasticizer migration even at very harsh condition, while ca. 7-78% of additives in PVC/DEHP was migrated out of samples, indicating that the HPCL can be used as an alternative plasticizer to remove the potential health risk from migrating phthalates during end use.

  20. Addition of poly (propylene glycol) to multiblock copolymer to optimize siRNA delivery

    PubMed Central

    Dai, Zhi; Arévalo, Maria T; Li, Junwei; Zeng, Mingtao

    2014-01-01

    Previous studies have examined different strategies for siRNA delivery with varying degrees of success. These include use of viral vectors, cationic liposomes, and polymers. Several copolymers were designed and synthesized based on blocks of poly(ethylene glycol) PEG, poly(propylene glycol) PPG, and poly(l-lysine). These were designated as P1, P2, and P3. We studied the copolymer self-assembly, siRNA binding, particle size, surface potential, architecture of the complexes, and siRNA delivery. Silencing of GFP using copolymer P3 to deliver GFP-specific siRNA to Neuro-2a cells expressing GFP was almost as effective as using Lipofectamine 2000, with minimal cytotoxicity. Thus, we have provided a new copolymer platform for siRNA delivery that we can continue to modify for improved delivery of siRNA in vitro and eventually in vivo. PMID:24424156

  1. Addition of poly (propylene glycol) to multiblock copolymer to optimize siRNA delivery.

    PubMed

    Dai, Zhi; Arévalo, Maria T; Li, Junwei; Zeng, Mingtao

    2014-01-01

    Previous studies have examined different strategies for siRNA delivery with varying degrees of success. These include use of viral vectors, cationic liposomes, and polymers. Several copolymers were designed and synthesized based on blocks of poly(ethylene glycol) PEG, poly(propylene glycol) PPG, and poly(l-lysine). These were designated as P1, P2, and P3. We studied the copolymer self-assembly, siRNA binding, particle size, surface potential, architecture of the complexes, and siRNA delivery. Silencing of GFP using copolymer P3 to deliver GFP-specific siRNA to Neuro-2a cells expressing GFP was almost as effective as using Lipofectamine 2000, with minimal cytotoxicity. Thus, we have provided a new copolymer platform for siRNA delivery that we can continue to modify for improved delivery of siRNA in vitro and eventually in vivo.

  2. Surface decorated poly(ester-ether-urethane)s nanoparticles: a versatile approach towards clinical translation.

    PubMed

    Piras, Anna Maria; Sandreschi, Stefania; Malliappan, Sivakumar Ponnurengam; Dash, Mamoni; Bartoli, Cristina; Dinucci, Dinuccio; Guarna, Francesco; Ammannati, Enrico; Masa, Marc; Múčková, Marta; Schmidtová, Ludmila; Chiellini, Emo; Chiellini, Federica

    2014-11-20

    Poly(ester-ether-urethane)s copolymers are a resourceful class of biopolymers for the preparation of nanocarriers for drug delivery applications. However, a simple clinical translation for this synthetic material with biological and quality features is still needed. In this view, poly(ε-caprolactone)-co-poly(ethylene glycol) copolymers were synthesized as semi-bulk pilot (Kg) scale under mild conditions in absence of catalyst, bearing functional termini such as fluorescein tag and anticancer targeting moieties. The obtained materials were processed into surface decorated paclitaxel (PTX) loaded nanoparticles (NPs). The NPs were fully characterized in vitro and in vivo biodistribution in healthy mice evidenced no sign of toxicity and lower levels of PTX in lung and spleen, compared to clinically applied PTX dosage form.

  3. VCO PLL Frequency Synthesizers for Spacecraft Transponders

    NASA Technical Reports Server (NTRS)

    Smith, Scott; Mysoor, Narayan; Lux, James; Cook, Brian

    2007-01-01

    Two documents discuss a breadboard version of advanced transponders that, when fully developed, would be installed on future spacecraft to fly in deep space. These transponders will be required to be capable of operation on any deepspace- communications uplink frequency channel between 7,145 and 7,235 MHz, and any downlink frequency channel between 8,400 and 8,500 MHz. The document focuses on the design and operation of frequency synthesizers for the receiver and transmitter. Heretofore, frequency synthesizers in deep-space transponders have been based on dielectric resonator oscillators (DROs), which do not have the wide tuning bandwidth necessary to tune over all channels in the uplink or downlink frequency bands. To satisfy the requirement for tuning bandwidth, the present frequency synthesizers are based on voltage-controlled-oscillator (VCO) phase-locked loops (PLLs) implemented by use of monolithic microwave integrated circuits (MMICs) implemented using inGaP heterojunction bipolar transistor (HBT) technology. MMIC VCO PLL frequency synthesizers similar to the present ones have been used in commercial and military applications but, until now, have exhibited too much phase noise for use in deep-space transponders. The present frequency synthesizers contain advanced MMIC VCOs, which use HBT technology and have lower levels of flicker (1/f) phase noise. When these MMIC VCOs are used with high-speed MMIC frequency dividers, it becomes possible to obtain the required combination of frequency agility and low phase noise.

  4. Characterization of synthesized and treated gem diamonds

    NASA Astrophysics Data System (ADS)

    Song, Ohsung

    2007-10-01

    Synthesized diamonds have been widely employed as polishing media for precise machining and noble substrates for microelectronics. The recent development of the split sphere press has led to the commercial HPHT (high pressure high temperature) synthesis of bulk gem diamonds from graphite and to the enhancement of low quality natural diamonds. Synthesized and treated diamonds are sometimes traded deceptively as high quality natural diamonds because it is hard to distinguish among these diamonds with conventional gemological characterization methods. Therefore, we need to develop a new identification method that is non-destructive, fast, and inexpensive. We proposed using new methods of UV fluorescence and X-ray Lang topography for checking the local HPHT stress field as well as using a vibrating sample magnetometer for checking ferromagnetic residue in synthesized diamonds to distinguish these diamonds from natural ones. We observe unique differences in the local stress field images in synthesized and treated diamonds using Lang topography and UV fluorescence characterization. Our result implies that our proposed methods may be appropriate for identification of the synthesized and treated diamonds.

  5. Synthesis, characterization and biological application of four novel metal-Schiff base complexes derived from allylamine and their interactions with human serum albumin: Experimental, molecular docking and ONIOM computational study.

    PubMed

    Kazemi, Zahra; Rudbari, Hadi Amiri; Sahihi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammadpoor-Baltork, Iraj; Gharaghani, Sajjad

    2016-09-01

    Novel metal-based drug candidate including VOL2, NiL2, CuL2 and PdL2 have been synthesized from 2-hydroxy-1-allyliminomethyl-naphthalen ligand and have been characterized by means of elemental analysis (CHN), FT-IR and UV-vis spectroscopies. In addition, (1)H and (13)C NMR techniques were employed for characterization of the PdL2 complex. Single-crystal X-ray diffraction technique was utilized to characterise the structure of the complexes. The Cu(II), Ni(II) and Pd(II) complexes show a square planar trans-coordination geometry, while in the VOL2, the vanadium center has a distorted tetragonal pyramidal N2O3 coordination sphere. The HSA-binding was also determined, using fluorescence quenching, UV-vis spectroscopy, and circular dichroism (CD) titration method. The obtained results revealed that the HSA affinity for binding the synthesized compounds follows as PdL2>CuL2>VOL2>NiL2, indicating the effect of metal ion on binding constant. The distance between these compounds and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Furthermore, computational methods including molecular docking and our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM) were carried out to investigate the HSA-binding of the compounds. Molecular docking calculation indicated the existence of hydrogen bond between amino acid residues of HSA and all synthesized compounds. The formation of the hydrogen bond in the HSA-compound systems leads to their stabilization. The ONIOM method was utilized in order to investigate HSA binding of compounds more precisely in which molecular mechanics method (UFF) and semi empirical method (PM6) were selected for the low layer and the high layer, respectively. The results show that the structural parameters of the compounds changed along with binding to HSA, indicating the strong interaction between the compounds and HSA. The value of binding constant depends on the extent of the resultant changes. This

  6. Poly(N-vinylpyrrolidone)-block-poly(vinyl acetate) as a drug delivery vehicle for hydrophobic drugs.

    PubMed

    Bailly, Nathalie; Thomas, Mark; Klumperman, Bert

    2012-12-10

    Poly((N-vinylpyrrolidone)-block-poly(vinyl acetate)) (PVP-b-PVAc) block copolymers of varying molecular weight and hydrophobic block lengths were synthesized via controlled radical polymerization and investigated as carriers for the solubilization of highly hydrophobic riminophenazine compounds. These compounds have recently been shown to exhibit a strong activity against a variety of cancer types. PVP-b-PVAc self-assembles into polymer vesicles in aqueous media, and the dialysis method was used to load the water-insoluble drug (clofazimine) into these polymer vesicles. The polymer vesicles were characterized by 1H NMR spectroscopy to confirm vesicle formation and the incorporation of the anticancer drugs into the polymer vesicles. Dynamic light scattering was used to determine the particle size and particle size distribution of the drug-loaded vesicles as well as the stability of the vesicles under physiological conditions. The size of the polymer vesicles did not increase upon loading with clofazimine, and the particle size of 180-200 nm and the narrow particle size distribution were maintained. The morphology of the vesicles was examined by transmission electron microscopy. The polymer vesicles had a relatively high drug loading capacity of 20 wt %. In vitro cytotoxicity studies of PVP-b-PVAc and drug-loaded PVP-b-PVAc were performed against MDA-MB-231 multidrug-resistant breast epithelial cancer cells and MCF12A nontumorigenic breast epithelial cells. In vitro experiments demonstrated that the PVP-b-PVAc drug carrier showed no cytotoxicity, which confirms the biocompatibility of the PVP-b-PVAc drug carrier. The results indicate that the present PVP-b-PVAc block copolymer could be a potential candidate as a drug carrier for hydrophobic drugs.

  7. Synthesis and characterization of poly(lactic acid-co-glycolic acid) complex microspheres as drug carriers.

    PubMed

    Wang, Fang; Liu, Xiuxiu; Yuan, Jian; Yang, Siqian; Li, Yueqin; Gao, Qinwei

    2016-10-01

    Poly(lactic-co-glycolic) acid (PLGA) is synthesized via melt polycondensation directly from lactic acid and glycolic acid with a feed molar ratio of 75/25. Bovine serum albumin, which is used as model protein, is entrapped into the poly(lactic-co-glycolic acid) microspheres with particle size of 260.9 ± 20.0 nm by the double emulsification method. Then it is the first report of producing more carboxyl groups by poly(lactic-co-glycolic acid) surface hydrolysis. The purpose is developing poly(lactic-co-glycolic acid) microspheres surface, which is modified with chitosan by chemical reaction between carboxyl groups and amine groups. The particle size and the positive zeta potential of the poly(lactic-co-glycolic acid)/chitosan microspheres are 388.2 ± 35.6 nm and 10.4 ± 2.9 mV, respectively. The drug loading ratio and encapsulation efficacy of poly(lactic-co-glycolic acid)/chitosan microspheres are 36.3% and 57.5%, which are higher than PLGA microspheres. Furthermore, the drug burst release of poly(lactic-co-glycolic acid)/chitosan microspheres at 10 h is decreased to 21.72% while the corresponding value of the poly(lactic-co-glycolic acid) microsphere is 64.56%. These results reveal that surface hydrolysis modification of poly(lactic-co-glycolic acid) is an efficient method to improve the negative potential and chemical reaction properties of the polymer. And furthermore, this study shows that chitosan-modified poly(lactic-co-glycolic acid) microspheres is a promising system for the controlled release of pharmaceutical proteins.

  8. Optoelectronic characteristics of inorganic/organic hybrid device based on poly(N-vinylcarbazole)/ cadmium selenide thin films.

    PubMed

    Tang, Aiwei; Teng, Feng; Hou, Yanbing; Xiong, Sha; Feng, Bin; Qian, Lei; Wang, Yongsheng

    2008-03-01

    Inorganic/organic hybrid light-emitting diodes were easily fabricated with a thin film containing water-soluble cadmium selenide nanocrystals and poly(N-vinylcarbazole) as an emitting layer by a spin-coating method. The cadmium selenide nanocrystals were synthesized in aqueous solution with L-cysteine hydrochloride as the stabilizer and were transferred from the aqueous solution into chloroform by a cationic surfactant cetyltrimethyl ammonium bromide. A broad emission spanning the whole visible wavelength range was obtained from the inorganic/organic hybrid devices whether poly(N-vinylcarbazole) was present in the devices or not, and the electroluminescence intensity of the devices increased as the applied voltages increased. However, an obvious blue-shift of the wavelength was observed with the increasing applied voltages in the device with poly(N-vinylcarbazole). Accordingly, the emission color of the device made with poly(N-vinylcarbazole) could be tuned from white to blue by varying the applied voltages, but the emission color of the device made without poly(N-vinylcarbazole) was almost constrained in the white region. This can be attributed to a limited contribution of poly(N-vinylcarbazole) emission to the electroluminescence spectra under the higher applied voltage. By comparing the electroluminescence intensity and the current-voltage characteristics of the devices made with and without poly(N-vinylcarbazole), the performance of the device with poly(N-vinylcarbazole) was improved greatly, which indicated that poly(N-vinylcarbazole) played an important role in the carrier injection and transportation in the device with poly(N-vinylcarbazole).

  9. Synthesis of poly(N-isopropylacrylamide) hydrogels by radiation polymerization and cross-linking

    SciTech Connect

    Nagaoka, Noriyasu; Kubota, Hitoshi; Katakai, Ryoichi; Safranj, Agneza; Yoshida, Masaru; Omichi, Hideki

    1993-12-20

    Poly(N-isopropylacrylamide) [poly(NIPAAm)] shows a typical thermal reversibility of phase transition in aqueous solutions. That is, it precipitates from solution above a critical temperature called the lower critical solution temperature (LCST) and dissolves below this temperature. When it is cross-linked, the obtained hydrogel collapses above LCST, while it swells and expands below LCST. This hydrogel has received much attention recently and has been used as a model system to demonstrate the validity of theories describing the coil-globule transition, swelling of networks, and folding and unfolding of biopolymers. It has also been proposed for various applications ranging from controlled drug delivery to solute separation. Poly(NIPAAm) hydrogel is usually synthesized at room temperature from an aqueous solution of the monomer by using a redox initiator composed of ammonium persulfate and N,N,N{prime},N{prime}-tetramethylethylenediamine in the presence of N,N{prime}-methylenebisacrylamide as a cross-linker. Since the LCST of poly(NIPAAm) is around 32 C, the polymerization at room temperature proceeds in a homogeneous solution. Recently, poly(NIPAAm) hydrogels were synthesized by starting the polymerization below the LCST and then elevating the temperature above it, by which method macroporous gels with fast temperature response were obtained. The idea is to apply a radiation--induced polymerization method for the synthesis of poly(NIPAAm) hydrogels. This method offers unique advantages for synthesis: it is a simple and additive-free process at all temperatures, and the degree of cross-linking can be easily controlled by irradiation conditions. Therefore, radiation methods are especially attractive for the synthesis of hydrogels with potential biomedical application where the residual chemical initiators may contaminate the product. It is possible to combine into one step the synthesis and sterilization of the product, and it is economically competitive.

  10. Synthesize, Synthesize, Synthesize.

    ERIC Educational Resources Information Center

    Nugent, Susan Monroe, Ed.

    1987-01-01

    Focusing on synthesis--the ability to recognize and create new ideas that subsume and relate to others--as one of the most sophisticated skills writers can attain, the articles in this journal present many ideas for teaching synthesis and a number of classroom approaches that combine the study of English with other fields. The following titles and…

  11. A poly(A) binding protein-specific sequence motif: MRTENGKSKGFGFVC binding to mRNA poly(A) and polynucleotides and its role on mRNA translation.

    PubMed

    Rubin, H N; Halim, M N; Leavis, P C

    1994-06-01

    A consensus sequence (GKSKGFGFV) was recognized in all the sequenced poly(A) binding proteins. We synthesized a 15-amino acid peptide (corresponding to 354-368 in the yeast poly(A) binding protein) which includes the consensus sequence to test its binding affinity to different nucleotides, polynucleotides and mRNA with or without a poly(A) tail. Biochemical and biophysical studies revealed that the 15-amino acid peptide has a strong binding affinity to poly(A) alone or poly(A) attached at the 3' end of mRNA. Circular dichroism spectroscopy demonstrated that the secondary structure of the 15-mer is consistent with that expected based on the structure of the native RNP domain. Furthermore, among the various mononucleotides performed in the present studies, ATP was preferentially found to bind to the 15-mer. To further examine the biological significance of the binding of the 15-mer to the poly(A) tail of mRNA, in vitro translation of the mRNA poly(A)+ in the presence of the 15-mer drastically increased globin synthesis by almost 2-fold, while translation of the deadenylated mRNA in the presence of the 15-mer almost did not alter the rate of incorporation of radiolabeled leucine into globin.

  12. An automated Teflon microfluidic peptide synthesizer.

    PubMed

    Zheng, Hui; Wang, Weizhi; Li, Xiaojun; Wang, Zihua; Hood, Leroy; Lausted, Christopher; Hu, Zhiyuan

    2013-09-07

    We present a microfluidic synthesizer made entirely of Teflon material for solid phase peptide synthesis (SPPS). Solvent-resistant perfluoroalkoxy (PFA) was used to construct chip-sized devices featuring multiple tri-layer pneumatic microvalves. Using these devices, model peptides were automatically synthesized and cleaved in situ in a continuous-flow manner. The total coupling and cleavage time was significantly reduced compared to conventional bulk reactors. The synthesis of a decapeptide, for instance, took less than 6 h using our device while it usually takes more than three days using conventional reactors.

  13. Improving hydrothermal carbonization by using poly(ionic liquid)s.

    PubMed

    Zhang, Pengfei; Yuan, Jiayin; Fellinger, Tim-Patrick; Antonietti, Markus; Li, Haoran; Wang, Yong

    2013-06-03

    Pores for thought: Porous nitrogen-doped carbon materials (HTC Carbon with PILs) composed of spherical nanoparticles, and also those with Au-Pd core-shell nanoparticles embedded (Au-Pd@N-Carbon) were synthesized. These materials can be prepared from sugars by hydrothermal carbonization (160-200 °C) in the presence of poly(ionic liquid)s (PILs), which act as a stabilizer, pore-generating agent, and nitrogen source.

  14. Aggregation behavior of poly(ethylene glycol-bl-propylene sulfide) di- and triblock copolymers in aqueous solution.

    PubMed

    Cerritelli, Simona; O'Neil, Conlin P; Velluto, Diana; Fontana, Antonella; Adrian, Marc; Dubochet, Jacques; Hubbell, Jeffrey A

    2009-10-06

    Block copolymers of poly(ethylene glycol)-bl-poly(propylene sulfide) (PEG-PPS) have recently emerged as a new macromolecular amphiphile capable of forming a wide range of morphologies when dispersed in water. To understand better the relationship between stability and morphology in terms of the relative and absolute block compositions, we have synthesized a collection of PEG-PPS block copolymers and quantified their critical aggregation concentration and observed their morphology using cryogenic transmission electron microscopy after thin film hydration with extrusion and after solvent dispersion from tetrahydrofuran, a solvent for both blocks. By understanding the relationship between aggregate character and block copolymer architecture, we have observed that whereas the relative block lengths control morphology, the stability of the aggregates upon dilution is determined by the absolute block length of the hydrophobic PPS block. We have compared results obtained with PEG-PPS to those obtained with poly(ethylene glycol)-bl-poly(propylene oxide)-bl-poly(ethylene glycol) block copolymers (Pluronics). The results reveal that the PEG-PPS aggregates are substantially more stable than Pluronic aggregates, by more than an order of magnitude. PEG-PPS can form a wide variety of stable or metastable morphologies in dilute solution within normal time and temperature ranges, whereas Pluronics can generally form only spherical micelles under the same conditions. On the basis of these results, block copolymers of PEG with poly(propylene sulfide) may present distinct advantages over those with poly(propylene glycol) for a number of applications.

  15. Complex Polymeric Architectures Synthesized and Functionalized using Robust Chemistries

    NASA Astrophysics Data System (ADS)

    Killops, Kathryn L.

    Niche applications for polymeric materials put stringent requirements on their properties and architecture. Although polymer synthesis techniques have improved significantly to produce well-defined materials with narrow molecular weight distributions from a variety of monomeric precursors, the final materials often require fine-tuning of the structure or functionality to achieve the properties necessary for a given high performance application. The ability to modify and synthesize soft materials in precise and predictable manner requires the use of robust, efficient, and orthogonal chemistries. The highly branched structure of dendrimers provides an ideal platform to rigorously evaluate the ability of a reaction to proceed with quantitative conversion and high specificity. In order to achieve a macromolecular structure having a monodisperse molecular weight of over 10,000 Da, highly efficient reactions must be used. The synthesis of dendrimers up to the fourth generation was accomplished using successive iterations of thiol--ene 'click' chemistry and esterification reactions. The high molecular weight dendrimers were subsequently derivitized at the periphery using a variety of functional groups to demonstrate the orthogonality of the thiol--ene reaction. An extension of this work provided direct comparison of the thermally- and photochemically-initiated thiol--ene reactions, as applied to the functionalization of polymers both along the backbone and at the chain ends. With block copolymers, access to nanoscale features is afforded by the propensity of two chemically-distinct, covalently-linked polymer chains phase separate into discrete domains. These nanoscopic features have important implications for high performance applications like microelectronics and water purification. Precise modification of these structures expands the number of applications that could benefit from their implementation. In the search for a poly(ethylene oxide)-based nanoparticle with

  16. Stereocomplexation of low molecular weight poly(L-lactic acid) and high molecular weight poly(D-lactic acid), radiation crosslinking PLLA/PDLA stereocomplexes and their characterization

    NASA Astrophysics Data System (ADS)

    Quynh, Tran Minh; Mai, Hoang Hoa; Lan, Pham Ngoc

    2013-02-01

    Poly(L-lactic acid)s (PLLAx) were synthesized from L-lactic acid by polycondensation. Different stereocomplexes were also obtained with equimolar mixtures of synthesized PLLAx and a commercial PDLA. The stereocomplexes were crosslinked with triallyl isocyanurate (TAIC) by gamma irradiation. Crosslinking density increased with radiation doses, the heavier the crosslinking network, the lower its swelling degree. The crosslinking structures were introduced in the stereocomplexes inhibiting the mobility for crystallization of PLLA molecules. Thermal and mechanical properties of PLA stereocomplexes were remarkably enhanced by radiation induced crosslinking. PLA stereocomplex does not seem to be degraded by PLLA degrading microorganisms existing in compost at room temperature, but the synthesized PLLA was significantly degraded.

  17. Synthesis, characterization, and self-assembly of linear poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ε-caprolactone) (PEO-PPO-PCL) copolymers.

    PubMed

    Xu, Lifang; Zhang, Zhiqing; Wang, Fang; Xie, Dongdong; Yang, Shan; Wang, Tao; Feng, Lijuan; Chu, Chengchai

    2013-03-01

    Amphiphilic triblock copolymers of PEO-PPO-PCL with various block compositions have been synthesized by ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) initiated by the OH group of methoxy-poly(ethylene oxide)-poly(propylene oxide) (Me-PEO-PPO). Their structures were confirmed by Fourier transform infrared (FT-IR) measurements, and their self-assembly in aqueous solution was studied using fluorescence spectroscopy, transmission electron microscopy (TEM), UV-vis spectra, differential scanning calorimetry (DSC), and surface tension. For the copolymers studied in this paper, the critical aggregation concentrations (CAC) ranged from 5×10(3) to 2 mg/L. The critical micelle concentrations (CMC) decreased with increasing PCL block length, and the downtrend was more significant in the short PCL block length. All of the three copolymers were capable of solubilizing hydrophobic molecules (pyrene) in aqueous solution and copolymers with a longer PCL block exhibited a stronger solubilizing ability. The TEM images showed that the size and morphology of the aggregations could be tuned by varying the compositions or the concentration.

  18. Application of poly(ethylene glycol)-b-poly(epsilon-caprolactone) copolymers with different Poly(ethylene glycol) contents for the preparation of PEG-coated nanoparticles.

    PubMed

    Hou, Jingwen; Qian, Changyun; Zhang, Yanting; Guo, Shengrong

    2013-02-01

    This work used one poly(ethylene glycol)-b-poly(epsilon-caprolactone) (PEG-b-PCL) copolymer with low PEG content as matrix material and the copolymers with high PEG content as emulsifier to prepare PEG-coated nanoparticles for controlled release of paclitaxel by solvent evaporation technique. The copolymers were synthesized by ring-opening polymerization and characterized by 1H NMR and gel permeation chromatography (GPC). The effects of the composition and concentration of the copolymers used as emulsifier on the diameters and encapsulation efficiency of nanoparticles were investigated. The mean hydrodynamic diameters of the nanoparticles measured by dynamic light scattering ranged from 70 to 160 nm. The higher PEG content of emulsifier led to bigger diameter of nanoparticles and the emulsifier concentration (0.1%-1.0%) had no obvious influence on the diameters. The paclitaxel-loaded nanoparticles could achieve a sustained drug release for 7 days. When 2%-30% (w/v) of inulin was used as cryoprotectant during freeze drying process, the lyophilized nanoparticles could be well reconstituted into aqueous solution and the hydrodynamic diameter was not obviously changed.

  19. Poly-3-hydroxy butyric acid interaction with the transgenic flax fibers: FT-IR and Raman spectra of the composite extracted from a GM flax

    NASA Astrophysics Data System (ADS)

    Wróbel-Kwiatkowska, Magdalena; Żuk, Magdalena; Szopa, Jan; Dymińska, Lucyna; Mączka, Mirosław; Hanuza, Jerzy

    2009-07-01

    The FT-IR and FT-Raman studies have been performed on commercial 3-hydroxy-butyric acid, commercial poly-3-hydroxy butyric acid as well as poly-3-hydroxy butyric acid (PHB) produced by bacteria. The data were compared to those obtained for poly-3-hydroxy butyric acid extracted from natural and genetically modified flax. Genetically modified flax was generated by expression of three bacterial genes coding for synthesis of poly-3-hydroxy butyric acid. Thus transgenic flaxes were enhanced with different amount of the PHB. The discussion of polymer structure and vibrational properties has been done in order to get insight into differences among these materials. The interaction between the cellulose of flax fibers and embedded poly-3-hydroxybutyric acid has been also discussed. The spectroscopic data provide evidences for structural changes in cellulose and in PHB when synthesized in fibers. Based on this data it is suggesting that cellulose and PHB interact by hydrogen and ester bonds.

  20. Syntheses of novel substituted-boranophosphate nucleosides.

    PubMed

    Vyakaranam, Kamesh; Rana, Geeta; Spielvogel, Bernard F; Maguire, John A; Hosmane, Narayan S

    2002-01-01

    A number of substituted (borano) nucleic acids, 3'-[diethylphosphite(cyano, carboxy, or carbamoyl) borano] deoxynucleosides (3a-4c) and 5'-[diethylphosphite(cyano or carboxy) borano] deoxynucleosides (6a-7d) were prepared by a variety of synthetic procedures. The syntheses of the pyrophosphates (2a-2c), as precursors for 3a-4c, are also described.

  1. Method and apparatus for synthesizing filamentary structures

    DOEpatents

    Height, Murray J.; Howard, Jack B.; Vandersande, John B.

    2008-02-26

    Method and apparatus for producing filamentary structures. The structures include single-walled nanotubes. The method includes combusting hydrocarbon fuel and oxygen to establish a non-sooting flame and providing an unsupported catalyst to synthesize the filamentary structure in a post-flame region of the flame. Residence time is selected to favor filamentary structure growth.

  2. Evaluating Text-to-Speech Synthesizers

    ERIC Educational Resources Information Center

    Cardoso, Walcir; Smith, George; Fuentes, Cesar Garcia

    2015-01-01

    Text-To-Speech (TTS) synthesizers have piqued the interest of researchers for their potential to enhance the L2 acquisition of writing (Kirstein, 2006), vocabulary and reading (Proctor, Dalton, & Grisham, 2007) and pronunciation (Cardoso, Collins, & White, 2012; Soler-Urzua, 2011). Despite their proven effectiveness, there is a need for…

  3. Digital Frequency Synthesizer For Radar Astronomy

    NASA Technical Reports Server (NTRS)

    Sadr, Ramin; Satorius, Edgar; Robinett, J. Loris, Jr.; Olson, Erlend

    1992-01-01

    Report discusses conceptual digital frequency synthesizer part of programmable local oscillator in radar-astronomy system. Phase must remain continuous during adjustments of frequency, phase noise must be low, and spectral purity must be high. Discusses theory of operation in some mathematical detail and presents new analysis of spectral purity of output.

  4. Characterization of the Role of Hexamer AGUAAA and Poly(A) Tail in Coronavirus Polyadenylation

    PubMed Central

    Peng, Yu-Hui; Lin, Ching-Houng; Lin, Chao-Nan; Lo, Chen-Yu; Tsai, Tsung-Lin; Wu, Hung-Yi

    2016-01-01

    Similar to eukaryotic mRNA, the positive-strand coronavirus genome of ~30 kilobases is 5’-capped and 3’-polyadenylated. It has been demonstrated that the length of the coronaviral poly(A) tail is not static but regulated during infection; however, little is known regarding the factors involved in coronaviral polyadenylation and its regulation. Here, we show that during infection, the level of coronavirus poly(A) tail lengthening depends on the initial length upon infection and that the minimum length to initiate lengthening may lie between 5 and 9 nucleotides. By mutagenesis analysis, it was found that (i) the hexamer AGUAAA and poly(A) tail are two important elements responsible for synthesis of the coronavirus poly(A) tail and may function in concert to accomplish polyadenylation and (ii) the function of the hexamer AGUAAA in coronaviral polyadenylation is position dependent. Based on these findings, we propose a process for how the coronaviral poly(A) tail is synthesized and undergoes variation. Our results provide the first genetic evidence to gain insight into coronaviral polyadenylation. PMID:27760233

  5. [Removal Congo Red from Aqueous Solution Using Poly (AM-co-DVB)].

    PubMed

    Zhang, Luan-luan; Liao, Yun-wen; Gao, He-jun; Wang, Zhong-zhi; Shuai, Chao

    2015-06-01

    Poly(AM-co-DVB) was synthesized by acrylamide(AM) and divinylbenzene(DVB) via the crosslinking reaction. The microscope structure and thermal stability of Poly(AM-co-DVB) were characterized by FT-IR, SEM and TG. Congo red (CR) was used to measure the adsorptive capacity of Poly (AM-co-DVB). The effects of initial pH, contact time and temperature on the adsorption of CR on Poly (AM-co-DVB) were investigated in this work. The kinetics, equilibrium, and thermodynamics of the adsorption process were also discussed. The results showed that the maximum adsorption capacities were 319.1 mg x g(-1) at pH = 7.25 and contact time = 3 h. The adsorption kinetics was well fitted by a pseudo-second-order model and the adsorption isotherms agreed well with the Langmuir model. The adsorption process was spontaneous process. Above all, the adsorption capacity of Poly (AM-co-DVB) on Congo red is significant.

  6. Magnetic poly(PEGMA-MAA) nanoparticles: photochemical preparation and potential application in drug delivery.

    PubMed

    Sun, Han-Wen; Zhang, Lian-Ying; Zhu, Xin-Jun; Wang, Xin-Fang

    2009-01-01

    Poly(PEGMA-MAA)-coated superparamagnetic nanoparticles were synthesized by in situ photochemical polymerization in magnetite aqueous suspension under UV irradiation. The magnetic poly(PEGMA-MAA) nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), photo correlation spectroscopy (PCS) and vibration sample magnetometry (VSM), respectively. The results indicated that the magnetic poly(PEGMA-MAA) nanoparticles were of regularly spherical shape and remained monodisperse. The average size measured in aqueous media was 96.4 nm, which was much bigger than that in dry state, the nanoparticles behaved superparamagnetic with saturated magnetization of 64.8 emu/g, the zeta potential was -18.3 mV at physiological pH 7.2, and the magnetic poly(PEGMA-MAA) nanoparticles had a high stability in vitro. A typical anti-inflammatory drug, ibuprofen, was used for drug loading, and the release behavior of ibuprofen in a simulated body fluid (SBF, pH 7.4) was studied. The results indicated that these novel magnetic nanoparticles had a high drug-loading capacity and favorable release properties for ibuprofen. The magnetic poly(PEGMA-MAA) nanoparticles are very promising for application in drug delivery.

  7. Helical Poly(5-alkyl-2,3-thiophene)s: Controlled Synthesis and Structure Characterization

    SciTech Connect

    Zhang, Hong-Hai; Ma, Chuanxu; Bonnesen, Peter V.; Zhu, Jiahua; Sumpter, Bobby G.; Carrillo, Jan-Michael Y.; Yin, Panchao; Wang, Yangyang; Li, An-Ping; Hong, Kunlun

    2016-07-12

    Whereas Poly(3-alkyl-2,5-thiophene)s (P3AT), with many potential applications, have been extensively investigated, their ortho-connected isomers, poly(5-alkyl-2,3-thiophene)s (P5AT), have never been reported because of the difficulty in their syntheses. We herein present the first synthesis of regioregular P5AT via controlled Suzuki cross-coupling polymerization with PEPPSI-IPr as catalyst, affording the polymers with tunable molecular weight, narrow polydispersity (PDI) and well-defined functional end groups at the gram scale. The helical geometry of P5AT was studied by a combination of NMR, small angle x-ray scattering (SAXS) and scanning tunneling microscopy (STM). Particularly, the single polymer chain of poly(5- 2 butyl-2,3-thiophene) (P5BT) on highly oriented pyrolytic graphite (HOPG) substrates with either M or P helical conformation was directly observed by STM. The comparison of UV-vis absorption between poly(5-hexyl-2,3-thiophene) (P5HT) (λ = 345 nm) and poly(3-hexyl-2,5- thiophene) (P3HT) (λ = 450 nm) indicated that the degree of conjugation of the backbone in P5HT is less than in P3HT, which may be a consequence of the helical geometry of the former compared to the more planar geometry of the latter. Moreover, we found that P5HT can emit green fluorescence under UV (λ = 360 nm) irradiation

  8. Helical Poly(5-alkyl-2,3-thiophene)s: Controlled Synthesis and Structure Characterization

    DOE PAGES

    Zhang, Hong-Hai; Ma, Chuanxu; Bonnesen, Peter V.; ...

    2016-07-12

    Whereas Poly(3-alkyl-2,5-thiophene)s (P3AT), with many potential applications, have been extensively investigated, their ortho-connected isomers, poly(5-alkyl-2,3-thiophene)s (P5AT), have never been reported because of the difficulty in their syntheses. We herein present the first synthesis of regioregular P5AT via controlled Suzuki cross-coupling polymerization with PEPPSI-IPr as catalyst, affording the polymers with tunable molecular weight, narrow polydispersity (PDI) and well-defined functional end groups at the gram scale. The helical geometry of P5AT was studied by a combination of NMR, small angle x-ray scattering (SAXS) and scanning tunneling microscopy (STM). Particularly, the single polymer chain of poly(5- 2 butyl-2,3-thiophene) (P5BT) on highly oriented pyrolyticmore » graphite (HOPG) substrates with either M or P helical conformation was directly observed by STM. The comparison of UV-vis absorption between poly(5-hexyl-2,3-thiophene) (P5HT) (λ = 345 nm) and poly(3-hexyl-2,5- thiophene) (P3HT) (λ = 450 nm) indicated that the degree of conjugation of the backbone in P5HT is less than in P3HT, which may be a consequence of the helical geometry of the former compared to the more planar geometry of the latter. Moreover, we found that P5HT can emit green fluorescence under UV (λ = 360 nm) irradiation« less

  9. Removal of diethyl phthalate from aqueous phase using magnetic poly(EGDMA-VP) beads.

    PubMed

    Özer, Elif Tümay; Osman, Bilgen; Kara, Ali; Beşirli, Necati; Gücer, Seref; Sözeri, Hüseyin

    2012-08-30

    The barium hexaferrite (BaFe(12)O(19)) containing magnetic poly(ethylene glycol dimethacrylate-vinyl pyridine), (mag-poly(EGDMA-VP)) beads (average diameter=53-212 μm) were synthesized and characterized. Their use as an adsorbent in the removal of diethyl phthalate (DEP) from an aqueous solution was investigated. The mag-poly(EGDMA-VP) beads were prepared by copolymerizing of 4-vinyl pyridine (VP) with ethylene glycol dimethacrylate (EGDMA). The mag-poly(EGDMA-VP) beads were characterized by N(2) adsorption/desorption isotherms (BET), vibrating sample magnetometer (VSM), X-ray powder diffraction (XRD), elemental analysis, scanning electron microscope (SEM) and swelling studies. At a fixed solid/solution ratio, the various factors affecting the adsorption of DEP from aqueous solutions such as pH, initial concentration, contact time and temperature were analyzed. The maximum DEP adsorption capacity of the mag-poly(EGDMA-VP) beads was determined as 98.9 mg/g at pH 3.0, 25°C. All the isotherm data can be fitted with both the Langmuir and the Dubinin-Radushkevich isotherm models. The pseudo first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models were used to describe the adsorption kinetics. The thermodynamic parameters obtained indicated the exothermic nature of the adsorption. The DEP adsorption capacity did not change after 10 batch successive reactions, demonstrating the usefulness of the magnetic beads in applications.

  10. Microwave-assisted preparation of poly(ionic liquids)-modified magnetic nanoparticles for pesticide extraction.

    PubMed

    Zhang, Ruizhe; Su, Ping; Yang, Lu; Yang, Yi

    2014-06-01

    Novel poly(ionic liquids) were synthesized and immobilized on prepared magnetic nanoparticles, which were used to extract pesticides from fruit and vegetable samples by dispersive solid-phase extraction prior to high-performance liquid chromatography analysis. Compared with monomeric ionic liquids, poly(ionic liquids) have a larger effective contact area and higher viscosity, so they can achieve higher extraction efficiency and be used repeatedly without a decrease in analyte recovery. The immobilized poly(ionic liquids) were rapidly separated from the sample matrix, providing a simple approach for sample pretreatment. The nature and volume of the desorption solvent and amount of poly(ionic liquid)-modified magnetic material were optimized for the extraction process. Under optimum conditions, calibration curves were linear (R(2) > 0.9988) for pesticide concentrations in the range of 0.100-10.000 μg/L. The relative standard deviations for repeated determinations of the four analytes were 2.29-3.31%. The limits of detection and quantification were 0.29-0.88 and 0.97-2.93 μg/L, respectively. Our results demonstrate that the developed poly(ionic liquid)-modified material is an effective absorbent to extract pesticides from fruit and vegetable samples.

  11. Influence of poly(ethylene glycol) as pore-generator on morphology and performance of chitosan/poly(vinyl alcohol) membrane adsorbents

    NASA Astrophysics Data System (ADS)

    Salehi, E.; Madaeni, S. S.

    2014-01-01

    Macroporous chitosan/poly(vinyl alcohol) membrane adsorbents were synthesized by solvent evaporation in the presence of poly(ethylene glycol) which was utilized as porogen. The membranes were applied for Cu(II) ion adsorption from water. SEM, AFM and wettability analyses were performed for membrane characterization. Insertion of poly(ethylene glycol) generated macrovoids in the dense structure of CS/PVA membranes through particulate leaching out mechanism. According to the static adsorption tests, the uptake capacity of the porous membranes is elevated (∼26 mg/g) compared to that of the dense membranes (∼10 mg/g). This phenomenon is attributed to the increase in the density of active sites, water affinity and surface roughness as a result of the porogen effects. The approachability of the ions to the active sites was also affected by these important parameters. Both size and density of the macrovoids increased with increasing PEG content from nil to 5 wt%. Fragility of the resultant porous structures prohibited synthesizing CS/PVA membranes with higher porogen contents. Desorption tests showed that the porous membranes were better regenerated in comparison to the dense membranes using Na2EDTA as eluant. Generally, the results suggested that the CS/PVA membranes, comprising PEG as pore-generator agent, are potential candidates for adsorption and elimination of Cu(II) ions from water.

  12. Zwitterionic Poly(amino acid methacrylate) Brushes

    PubMed Central

    2014-01-01

    A new cysteine-based methacrylic monomer (CysMA) was conveniently synthesized via selective thia-Michael addition of a commercially available methacrylate-acrylate precursor in aqueous solution without recourse to protecting group chemistry. Poly(cysteine methacrylate) (PCysMA) brushes were grown from the surface of silicon wafers by atom-transfer radical polymerization. Brush thicknesses of ca. 27 nm were achieved within 270 min at 20 °C. Each CysMA residue comprises a primary amine and a carboxylic acid. Surface zeta potential and atomic force microscopy (AFM) studies of the pH-responsive PCysMA brushes confirm that they are highly extended either below pH 2 or above pH 9.5, since they possess either cationic or anionic character, respectively. At intermediate pH, PCysMA brushes are zwitterionic. At physiological pH, they exhibit excellent resistance to biofouling and negligible cytotoxicity. PCysMA brushes undergo photodegradation: AFM topographical imaging indicates significant mass loss from the brush layer, while XPS studies confirm that exposure to UV radiation produces surface aldehyde sites that can be subsequently derivatized with amines. UV exposure using a photomask yielded sharp, well-defined micropatterned PCysMA brushes functionalized with aldehyde groups that enable conjugation to green fluorescent protein (GFP). Nanopatterned PCysMA brushes were obtained using interference lithography, and confocal microscopy again confirmed the selective conjugation of GFP. Finally, PCysMA undergoes complex base-catalyzed degradation in alkaline solution, leading to the elimination of several small molecules. However, good long-term chemical stability was observed when PCysMA brushes were immersed in aqueous solution at physiological pH. PMID:24884533

  13. Amphiphilic cationic [dendritic poly(L-lysine)]-block-poly(L-lactide)-block-[dendritic poly(L-lysine)]s in aqueous solution: self-aggregation and interaction with DNA as gene delivery carriers.

    PubMed

    Zhu, Yingdan; Sheng, Ruilong; Luo, Ting; Li, Hui; Sun, Wenyan; Li, Yang; Cao, Amin

    2011-02-11

    A new series of triblock [dendritic poly(L-lysine)]-block-PLLA-block-[dendritic poly(L-lysine)]s (DL(2) -PLLA-DL(2) ) with PLLA block lengths of 11.5-26.5 and double 2-generation PLL dendrons DL(2) as model cationic amphiphiles were synthesized and characterized. Their CAC, self-aggregation and plasmid DNA binding affinities in pure water and PBS were studied. The PLLA block length dependence of particle size, morphology and ξ potential for organized pDNA/amphiphile polyplex aggregates were examined. Finally, toxicities of these DL(2) -PLLA-DL(2) amphiphiles and their polyplexes were assayed by MTT with HeLa, SMMC-7721 and COS-7 cells, and COS-7 cell luciferase and eGFP gene transfection efficacies with these amphiphiles as the delivery carriers were investigated.

  14. Maize mitochondria synthesize organ-specific polypeptides

    SciTech Connect

    Newton, K.J.; Walbot, V.

    1985-10-01

    The authors detected both quantitative and qualitative organ-specific differences in the total protein composition of mitochondria of maize. Labeling of isolated mitochondria from each organ demonstrated that a few protein differences are due to changes in the polypeptides synthesized by the organelle. The synthesis of developmental stage-specific mitochondrial polypeptides was found in the scutella of developing and germinating kernels. The approximately 13-kDa polypeptide synthesized by mitochondria from seedlings of the Texas (T) male-sterile cytoplasm was shown to be constitutively expressed in all organs of line B37T tested. Methomyl, an insecticide known to inhibit the growth of T sterile plants, was shown to be an effective inhibitor of protein synthesis in mitochondria from T plants.

  15. Genome Mining for Ribosomally Synthesized Natural Products

    PubMed Central

    Velásquez, Juan E.; van der Donk, Wilfred

    2011-01-01

    In recent years, the number of known peptide natural products that are synthesized via the ribosomal pathway has rapidly grown. Taking advantage of sequence homology among genes encoding precursor peptides or biosynthetic proteins, in silico mining of genomes combined with molecular biology approaches has guided the discovery of a large number of new ribosomal natural products, including lantipeptides, cyanobactins, linear thiazole/oxazole-containing peptides, microviridins, lasso peptides, amatoxins, cyclotides, and conopeptides. In this review, we describe the strategies used for the identification of these ribosomally-synthesized and posttranslationally modified peptides (RiPPs) and the structures of newly identified compounds. The increasing number of chemical entities and their remarkable structural and functional diversity may lead to novel pharmaceutical applications. PMID:21095156

  16. Syntheses and studies of organosilicon compounds

    SciTech Connect

    Xie, Ren

    1999-02-12

    The syntheses of polycarbosilanes and polysilanes as silicon carbide ceramic precursors have been active research areas in the Barton Research Group. In this thesis, the work is focused on the preparation of polycarbosilanes and polysilanes as stoichiometric silicon carbide precursor polymers. The syntheses of the precursor polymers are discussed and the conversions of these precursors to silicon carbide via pyrolysis are reported. The XRD pattern and elemental analyses of the resulting silicon carbide ceramics are presented. Silicon monoxide is an important intermediate in the production of silicon metal. The existence of silicon monoxide in gap phase has been widely accepted. In the second part of this thesis, the generation of gaseous silicon monoxide in four different reactors and the reactions of gaseous silicon monoxide towards organic compounds are discussed.

  17. Synthesis and Properties of pH-, Thermo-, and Salt-Sensitive Modified Poly(aspartic acid)/Poly(vinyl alcohol) IPN Hydrogel and Its Drug Controlled Release

    PubMed Central

    Lu, Jingqiong; Li, Yinhui; Hu, Deng; Chen, Xiaoling; Liu, Yongmei; Wang, Liping; Zhao, Yansheng

    2015-01-01

    Modified poly(aspartic acid)/poly(vinyl alcohol) interpenetrating polymer network (KPAsp/PVA IPN) hydrogel for drug controlled release was synthesized by a simple one-step method in aqueous system using poly(aspartic acid) grafting 3-aminopropyltriethoxysilane (KH-550) and poly(vinyl alcohol) (PVA) as materials. The hydrogel surface morphology and composition were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The thermal stability was analyzed by thermogravimetric analysis (TGA). The swelling properties and pH, temperature, and salt sensitivities of KPAsp, KPAsp/PVA semi-interpenetrating polymer network (semi-IPN), and KPAsp/PVA IPN hydrogels were also investigated. All of the three hydrogels showed ampholytic pH-responsive properties, and swelling behavior was also extremely sensitive to the temperature, ionic strength, and cationic species. Finally, the drug controlled release properties of the three hydrogels were evaluated and results indicated that three hydrogels could control drug release by external surroundings stimuli. The drug controlled release properties of KPAsp/PVA IPN hydrogel are the most outstanding, and the correlative measured release profiles of salicylic acid at 37°C were 32.6 wt% at pH = 1.2 (simulated gastric fluid) and 62.5 wt% at pH = 7.4 (simulated intestinal fluid), respectively. These results indicated that KPAsp/PVA IPN hydrogels are a promising carrier system for controlled drug delivery. PMID:26351630

  18. Synthesis and optoelectronic properties of nanocomposites comprising of poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) block copolymer and graphene nanosheets.

    PubMed

    Chiu, Po-Chun; Su, Reagen Ying-Tai; Yeh, Je-Yuan; Yeh, Cheng-Yang; Tsiang, Raymond Chien-Chao

    2013-06-01

    A novel conjugated block copolymer, poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) (PFBPT) and its nanocomposite containing graphene sheets were synthesized for enhancing optoelectronic performance. Graphene sheets were in-situ formed in the polymer matrix via a reduction of octadecylamine-functionalized graphite oxide, where the graphite oxide came from acidification and exfoliation of graphite. The blue-green light-emitting poly(9,9-dioctylfluorene) block and red-orange light-emitting poly(3-hexylthiophene) block exhibit a combined white electroluminescence when the composite materials were fabricated as the emitting layer of a polymeric light-emitting diode (PLED). Graphene does not alter the optical characteristics wavelength of PFBPT but electric conductivity increases with the amount of graphene. The HOMO and LUMO were measured and the band gap is smaller with existence of graphene. The threshold voltage decreases with an increase in the graphene content. The device fabricated with PFBPT/graphene nanocomposite containing 1% graphene has a maximum white-light luminescence at a voltage of 9.0 V.

  19. Evaluation of CO2-philicity of poly(vinyl acetate) and poly(vinyl acetate-alt-maleate) copolymers through molecular modeling and dissolution behavior measurement.

    PubMed

    Hu, Dongdong; Sun, Shaojun; Yuan, Peiqing; Zhao, Ling; Liu, Tao

    2015-02-19

    Multiscale molecular modeling and dissolution behavior measurement were both used to evaluate the factors conclusive on the CO2-philicity of poly(vinyl acetate) (PVAc) homopolymer and poly(vinyl acetate-alt-maleate) copolymers. The ab initio calculated interaction energies of the candidate CO2-philic molecule models with CO2, including vinyl acetate dimer (VAc), dimethyl maleate (DMM), diethyl maleate (DEM), and dibutyl maleate (DBM), showed that VAc was the most CO2-philc segment. However, the cohesive energy density, solubility parameter, Flory-Huggins parameter, and radial distribution functions calculated by using the molecular dynamics simulations for the four polymer and polymer-CO2 systems indicated that poly(VAc-alt-DBM) had the most CO2-philicity. The corresponding polymers were synthesized by using free radical polymerization. The measurement of cloud point pressures of the four polymers in CO2 also demonstrated that poly(VAc-alt-DBM) had the most CO2-philicity. Although copolymerization of maleate, such as DEM or DBM, with PVAc reduced the polymer-CO2 interactions, the weakened polymer-polymer interaction increased the CO2-philicity of the copolymers. The polymer-polymer interaction had a significant influence on the CO2-philicity of the polymer. Reduction of the polymer-polymer interaction might be a promising strategy to prepare the high CO2-philic polymers on the premise that the strong polymer-CO2 interaction could be maintained.

  20. Method of synthesizing a low density material

    DOEpatents

    Lorensen, L.E.; Monaco, S.B.

    1987-02-27

    A novel method of synthesizing a polymeric material of low density of the order of 50mg/cc or less. Such a low density material has applications in many areas including laser target fabrication. The method comprises preparing a polymer blend of two incompatible polymers as a major and a minor phase by mixing them and extruding the mixture, and then selectively extracting the major component, to yield a fine, low density structure.

  1. Villain's fractal growth of poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] J-aggregates onto layer-by-layer films and its effect on film absorbance spectrum

    NASA Astrophysics Data System (ADS)

    Ferreira, Quirina; António Ribeiro, Paulo; Raposo, Maria

    2013-06-01

    Morphology of poly(allylamine hydrochloride) and poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) layer-by-layer (LBL) films is shown to influence the orientation of PAZO chromophores with respect to solid support surface, which in turn is related with observed red-shifts changes of the chromophore absorbance peak position relative to that of solution spectrum, as the bilayers are being deposited. For the first bilayers, an increase of red shift values is observed, while roughness and grain radius are kept practically constant; after the 5th bilayer, the red-shift values decrease, while grain sizes increase and the number of grains decreases. This behavior is consistent with adsorption of coiled PAZO molecules, treated as pseudo-particles, with the chromophores head-to-head oriented-J aggregates. These aggregates adsorb perpendicularly to the substrate surface for the first layers and, as roughness and grain radius increase, the adsorption of the J aggregates takes place parallel to the solid support surface, which gives rise to a decrease in the red shift value. Moreover, the adsorption of these pseudo-particles follows a fractal growth characterized by a scaling exponent of α = 0.80 ± 0.02 and a temporal growth exponent of β = 0.17 ± 0.02. These values suggest a layer growth according with Villain model, which accounts for the interactions between deposited particles and the surface. This is in accordance with the electrostatic forces driving LbL film formation and accounts for the observed morphology behavior for the different number of layers.

  2. Poly(ethylene oxide) functionalization

    DOEpatents

    Pratt, Russell Clayton

    2014-04-08

    A simple procedure is provided by which the hydroxyl termini of poly(ethylene oxide) can be appended with functional groups to a useful extent by reaction and precipitation. The polymer is dissolved in warmed toluene, treated with an excess of organic base and somewhat less of an excess of a reactive acylating reagent, reacted for several hours, then precipitated in isopropanol so that the product can be isolated as a solid, and salt byproducts are washed away. This procedure enables functionalization of the polymer while not requiring laborious purification steps such as solvent-solvent extraction or dialysis to remove undesirable side products.

  3. Controlled release of curcumin from poly(HEMA-MAPA) membrane.

    PubMed

    Caka, Müşerref; Türkcan, Ceren; Aktaş Uygun, Deniz; Uygun, Murat; Akgöl, Sinan; Denizli, Adil

    2017-05-01

    In this work, poly(HEMA-MAPA) membranes were prepared by UV-polymerization technique. These membranes were characterized by SEM, FTIR, and swelling studies. Synthesized membranes had high porous structure. These membranes were used for controlled release of curcumin which is already used as folk remedy and used as drug for some certain diseases and cancers. Curcumin release was investigated for various pHs and temperatures. Optimum drug release yield was found to be as 70% at pH 7.4 and 37 °C within 2 h period. Time-depended release of curcumin was also investigated and its slow release from the membrane demonstrated within 48 h.

  4. Poly(N-arylenebenzimidazole)s via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Jr., Joseph G. (Inventor)

    1996-01-01

    Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

  5. Clickable Poly(ionic liquids): A Materials Platform for Transfection.

    PubMed

    Freyer, Jessica L; Brucks, Spencer D; Gobieski, Graham S; Russell, Sebastian T; Yozwiak, Carrie E; Sun, Mengzhen; Chen, Zhixing; Jiang, Yivan; Bandar, Jeffrey S; Stockwell, Brent R; Lambert, Tristan H; Campos, Luis M

    2016-09-26

    The potential applications of cationic poly(ionic liquids) range from medicine to energy storage, and the development of efficient synthetic strategies to target innovative cationic building blocks is an important goal. A post-polymerization click reaction is reported that provides facile access to trisaminocyclopropenium (TAC) ion-functionalized macromolecules of various architectures, which are the first class of polyelectrolytes that bear a formal charge on carbon. Quantitative conversions of polymers comprising pendant or main-chain secondary amines were observed for an array of TAC derivatives in three hours using near equimolar quantities of cyclopropenium chlorides. The resulting TAC polymers are biocompatible and efficient transfection agents. This robust, efficient, and orthogonal click reaction of an ionic liquid, which we term ClickabIL, allows straightforward screening of polymeric TAC derivatives. This platform provides a modular route to synthesize and study various properties of novel TAC-based polymers.

  6. Radiation synthesis of nanosilver nanohydrogels of poly(methacrylic acid)

    NASA Astrophysics Data System (ADS)

    Gupta, Bhuvanesh; Gautam, Deepti; Anjum, Sadiya; Saxena, Shalini; Kapil, Arti

    2013-11-01

    Nanosilver nanohydrogels (nSnH) of poly(methacrylic acid) were synthesized and stabilized using gamma irradiation. The main objective of this study was to develop silver nanoparticles and to evaluate the antimicrobial activity. Radiation helps in the polymerization, crosslinking and reduction of silver nitrate as well. Highly stable and uniformly distributed silver nanoparticles have been obtained within hydrogel network by water in oil nanoemulsion polymerization and were evaluated by dynamic light scattering (DLS) and transmission electron microscopy (TEM) respectively. TEM showed almost spherical and uniform distribution of silver nanoparticles through the hydrogel network. The mean size of silver nanoparticles ranging is 10-50 nm. The nanohydrogels showed good swelling in water. Antibacterial studies of nSnH suggest that it can be a good candidate as coating material in biomedical applications.

  7. Poly(1,3,4-oxadiazoles) via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Wolf, Peter (Inventor)

    1992-01-01

    Poly(1,3,4-oxadiazoles) (POX) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) 1,3,4-oxadiazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as sulfolane or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) 1,3,4-oxadiazole monomers are synthesized by reacting 4-hydroxybenzoic hydrazide with phenyl 4-hydrobenzoate in the melt and also by reacting aromatic dihydrazides with two moles of phenyl 4-hydroxybenzoate in the melt. This synthetic route has provided high molecular weight POX of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the large variety of activated aromatic dihalides which are available.

  8. Hysteresis Behaviors of Poly (Naphthalene Quinone) Radical Electrorheological Fluid

    NASA Astrophysics Data System (ADS)

    Choi, Hyoung J.; Cho, Min S.; Jhon, Myung S.

    As a potential electrorheological(ER) material, poly(naphthalene quinone) radical (PNQR) ER fluid was prepared, and its rheological behavior and hysteresis phenomenon were investigated. PNQR was synthesized by Friedel-Crafts acylation between naphthalene and phthalic anhydride, using zinc chloride as a catalyst at 256°C. A Physica rheometer equipped with a high voltage generator was used to measure the rheological properties of the ER fluids, which were prepared by dispersing PNQR in silicone oil at several particle concentrations. Shear stresses were observed to decrease as shear rate increased in the region of slow deformation rate. It was further found that ER fluid showed different hysteresis behaviors according to the shear rate ranges; thixotropy was observed in the low shear rate region (0.007-0.51/s) and anti-thixotropy in the high shear rate region (0.5-10001/s). Controlled shear stress mode was also applied to observe similar behaviors.

  9. Poly(N-arylenbenzimidazoles) via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1995-01-01

    Novel poly(N-arylenebenzimidazole)s (PNABIs) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl N-arylenebenzimidazole) monomers are synthesized by reacting phenyl 4-hydroxybenzoate with bis(2-aminoanilino) arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyl N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

  10. Poly(vinylidene fluoride) Containing Phosphonic Acid as Anticorrosion Coating for Steel.

    PubMed

    Banerjee, Sanjib; Wehbi, Mohammad; Manseri, Abdellatif; Mehdi, Ahmad; Alaaeddine, Ali; Hachem, Ali; Ameduri, Bruno

    2017-02-22

    Vinylidene fluoride (VDF)-based copolymers bearing pendant phosphonic acid function for potential application as anticorrosion coatings were synthesized via free radical copolymerization of VDF with a new phosphorus containing 2-trifluoromethacrylate monomer, (dimethoxyphosphoryl)methyl 2-(trifluoromethyl)acrylate (MAF-DMP). MAF-DMP was prepared from 2-trifluoromethacrylic acid in 60% overall yield. Radical copolymerizations of VDF with MAF-DMP initiated by tert-amyl peroxy-2-ethylhexanoate at varying ([VDF]0/[MAF-DMP]0) feed ratios led to several poly(VDF-co-MAF-DMP) copolymers having different molar percentages of VDF (79-96%) and number-average molecular weights (Mn's) up to ca. 10 000 g mol(-1) in fair yields (47-53%). Determination of the composition and microstructure of all the synthesized copolymers was done by (1)H and (19)F NMR spectroscopies. The monomer reactivity ratios of this new VDF/MAF-DMP pair were also determined (rVDF = 0.76 ± 0.34 and rMAF-DMP = 0 at 74 °C). The resulting poly(VDF-co-MAF-DMP) copolymers exhibited high melting temperature (162-171 °C, with respect to the VDF content), and the degree of crystallinity reached up to 51%. Finally, the pendant dimethyl phosphonate ester groups of the synthesized poly(VDF-co-MAF-DMP) copolymer were quantitatively hydrolyzed, giving rise to novel phosphonic acid-functionalized PVDF (PVDF-PA). In comparison to hydrophobic poly(VDF-co-MAF-DMP) copolymers (the water contact angle, WCA, was 98°), the hydrophilic character of the PVDF-PA was found to be surprisingly rather pronounced, exhibiting low WCA (15°). Finally, steel plates coated with PVDF-PA displayed satisfactory anticorrosion properties under simulated seawater environment.

  11. Thermally-responsive poly(ester urethane)s

    NASA Astrophysics Data System (ADS)

    Pierce, Benjamin Franklin

    Thermally-responsive materials are quite useful in the biomedical field, but their full potential has yet to be realized. For example, polyurethanes are capable of exhibiting shape-memory properties, or the ability to change shape upon the application of a stimulus, but only a few practical thermally responsive polyurethanes have been reported due to the lack of novel starting materials and optimized systems. This work describes the synthesis of several degradable polymers and the characterization of their thermally responsive behavior. First, several amorphous polyester prepolymers are synthesized and incorporated in thermoplastic poly(ester urethane)s, which are highly elastic but display impractical thermal properties. Their potential as degradable implants is investigated, as well as their bulk and surface properties. These systems are then optimized and tailored for more practical purposes, resulting in the synthesis of thermoset elastomers based on poly(1,4-cyclohexanedimethanol 1,4-cyclohexanedicarboxylate) (PCCD) prepolymers that display a broad range of useful mechanical properties, thermal properties, and shape-memory properties. A novel method for controlling a microscopic and nanoscopic topographical shape-memory phenomenon is presented. Finally, the synthesis of amine-functionalized polyesters is presented. All materials are characterized by 1H and 13C NMR, GPC, DSC, TGA, and Instron.

  12. Targeting poly(ADP-ribose) polymerase activity for cancer therapy

    PubMed Central

    Mégnin-Chanet, Frédérique; Bollet, Marc A.

    2010-01-01

    Poly(ADP-ribosyl)ation is a ubiquitous protein modification found in mammalian cells that modulates many cellular responses, including DNA repair. The poly(ADP-ribose) polymerase (PARP) family catalyze the formation and addition onto proteins of negatively charged ADP-ribose polymers synthesized from NAD+. The absence of PARP-1 and PARP-2, both of which are activated by DNA damage, results in hypersensitivity to ionizing radiation and alkylating agents. PARP inhibitors that compete with NAD+ at the enzyme’s activity site are effective chemo- and radiopotentiation agents and, in BRCA-deficient tumors, can be used as single-agent therapies acting through the principle of synthetic lethality. Through extensive drug-development programs, third-generation inhibitors have now entered clinical trials and are showing great promise. However, both PARP-1 and PARP-2 are not only involved in DNA repair but also in transcription regulation, chromatin modification, and cellular homeostasis. The impact on these processes of PARP inhibition on long-term therapeutic responses needs to be investigated. PMID:20725763

  13. Thiol-ene Clickable Poly(glycidol) Hydrogels for Biofabrication.

    PubMed

    Stichler, Simone; Jungst, Tomasz; Schamel, Martha; Zilkowski, Ilona; Kuhlmann, Matthias; Böck, Thomas; Blunk, Torsten; Teßmar, Jörg; Groll, Jürgen

    2017-01-01

    In this study we introduce linear poly(glycidol) (PG), a structural analog of poly(ethylene glycol) bearing side chains at each repeating unit, as polymer basis for bioink development. We prepare allyl- and thiol-functional linear PG that can rapidly be polymerized to a three-dimensionally cross-linked hydrogel network via UV mediated thiol-ene click reaction. Influence of polymer concentration and UV irradiation on mechanical properties and swelling behavior was examined. Thiol-functional PG was synthesized in two structural variations, one containing ester groups that are susceptible to hydrolytic cleavage, and the other one ester-free and stable against hydrolysis. This allowed the preparation of degradable and non-degradable hydrogels. Cytocompatibility of the hydrogel was demonstrated by encapsulation of human bone marrow-derived mesenchymal stem cells (hBMSCs). Rheological properties of the hydrogels were adjusted for dispense plotting by addition of high molecular weight hyaluronic acid. The optimized formulation enabled highly reproducible plotting of constructs composed of 20 layers with an overall height of 3.90 mm.

  14. Biodegradable poly(ethylenimine) for plasmid DNA delivery.

    PubMed

    Ahn, Cheol-Hee; Chae, Su Young; Bae, You Han; Kim, Sung Wan

    2002-04-23

    Poly(ethylenimine) (PEI) has been known as an efficient gene carrier with the highest cationic charge potential. High transfection efficiency of PEI, along with its cytotoxicity, strongly depends on the molecular weight. Synthesis of cationic copolymers derived from the low molecular weight of PEI and hydrophilic poly(ethylene glycol) (PEG), which are water soluble and degradable under physiological conditions, was investigated for plasmid delivery. Hydrophilic PEG is expected to reduce the toxicity of the copolymer, improve the poor solubility of the PEI and DNA complexes, and help to introduce degradable bonds by reaction with the primary amines in the PEI. Considering the dependence of transfection efficiency and cytotoxicity on the molecular weight of the PEI, high transfection efficiency is expected from an increased molecular weight of the copolymer and low cytotoxicity from the introduction of PEG and the degradation of the copolymer into low molecular weight PEIs. Reaction conditions were carefully controlled to produce water soluble copolymers. Results from a gel retardation assay and zetapotentiometer indicated that complete neutralization of the complexes was achieved at the charge ratios of copolymer/pSV-beta-gal plasmid from 0.8 to 1.0 with the mean particle size of the polyplexes ranging from 129.8+/-0.9 to 151.8+/-3.4 nm. In vitro transfection efficiency of the synthesized copolymer increased up to three times higher than that of starting low molecular weight PEI, while the cell viability was maintained over 80%.

  15. Poly(Limonene Thioether) Scaffold for Tissue Engineering.

    PubMed

    Fischer, Kristin M; Morgan, Kathy Ye; Hearon, Keith; Sklaviadis, Demetra; Tochka, Zachary L; Fenton, Owen S; Anderson, Daniel G; Langer, Robert; Freed, Lisa E

    2016-04-06

    A photocurable thiol-ene network polymer, poly(limonene thioether) (PLT32o), is synthesized, characterized, fabricated into tissue engineering scaffolds, and demonstrated in vitro and in vivo. Micromolded PLT32o grids exhibit compliant, elastomeric mechanical behavior similar to grids made of poly(glycerol sebacate) (PGS), an established biomaterial. Multilayered PL32o scaffolds with regular, geometrically defined pore architectures support heart cell seeding and culture in a manner similar to multilayered PGS scaffolds. Subcutaneous implantation of multilayered PLT32o scaffolds with cultured heart cells provides long-term 3D structural support and retains the exogenous cells, whereas PGS scaffolds lose both their structural integrity and the exogenous cells over 31 d in vivo. PLT32o membrane implants retain their dry mass, whereas PGS implants lose 70 percent of their dry mass by day 31. Macrophages are initially recruited to PLT32o and PGS membrane implants but are no longer present by day 31. Facile synthesis and processing in combination with the capability to support heart cells in vitro and in vivo suggest that PLT32o can offer advantages for tissue engineering applications where prolonged in vivo maintenance of 3D structural integrity and elastomeric mechanical behavior are required.

  16. Metal silicide/poly-Si Schottky diodes for uncooled microbolometers

    PubMed Central

    2013-01-01

    Nickel silicide Schottky diodes formed on polycrystalline Si 〈P〉 films are proposed as temperature sensors of monolithic uncooled microbolometer infrared focal plane arrays. The structure and composition of nickel silicide/polycrystalline silicon films synthesized in a low-temperature process are examined by means of transmission electron microscopy. The Ni silicide is identified as a multi-phase compound composed of 20% to 40% of Ni3Si, 30% to 60% of Ni2Si, and 10% to 30% of NiSi with probable minor content of NiSi2 at the silicide/poly-Si interface. Rectification ratios of the Schottky diodes vary from about 100 to about 20 for the temperature increasing from 22℃ to 70℃; they exceed 1,000 at 80 K. A barrier of around 0.95 eV is found to control the photovoltage spectra at room temperature. A set of barriers is observed in photo-electromotive force spectra at 80 K and attributed to the Ni silicide/poly-Si interface. Absolute values of temperature coefficients of voltage and current are found to vary from 0.3%℃ to 0.6%/℃ for forward bias and around 2.5%/℃ for reverse bias of the diodes. PMID:23594606

  17. Lipase-catalyzed enantioselective synthesis of (R,R)-lactide from alkyl lactate to produce PDLA (poly D-lactic acid) and stereocomplex PLA (poly lactic acid).

    PubMed

    Jeon, Byoung Wook; Lee, Jumin; Kim, Hyun Sook; Cho, Dae Haeng; Lee, Hyuk; Chang, Rakwoo; Kim, Yong Hwan

    2013-10-20

    R-lactide, a pivotal monomer for the production of poly (D-lactic acid) (PDLA) or stereocomplex poly (lactic acid) (PLA) was synthesized from alkyl (R)-lactate through a lipase-catalyzed reaction without racemization. From among several types of lipase, only lipase B from Candida antarctica (Novozym 435; CAL-B) was effective in the reaction that synthesized (R,R)-lactide. Enantiopure (R,R)-lactide, which consisted of over 99% enantiomeric excess, was synthesized from methyl (R)-lactate through CAL-B catalysis. Removal of the methanol by-product was critical to obtain a high level of lactide conversion. The (R,R)-lactide yield was 56% in a reaction containing 100 mg of Novozym 435, 10 mM methyl (R)-lactate and 1500 mg of molecular sieve 5A in methyl tert-butyl ether (MTBE). The important monomer (R,R)-lactide that is required for the production of the widely recognized bio-plastic PDLA and the PLA stereocomplex can be obtained using this novel synthetic method.

  18. Water and drug transport in radiation-crosslinked poly(2-methoxyethylacrylate- co-dimethyl acrylamide) and poly(2-methoxyethylacrylate- co-acrylamide) hydrogels

    NASA Astrophysics Data System (ADS)

    Martellini, Flavia; Mei, Lúcia H. I.; Baliño, Jorge L.; Carenza, Mario

    2003-02-01

    Hydrogels of poly( N, N'-dimethylacrylamide- co-2-methoxyethylacrylate) and poly(acrylamide- co-2-methoxyethylacrylate) have been synthesized by radiation polymerization in dimethylformamide solution with trimethylolpropane trimethacrylate as a crosslinker. In this work, some investigations on the in vitro release of gentamicin sulphate, an antibiotic entrapped in the hydrogels, are reported. The kinetics of drug release from hydrogels matrices were examined and the results indicate that the release for the proposed geometry practically occurs in the first 24 h. The fractional cumulative release of the drug from the DMAA/MOEA matrices is linear when plotted against the square root of time, pointing out a Fickian process. On the other hand, AAm/MOEA matrices showed an initial non-Fickian behaviour, probably indicating a comparable rates of Fickian diffusion and polymer relaxation.

  19. Synthesis, characterization and comparison of polyaniline 1D-structure controlled by poly(L-lactide) and poly(D-lactide)

    NASA Astrophysics Data System (ADS)

    Gu, Zhou-Jie; Shen, Qing

    2016-01-01

    1D-structural polyaniline (PANI) was controllably synthesized by utilizing the poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) as controllers. FESEM images showed that the morphology of 1D-structural PANI controlled by PDLA likes a joint obviously unlike PLLA controlled vertebra structure reported previously. To set the ratio of ANI/PLLA (ml/g) at 0.45/0.135, 0.45/0.270 and 0.45/0.540, the formed PANI 1D structure was changed in the cross-section as four round leaves, four non-round leaves and four sharp leaves, respectively. FTIR and XRD analysis indicated that the PLLA and PDLA both were doped in PANI chains while the PLLA was strongly in the electrons delocalization than that of the PDLA due probably to the L-type stronger in crystal polymorphism than that of the D-type.

  20. Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)-block-poly(methyl methacrylate) Block Polymers for Lithography.

    SciTech Connect

    Kennemur, Justin; Yao, Li; Bates, Frank Stephen; Hillmyer, Marc

    2014-01-01

    A series of poly(cyclohexylethylene)-block-poly- (methyl methacrylate) (PCHE PMMA) diblock copolymers with varying molar mass (4.9 kg/mol Mn 30.6 kg/mol) and narrow molar mass distribution were synthesized through a combination of anionic and atom transfer radical polymerization (ATRP) techniques. Heterogeneous catalytic hydrogenation of -(hydroxy)polystyrene (PS-OH) yielded -(hydroxy)poly(cyclohexylethylene) (PCHEOH) with little loss of hydroxyl functionality. PCHE-OH was reacted with -bromoisobutyryl bromide (BiBB) to produce an ATRP macroinitiator used for the polymerization of methyl methacrylate. PCHE PMMA is a glassy, thermally stable material with a large effective segment segment interaction parameter, eff = (144.4 6.2)/T (0.162 0.013), determined by meanfield analysis of order-to-disorder transition temperatures (TODT) measured by dynamic mechanical analysis and differential scanning calorimetry. Ordered lamellar domain pitches (9 D 33 nm) were identified by small-angle X-ray scattering from neat BCPs containing 43 52 vol % PCHE ( f PCHE). Atomic force microscopy was used to show 7.5 nm lamellar features (D = 14.8 nm) which are some of the smallest observed to date. The lowest molar mass sample (Mn = 4.9 kg/mol, f PCHE = 0.46) is characterized by TODT = 173 3 C and sub-5 nm nanodomains, which together with the sacrificial properties of PMMA and the high overall thermal stability place this material at the forefront of high- systems for advanced nanopatterning applications.

  1. Pluronic-poly (acrylic acid)-cysteine/Pluronic L121 mixed micelles improve the oral bioavailability of paclitaxel.

    PubMed

    Zhao, Yanli; Li, Yanli; Ge, Jianjun; Li, Na; Li, Ling-Bing

    2014-11-01

    The aim of the study is to synthesize a thiolated Pluronic copolymer, Pluronic-poly (acrylic acid)-cysteine copolymer, to construct a mixed micelle system with the Pluronic-poly (acrylic acid)-cysteine copolymer and Pluronic L121 (PL121) and to evaluate the potential of these mixed micelles as an oral drug delivery system for paclitaxel. Compared with Pluronic-poly (acrylic acid)-cysteine micelles, drug-loading capacity of Pluronic-poly (acrylic acid)-cysteine/PL121 mixed micelles was increased from 0.4 to 2.87%. In vitro release test indicated that Pluronic-poly (acrylic acid)-cysteine/PL121 mixed micelles exhibited a pH sensitivity. The permeability of drug-loaded micelles in the intestinal tract was studied with an in situ perfusion method in rats. The presence of verapamil and Pluronic both improved the intestinal permeability of paclitaxel, which further certified the inhibition effect of thiolated Pluronic on P-gp. In pharmacokinetic study, the area under the plasma concentration-time curve (AUC0→∞) of paclitaxel-loaded mixed micelles was four times greater than that of the paclitaxel solution (p < 0.05). In general, Pluronic-poly (acrylic acid)-cysteine/PL121 micelles were proven to be a potential oral drug delivery system for paclitaxel.

  2. Electrochemical properties of electrospun poly(5-cyanoindole) submicron-fibrous electrode for zinc/polymer secondary battery

    NASA Astrophysics Data System (ADS)

    Cai, Zhijiang; Guo, Jie; Yang, Haizheng; Xu, Yi

    2015-04-01

    This study aims to develop an aqueous zinc/electrospun poly(5-cyanoindole) fibers secondary battery system. Zn foil and ZnCl2 are used as anode active materials and the electrolytic solution, respectively. Poly(5-cyanoindole) synthesized by chemical oxidation is electrospun into fibers and used as cathode active materials. FTIR and NMR test are carried out to investigate the chemical structure of poly(5-cyanoindole). Surface properties of electrospun poly(5-cyanoindole) fibers are studied by SEM, TEM, and BET. The performance of zinc/electrospun poly(5-cyanoindole) fibers battery system is evaluated in term of electrical conductivity, cyclic voltammogram, electrochemical impedance spectroscopy, discharge capacity and durability test. The cell achieves 2.0 V electromotive force with about 107-61 Ah Kg-1 discharge capacity at 0.2C-10C rate. At 800th cycle, the discharge capacity remains 80-57 Ah Kg-1 at 0.2C-2C rate, which is about 75-63% of the maximum discharge capacity. These results indicate that the cell has very excellent cyclic properties as well as fast charge/discharge properties. Electrospun poly(5-cyanoindole) fibers have been proved to be a better candidate than polyindole powder as cathode material in zinc/polymer battery.

  3. The nuclear poly(A) binding protein of mammals, but not of fission yeast, participates in mRNA polyadenylation.

    PubMed

    Kühn, Uwe; Buschmann, Juliane; Wahle, Elmar

    2017-04-01

    The nuclear poly(A) binding protein (PABPN1) has been suggested, on the basis of biochemical evidence, to play a role in mRNA polyadenylation by strongly increasing the processivity of poly(A) polymerase. While experiments in metazoans have tended to support such a role, the results were not unequivocal, and genetic data show that the S. pombe ortholog of PABPN1, Pab2, is not involved in mRNA polyadenylation. The specific model in which PABPN1 increases the rate of poly(A) tail elongation has never been examined in vivo. Here, we have used 4-thiouridine pulse-labeling to examine the lengths of newly synthesized poly(A) tails in human cells. Knockdown of PABPN1 strongly reduced the synthesis of full-length tails of ∼250 nucleotides, as predicted from biochemical data. We have also purified S. pombe Pab2 and the S. pombe poly(A) polymerase, Pla1, and examined their in vitro activities. Whereas PABPN1 strongly increases the activity of its cognate poly(A) polymerase in vitro, Pab2 was unable to stimulate Pla1 to any significant extent. Thus, in vitro and in vivo data are consistent in supporting a role of PABPN1 but not S. pombe Pab2 in the polyadenylation of mRNA precursors.

  4. Constructing polyamidoamine dendrons from poly(poly(ethylene glycol) monomethacrylate) brushes grafted from planar silicon hydride surfaces for biomedical applications

    NASA Astrophysics Data System (ADS)

    Liu, Xiang; Zheng, Hong-Ning; Yan, Qin; Wang, Cuie; Ma, Yin-Zhou; Tang, Yan-Chun; Xiao, Shou-Jun

    2011-06-01

    A facile approach was established to construct polyamidoamine (PAMAM) dendrons from polymer brushes of poly(poly(ethylene glycol) monomethacrylate) (Si-g-P(PEGMA-OH)) grafted from a planar silicon hydride surface. First the Si-g-P(PEGMA-OH) brushes were grown via surface-initiated atom transfer radical polymerization with robust Si-C links on silicon surfaces. The side-chain hydroxyl groups of Si-g-P(PEGMA-OH) were chlorinated with thionyl chloride and further chlorines were substituted with amino groups of ethylenediamine, giving terminal primary amines. Borrowing the solution synthesis approach, we constructed second and third generations of PAMAM dendrons on-chip by surface-initiated alternative growth of two monomers, methyl acrylate and ethylenediamine. Two applications of silicon-based PAMAM dendrons were shown: the dense amino groups were activated via a cross-linker, N-succinimidyl-6-maleimidylhexanoate, to capture a free-thiol-carrying peptide of oxytocin and the third generation of PAMAM dendrons was used as a platform to on-chip synthesize a three amino acid peptide of Arg-Gly-Asp (RGD). The above conclusions were mainly derived from a home-built multiple transmission-reflection infrared spectroscopy, and complemented by X-ray photoelectron spectroscopy, UV-Vis spectroscopy and matrix-assisted laser desorption/ionization-time of flight-mass spectrometry.

  5. Structural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) copolymer by nuclear magnetic resonance and mass spectrometry.

    PubMed

    Giordanengo, Rémi; Viel, Stéphane; Hidalgo, Manuel; Allard-Breton, Béatrice; Thévand, André; Charles, Laurence

    2009-11-03

    Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have been combined to achieve the complete microstructural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) (PMAA-PMMA) copolymer synthesized by nitroxide-mediated polymerization. Various PMAA-PMMA species could be identified which mainly differ in terms of terminaisons. 1H and 13C NMR experiments revealed the structure of the end-groups as well as the proportion of each co-monomer in the copolymers. These end-group masses were further confirmed from m/z values of doubly charged copolymer anions detected in the single stage mass spectrum. In contrast, copolymer composition derived from MS data was not consistent with NMR results, obviously due to strong mass bias well known to occur during electrospray ionization of these polymeric species. Tandem mass spectrometry could reveal the random nature of the copolymer based on typical dissociation reactions, i.e., water elimination occurred from any two contiguous MAA units while MAA-MMA pairs gave rise to the loss of a methanol molecule. Polymer backbone cleavages were also observed to occur and gave low abundance fragment ions which allowed the structure of the initiating end-group to be confirmed.

  6. In vitro release of clomipramine HCl and buprenorphine HCl from poly adipic anhydride (PAA) and poly trimethylene carbonate (PTMC) blends.

    PubMed

    Dinarvand, Rassoul; Alimorad, Mohammed Massoud; Amanlou, Massoud; Akbari, Hamid

    2005-10-01

    Controlled drug-delivery technology is concerned with the systematic release of a pharmaceutical agent to maintain a therapeutic level of the drug in the body for modulated and/or prolonged periods of time. This may be achieved by incorporating the therapeutic agent into a degradable polymer vehicle, which releases the agent continuously as the matrix erodes. In this study, poly trimethylene carbonate (PTMC), an aliphatic polycarbonate, and poly adipic anhydride (PAA), an aliphatic polyanhydride, were synthesized via melt condensation and ring-opening polymerization of trimethylene carbonate and adipic acid, respectively. The release of clomipramine HCl and buprenorphine HCl from discs prepared with the use of PTMC-PAA blends in phosphate buffer (pH 7.4) are also described. Clomipramine HCl and buprenorphine HCl were both used as hydrophilic drug models. Theoretical treatment of the data with the Peppas model revealed that release of clomipramine HCl (5%) in devices containing 70% PTMC or more followed a Fickian diffusion model. However, the releases of buprenorphine HCl (5%) in the same devices were anomalous. For devices containing 50% and more PAA, surface erosion may play a significant role in the release of both molecules.

  7. A thermosensitive hydrogel based on biodegradable amphiphilic poly(ethylene glycol) polycaprolactone poly(ethylene glycol) block copolymers

    NASA Astrophysics Data System (ADS)

    Gong, Chang Yang; Qian, Zhi Yong; Liu, Cai Bing; Juan Huang, Mei; Gu, Ying Chun; Wen, Yan Jun; Kan, Bing; Wang, Ke; Dai, Mei; Li, Xing Yi; Gou, Ma Ling; Tu, Ming Jing; Wei, Yu Quan

    2007-06-01

    A series of low molecular weight poly(ethylene glycol)-polycaprolactone-poly(ethylene glycol) (PEG-PCL-PEG) biodegradable block copolymers were successfully synthesized using isophorone diisocyanate (IPDI) as the coupling agent, and were characterized using 1H NMR and Fourier transform infrared spectroscopy. The aqueous solutions of the PEG-PCL-PEG copolymers displayed a special thermosensitive gel-sol transition when the concentration was above the corresponding critical gel concentration. Gel-sol phase diagrams were recorded using the test-tube-inversion method; they depended on the hydrophilic/hydrophobic balance in the macromolecular structure, as well as some other factors, including the heating history, volume, and the ageing time of the copolymer aqueous solutions and dissolution temperature of the copolymers. As a result, the gel-sol transition temperature range could be altered, which might be very useful for application in injectable drug delivery systems. This work was financially supported by the Chinese Key Basic Research Program (2004CB518800 and 2004CB518807), and the Sichuan Key Project of Science and Technology (06(05SG022-021-02)).

  8. Actuator based on sulfonated comb copolymer of poly (ethylene-co-vinyl alcohol) grafted by poly (ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Gong, Guifen; Li, Lei; Zhang, Yujun

    2007-07-01

    Comb copolymer consisting of poly (ethylene-co-vinyl alcohol) (EVAL) as backbone and poly (ethylene glycol) (PEG) as side chains (EVAL-g-PEG) has been synthesized, then it was sulfonated by 1,3-propane sultone to get the final ionomer (EVAL-g-SPEG), and ionic polymer-metal composite (IPMC) based on EVAL-g-SPEG was prepared through electroless deposition of platinum onto the surfaces of EVAL-g-SPEG membrane. The graft copolymers were characterized with respect to molecular weight using gel permeation chromatography (GPC) and composition using 1H-NMR. The results showed that the No. of PEG graft of the side chains is n=1, 2 and others. Thermal properties were examined by DSC and TG. The melt temperature (T m) and glass transition temperature (T g) of the comb copolymer increase with the increasing length and the number of the side chains. Moreover, the deformation performance of IPMC material was tested and its results show that the starting response voltage of IPMC actuator decreases with the increasing IEC value. On the other hand, the starting response voltage increases with the decreased side chain length. The IPMC with n=2 side chain length of PEG has the maximum tip displacement, and the maximum tip displacement of IPMC membrane generally decreases with the side chain length of EVAL-g-SPEG. This feature may be the reflection of two opposite effects, namely the decreasing ion densities and increasing water sorption of the membrane.

  9. Preparation and solution behavior of a thermoresponsive diblock copolymer of poly(ethyl glycidyl ether) and poly(ethylene oxide).

    PubMed

    Ogura, Michihiro; Tokuda, Hiroyuki; Imabayashi, Shin-ichiro; Watanabe, Masayoshi

    2007-08-28

    A thermoresponsive diblock copolymer, poly(ethyl glycidyl ether)-block-poly(ethylene oxide) (PEGE-b-PEO), is synthesized by successive anionic ring-opening polymerization of ethyl glycidyl ether and ethylene oxide using 2-phenoxyethanol as a starting material, and its solution behavior is elucidated in water. In a dilute 1 wt % solution, the temperature-dependent alteration in the polymer hydrodynamic radius (RH) is measured in the temperature range between 5 and 45 degrees C by pulse-gradient spin-echo NMR and dynamic light scattering. The RH value increased with temperature in two steps, where the first step at 15 degrees C corresponds to the core-shell micelle formation and the second step at 40 degrees C corresponds to the aggregation of the core-shell micelles. The formation of the core-shell micelles is supported by the solubilization of a dye (1,6-diphenyl-1,3,5-hexatriene) in the hydrophobic core, which is recognized for a copolymer solution in the temperature range between 20 and 40 degrees C. In this temperature range, the core-shell micelles and the unimers coexist and the fraction of the former gradually increases with increasing temperature, suggesting equilibrium between the micelles and the unimers. In the concentrated regime (40 wt % solution), the solution forms a gel and the small-angle X-ray scattering measurements reveal the successive formation of hexagonal and lamellar liquid crystal phases with increasing temperature.

  10. Poly(ester urea)-Based Adhesives: Improved Deployment and Adhesion by Incorporation of Poly(propylene glycol) Segments.

    PubMed

    Zhou, Jinjun; Bhagat, Vrushali; Becker, Matthew L

    2016-12-14

    The adhesive nature of mussels arises from the catechol moiety in the 3,4-dihydroxyphenylalanine (DOPA) amino acid, one of the many proteins that contribute to the unique adhesion properties of mussels. Inspired by these properties, many biomimetic adhesives have been developed over the past few years in an attempt to replace adhesives such as fibrin, cyanoacrylate, and epoxy glues. In the present work, we synthesized ethanol soluble but water insoluble catechol functionalized poly(ester urea) random copolymers that help facilitate delivery and adhesion in wet environments. Poly(propylene glycol) units incorporated into the polymer backbone impart ethanol solubility to these polymers, making them clinically relevant. A catechol to cross-linker ratio of 10:1 with a curing time of 4 h exceeded the performance of commercial fibrin glue (4.8 ± 1.4 kPa) with adhesion strength of 10.6 ± 2.1 kPa. These adhesion strengths are significant with the consideration that the adhesion studies were performed under wet conditions.

  11. Hyperbranched poly(glycidol)/poly(ethylene oxide) crosslinked hydrogel for tissue engineering scaffold using e-beams.

    PubMed

    Haryanto; Singh, Deepti; Huh, Pil Ho; Kim, Seong Cheol

    2016-01-01

    A microporous hydrogel scaffold was developed from hyperbranched poly(glycidol) (HPG) and poly(ethylene oxide) (PEO) using electron beam (e-beam) induced cross-linking for tissue engineering applications. In this study, HPG was synthesized from glycidol using trimethylol propane as a core initiator and cross-linked hydrogels were made using 0, 10, 20, and 30% HPG with respect to PEO. The effects of %-HPG on the swelling ratio, cross-linking density, mechanical properties, morphology, degradation, and cytotoxicity of the hydrogel scaffolds were then investigated. Increasing the HPG content increased the pore size of the hydrogel scaffold, as well as the porosity, elongation at break, degree of degradation and swelling ratio. In contrast, the presence of HPG decreased the cross-linking density of the hydrogel. There was no significant difference in compressive modulus and tensile strength of all compositions. The pore size of hydrogel scaffolds could be easily tailored by controlling the content of HPG in the polymer blend. Evaluation of the cytotoxicity demonstrated that HPG/PEO hydrogel scaffold has potential for use as a matrix for cellular attachment and proliferation. These results indicate that cross-linked HPG/PEO hydrogel can function as a potential material for tissue engineering scaffolds. Moreover, a facile method to prepare hydrogel microporous scaffolds for tissue engineering by e-beam irradiation was developed.

  12. Thermal Conductivity Measurement of Synthesized Mantle Minerals

    NASA Astrophysics Data System (ADS)

    Asimow, P. D.; Luo, S.; Mosenfelder, J. L.; Liu, W.; Staneff, G. D.; Ahrens, T. J.; Chen, G.

    2002-12-01

    Direct thermal conductivity (k) measurement of mantle minerals is crucial to constrain the thermal profile of the Earth as well as geodynamic studies of the mantle (e.g., to determine the Rayleigh number). We have embarked on systematic multi-anvil syntheses of dense polycrystalline specimens of mantle phases of adequate size and zero porosity for precise thermal conductivity measurements by the 3ω method (\\textit{Cahill and Pohl, Phys. Rev. B, 1987}) under elevated temperatures (T). Coesite and stishovite (see \\textit{Luo et al., GRL, 2002}) as well as majorite and wadsleyite have been synthesized; ringwoodite and perovskite are scheduled. Preliminary thermal conductivity measurements at ambient pressure on coesite (120 - 300 K, 9.53 Wm-1K-1 at 300 K) are consistent with prior room temperature data (\\textit{Yukutake & Shimada, PEPI, 1978}), while our stishovite data at 300 K appear to be low (1.96 Wm-1K-1). Efforts are being made to extend the measurement to higher temperatures (e.g., above Debye temperature Θ D), thus allowing determination of k(T) relationship (say, k~ T-n); success will depend on the decomposition kinetics of these metastable phases. The pressure dependence of k of these synthesized samples can also be measured (\\textit{e.g., Osako et al., HPMPS-6, 2002; Xu et al., EOS, 2001}). Recent thermal conductivity measurement on LiF and Al2O_3 from shock wave loading (\\textit{Holland & Ahrens, 1998}) is consistent with the modeling on MgO and Al2O_3 (\\textit{Manga & Jeanloz, JGR, 1997}) with classical theories. Thus, k values at modest pressures and T (say, above Θ D) would allow extrapolation of k to appropriate mantle conditions.

  13. Co-axial capillaries microfluidic device for synthesizing size- and morphology-controlled polymer core-polymer shell particles.

    PubMed

    Chang, Zhenqi; Serra, Christophe A; Bouquey, Michel; Prat, Laurent; Hadziioannou, Georges

    2009-10-21

    An easy assembling-disassembling co-axial capillaries microfluidic device was built up for the production of double droplets. Uniform polymer core-polymer shell particles were synthesized by polymerizing the two immiscible monomer phases composing the double droplet. Thus poly(acrylamide) core-poly(tri(propylene glycol) diacrylate) shell particles with controlled core diameter and shell thickness were simply obtained by adjusting operating parameters. An empirical law was extracted from experiments to predict core and shell sizes. Additionally uniform and predictable non-spherical polymer objects were also prepared without adding shape-formation procedures in the experimental device. An empirical equation for describing the lengths of rod-like polymer particles is also presented.

  14. Evaluating and synthesizing broadcasting satellite systems

    NASA Technical Reports Server (NTRS)

    Knouse, G. H.

    1974-01-01

    A system model and a computer program have been developed which are representative of broadcasting satellite systems employing several types of receiving terminals. The program provides a user-oriented tool for (1) evaluating performance/cost tradeoffs, (2) synthesizing minimum cost systems for a given set of system requirements, and (3) performing sensitivity analyses to identify critical user requirements, system parameters, and technology. The types of systems which can be evaluated are described, and the capabilities of the program are illustrated by means of several examples.

  15. Syntheses of Synthetic Hydrocarbons Via Alpha Olefins.

    DTIC Science & Technology

    1981-10-01

    Chem. Educ., 42, 502 (1965). 4. A. Priola, C. Corna , and S. Cesca, Macromolecules, 13, 1110 (1980). 5. R. F . Brown, Organic Chemistry, Wadsworth...AD-A110 380 GULF RESEARCH AND DEVELOPENT Co PITTSBURGH PA F /G T/A 1 SYNTHESES OF SYNTHETIC HYDROCARBONS VIA ALPHA OLEFINS.(U) OCT 81 B L CUPPLES, A...FOR THE COMMANDER F . D. CHERRY, Chief Nonmetallic Materials Division "If your address has changed, if you wish to be removed from our mailing list

  16. Poly(A)-Driven and Poly(A)-Assisted Termination: Two Different Modes of Poly(A)-Dependent Transcription Termination

    PubMed Central

    Yeung, George; Choi, Louis M.; Chao, Lily C.; Park, Noh Jin; Liu, Dahai; Jamil, Amer; Martinson, Harold G.

    1998-01-01

    We mapped the elements that mediate termination of transcription downstream of the chicken βH- and βA-globin gene poly(A) sites. We found no unique element and no segment of 3′-flanking DNA to be significantly more effective than any other. When we replaced the native 3′-flanking DNA with bacterial DNA, it too supported transcription termination. Termination in the bacterial DNA depended on a functional poly(A) signal, which apparently compelled termination to occur in the downstream DNA with little regard for its sequence. We also studied premature termination by poorly processive polymerases close to the promoter. The rate of premature termination varied for different DNA sequences. However, the efficiencies of poly(A)-driven termination and promoter-proximal premature termination varied similarly on different DNAs, suggesting that poly(A)-driven termination functions by returning the transcription complex to a form which resembles a prior state of low processivity. The poly(A)-driven termination described here differs dramatically from the poly(A)-assisted termination previously described for the simian virus 40 (SV40) early transcription unit. In the SV40 early transcription unit, essentially no termination occurs downstream of the poly(A) site unless a special termination element is present. The difference between the βH-globin and SV40 modes of termination is governed by sequences in the upstream DNA. For maximum efficiency, the βH-globin poly(A) signal required the assistance of upstream enhancing sequences. Moreover, the SV40 early poly(A) signal also drove termination in βH-globin style when it was placed in a βH-globin sequence context. These studies were facilitated by a rapid, improved method of run-on transcription analysis, based on the use of a vector containing two G-free cassettes. PMID:9418875

  17. Biogenic synthesized nanoparticles and their applications

    NASA Astrophysics Data System (ADS)

    Singh, Abhijeet; Sharma, Madan Mohan

    2016-05-01

    In the present scenario, there are growing concerns over the potential impacts of bioengineered nanoparticles in the health sector. However, our understanding of how bioengineered nanoparticles may affect organisms within natural ecosystems, lags far behind our rapidly increasing ability to engineer novel nanoparticles. To date, research on the biological impacts of bioengineered nanoparticles has primarily consisted of controlled lab studies of model organisms with single species in culture media. Here, we described a cost effective and environment friendly technique for green synthesis of silver nanoparticles. Silver nanoparticles were successfully synthesized from 1 mM AgNO3 via a green synthesis process using leaf extract as reducing as well as capping agent. Nanoparticles were characterized with the help of UV-vis absorption spectroscopy, X-ray diffraction and TEM analysis which revealed the size of nanoparticles of 30-40 nm size. Further the nanoparticles synthesized by green route are found highly toxic against pathogenic bacteria and plant pathogenic fungi viz. Escherichia coli, Pseudomonas syringae and Sclerotiniasclerotiorum. The most important outcome of this work will be the development of value-added products and protection of human health from pathogens viz., bacteria, virus, fungi etc.

  18. Synthesizing new, high-temperature superconductors

    NASA Astrophysics Data System (ADS)

    Weaver, Claire; Aronson, Meigan

    2015-03-01

    Currently, there is no accepted theory behind type-II, high-temperature superconductors, but there is a distinct relationship between anti-ferromagnetism and superconductivity. Our research focuses on synthesizing new superconducting materials by observing the link between atomic structure and magnetic moments of anti-ferromagnetic compounds and attempting to reproduce the molecular physics of these known materials in new compounds. Consider the square-planar arrangement of the transition metal Fe in the Fe-pnictide superconductors of the ZrCuSiAs ``11 11'' and the ThCr2Si2 ``122'' structure types. We believe that the physics behind this superconductor, where Fe has d6 valence electrons, contributes to the superconducting state, not the presence of Fe itself. For this reason, we are synthesizing materials containing neighboring transition metals, like Mn and Co, combined with other elements in similar crystal lattice arrangements, having ionization properties that hopefully impose d6 valence electrons on the transition metals. This project was supported in part by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory Internships Program (SULI).

  19. Novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer micelles loading curcumin: preparation, characterization, and in vitro evaluation.

    PubMed

    Lv, Li; Shen, Yuanyuan; Li, Min; Xu, Xiaofen; Li, Mingna; Guo, Shengrong; Huang, Shengtang

    2013-01-01

    A novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer (4-arm PEG-b-PAE) was synthesized by esterization of 4-arm poly(ethylene glycol) and poly(anhydride-esters) which was obtained by melt polycondensation of α -, ω -acetic anhydride terminated poly(L-lactic acid). The obtained 4-arm PEG-b-PAE was characterized by (1)H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL). The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

  20. Electrochemical preparation of poly(methylene blue)/graphene nanocomposite thin films

    SciTech Connect

    Erçarıkcı, Elif; Dağcı, Kader; Topçu, Ezgi; Alanyalıoğlu, Murat

    2014-07-01

    Highlights: • Poly(MB)/graphene thin films are prepared by a simple electrochemical approach. • Graphene layers in the film show a broad band in visible region of absorbance spectra. • Morphology of composite films indicates both disordered and ordered regions. • XRD reveals that nanocomposite films include rGO layers after electropolymerization process. • Chemically prepared graphene is better than electrochemically prepared graphene for electrooxidation of nitrite. - Abstract: Poly(methylene blue)/graphene nanocomposite thin films were prepared by electropolymerization of methylene blue in the presence of graphene which have been synthesized by two different methods of a chemical oxidation process and an electrochemical approach. Synthesized nanocomposite thin films were characterized by using cyclic voltammetry, UV–vis. absorption spectroscopy, powder X-ray diffraction, and scanning tunneling microscopy techniques. Electrocatalytical properties of prepared poly(methylene blue)/graphene nanocomposite films were compared toward electrochemical oxidation of nitrite. Under optimized conditions, electrocatalytical effect of nanocomposite films of chemically prepared graphene through electrochemical oxidation of nitrite was better than that of electrochemically prepared graphene.

  1. Engineering of poly(ethylene glycol) chain-tethered surfaces to obtain high-performance bionanoparticles

    PubMed Central

    Nagasaki, Yukio

    2010-01-01

    A poly(ethylene glycol)-b-poly[2-(N,N-dimethylamino)ethyl methacrylate] block copolymer possessing a reactive acetal group at the end of the poly(ethylene glycol) (PEG) chain, that is, acetal-PEG-b-PAMA, was synthesized by a proprietary polymerization technique. Gold nanoparticles (GNPs) were prepared using the thus-synthesized acetal-PEG-b-PAMA block copolymer. The PEG-b-PAMA not only acted as a reducing agent of aurate ions but also attached to the nanoparticle surface. The GNPs obtained had controlled sizes and narrow size distributions. They also showed high dispersion stability owing to the presence of PEG tethering chains on the surface. The same strategy should also be applicable to the fabrication of semiconductor quantum dots and inorganic porous nanoparticles. The preparation of nanoparticles in situ, i.e. in the presence of acetal-PEG-b-PAMA, gave the most densely packed polymer layer on the nanoparticle surface; this was not observed when coating preformed nanoparticles. PEG/polyamine block copolymer was more functional on the metal surface than PEG/polyamine graft copolymer, as confirmed by angle-dependent x-ray photoelectron spectroscopy. We successfully solubilized the C60 fullerene into aqueous media using acetal-PEG-b-PAMA. A C60/acetal-PEG-b-PAMA complex with a size below 5 nm was obtained by dialysis. The preparation and characterization of these materials are described in this review. PMID:27877362

  2. Poly(arylene ether ketone) carrying hyperquaternized pendants: Preparation, stability and conductivity

    NASA Astrophysics Data System (ADS)

    Shen, Kunzhi; Zhang, Zhenpeng; Zhang, Haibo; Pang, Jinhui; Jiang, Zhenhua

    2015-08-01

    A new strategy to synthesize comb-shaped poly(arylene ether ketone) ionomers with hyperquaternized pendants was detailed in this work. Poly(arylene ether ketone) with electron-rich phenyl rings on the side chain was copolymerized. These electron-rich phenyl rings which could be chloromethylated and serve as precursors to cationic sites, are introduced during monomer synthesis. After chloromethylation and quaternization on the side chain, these resulting anion exchange membranes exhibit high conductivities and good dimensional stability, which benefit from the side chain type structure. The highest chloride conductivity of 0.047 S cm-1 was observed in PAEK-QTPM-30 (IEC = 1.58 mmol g-1) and swelling ratio is 31.7% at 80 °C. The structural properties of the synthesized poly(arylene ether ketone)s were investigated by 1H NMR spectroscopy. The anion exchange membranes showed excellent thermal stability up to 200 °C under nitrogen and good chemical stability for high conductivity after treating in alkaline condition up to 30 days. These membranes were studied by IEC, water uptake, dimensional stability. The nano-phase separation from ionic aggregation was confirmed by SAXS. This work implies a viable strategy to improve the performance of anion exchange membranes.

  3. Poly(PS-b-DMA) Micelles for Reactive Oxygen Species Triggered Drug Release

    PubMed Central

    Gupta, Mukesh K.; Meyer, Travis A.; Nelson, Christopher E.; Duvall, Craig L.

    2013-01-01

    A new micelle drug carrier that consists of a diblock polymer of propylene sulfide (PS) and N,N-dimethylacrylamide (poly(PS74−b-DMA310)) has been synthesized and characterized for site-specific release of hydrophobic drugs to sites of inflammation. Propylene sulfide was first polymerized using a thioacyl group transfer (TAGT) method with the RAFT chain transfer agent (CTA) 4-cyano-4-(ethylsulfanylthiocarbonylsulfanyl) pentanoic acid (CEP), and the resultant poly(PS74−CEP) macro-CTA was used to polymerize a second polymer block of DMA using reversible addition-fragmentation chain transfer (RAFT). The formation of the poly(PS74−b-DMA310) diblock polymer was confirmed by 1H NMR spectra and gel permeation chromatography (GPC). poly(PS74−b-DMA310) formed 100 nm micelles in aqueous media as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Micelles loaded with the model drugs Nile red and DiO were used to demonstrate the ROS-dependent drug release mechanism of these micelles following treatment with hydrogen peroxide (H2O2), 3-morpholinosydnonimine (SIN-1), and peroxynitrite. These oxidants were found to oxidize the micelle PPS core, making it more hydrophilic and triggering micelle disassembly and cargo release. Delivery of poly(PS74−b-DMA310) micelles dual-loaded with the Förster Resonance Energy Transfer (FRET) fluorophore pair DiI and DiO was used to prove that endogenous oxidants generated by lipopolysaccharide (LPS)-treated RAW 264.7 macrophages significantly increased release of nanocarrier contents relative to macrophages that were not activated. In vitro studies also demonstrated that the poly(PS74−b-DMA310) micelles were cytocompatible across a broad range of concentrations. These combined data suggest that the poly(PS74−b-DMA310) micelles synthesized using a combination of TAGT and RAFT have significant potential for site-specific drug delivery to tissues with high levels of oxidative stress. PMID:22889714

  4. Complete genome sequence of Bacillus amyloliquefaciens LL3, which exhibits glutamic acid-independent production of poly-γ-glutamic acid.

    PubMed

    Geng, Weitao; Cao, Mingfeng; Song, Cunjiang; Xie, Hui; Liu, Li; Yang, Chao; Feng, Jun; Zhang, Wei; Jin, Yinghong; Du, Yang; Wang, Shufang

    2011-07-01

    Bacillus amyloliquefaciens is one of most prevalent Gram-positive aerobic spore-forming bacteria with the ability to synthesize polysaccharides and polypeptides. Here, we report the complete genome sequence of B. amyloliquefaciens LL3, which was isolated from fermented food and presents the glutamic acid-independent production of poly-γ-glutamic acid.

  5. Physicochemical and morphological properties of poly (acrylamide) and methylcellulose hydrogels: rffects of monomer, crosslinker and polysaccharide compositions, polymer engineering and science

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper describes the physicochemical (mechanical and swelling) and morphological characterization of poly (acrylamide) and methylcellulose (PAAm-MC) hydrogels synthesized with different formulations by the free radical polymerization method. The structure-property relationship of the PAAm-MC hyd...

  6. Synthesis and photocatalytic activity of poly(triazine imide).

    PubMed

    Ham, Yeilin; Maeda, Kazuhiko; Cha, Dongkyu; Takanabe, Kazuhiro; Domen, Kazunari

    2013-01-01

    Poly(triazine imide) was synthesized with incorporation of Li(+) and Cl(-) ions (PTI/Li(+)Cl(-)) to form a carbon nitride derivative. The synthesis of this material by the temperature-induced condensation of dicyandiamide was examined both in a eutectic mixture of LiCl-KCl and without KCl. On the basis of X-ray diffraction measurements of the synthesized materials, we suggest that a stoichiometric amount of LiCl is necessary to obtain the PTI/Li(+)Cl(-) phase without requiring the presence of KCl at 873 K. PTI/Li(+)Cl(-) with modification by either Pt or CoO(x) as cocatalyst photocatalytically produced H(2) or O(2), respectively, from water. The production of H(2) or O(2) from water indicates that the valence and conduction bands of PTI/Li(+)Cl(-) were properly located to achieve overall water splitting. The treatment of PTI/Li(+)Cl(-) with [Pt(NH(3))(4)](2+) cations enabled the deposition of Pt through ion exchange, demonstrating photocatalytic activity for H(2) evolution, while treatment with [PtCl(6)](2-) anions resulted in no Pt deposition. This was most likely because of the preferential exchange between Li(+) ions and [Pt(NH(3))(4)](2+) cations.

  7. Synthesis and characterization of poly(methoxyl ethylene glycol-caprolactone-co-methacrylic acid-co-poly(ethylene glycol) methyl ether methacrylate) pH-sensitive hydrogel for delivery of dexamethasone.

    PubMed

    Wang, Ke; Xu, Xu; Wang, YuJun; Yan, Xi; Guo, Gang; Huang, MeiJuan; Luo, Feng; Zhao, Xia; Wei, YuQuan; Qian, ZhiYong

    2010-04-15

    In this work, a novel pH-sensitive hydrogels based on macromonomer of methoxyl poly(ethylene glycol)-poly(caprolactone)-acryloyl chloride (MPEG-PCL-AC, PCE-AC), poly(ethylene glycol) methyl ether methacrylate (MPEGMA), and methacrylic acid (MAA) were successfully synthesized by heat-initiated free radical polymerization method. The obtained macromonomers and hydrogels were characterized by (1)H NMR and FT-IR, respectively. Morphology study, swelling behavior, in vitro drug release behavior, acute oral toxicity of hydrogels, and cytotoxicity of PCE-AC macromonomer were also investigated in this paper. Finally, the hydrogels demonstrated that the sharp change in different pH value, thus believing to be promising the suitability of the candidate for oral drug-delivery systems.

  8. Algorithm That Synthesizes Other Algorithms for Hashing

    NASA Technical Reports Server (NTRS)

    James, Mark

    2010-01-01

    An algorithm that includes a collection of several subalgorithms has been devised as a means of synthesizing still other algorithms (which could include computer code) that utilize hashing to determine whether an element (typically, a number or other datum) is a member of a set (typically, a list of numbers). Each subalgorithm synthesizes an algorithm (e.g., a block of code) that maps a static set of key hashes to a somewhat linear monotonically increasing sequence of integers. The goal in formulating this mapping is to cause the length of the sequence thus generated to be as close as practicable to the original length of the set and thus to minimize gaps between the elements. The advantage of the approach embodied in this algorithm is that it completely avoids the traditional approach of hash-key look-ups that involve either secondary hash generation and look-up or further searching of a hash table for a desired key in the event of collisions. This algorithm guarantees that it will never be necessary to perform a search or to generate a secondary key in order to determine whether an element is a member of a set. This algorithm further guarantees that any algorithm that it synthesizes can be executed in constant time. To enforce these guarantees, the subalgorithms are formulated to employ a set of techniques, each of which works very effectively covering a certain class of hash-key values. These subalgorithms are of two types, summarized as follows: Given a list of numbers, try to find one or more solutions in which, if each number is shifted to the right by a constant number of bits and then masked with a rotating mask that isolates a set of bits, a unique number is thereby generated. In a variant of the foregoing procedure, omit the masking. Try various combinations of shifting, masking, and/or offsets until the solutions are found. From the set of solutions, select the one that provides the greatest compression for the representation and is executable in the

  9. Degradability in vitro of polyurethanes based on synthetic atactic poly[(R,S)-3-hydroxybutyrate].

    PubMed

    Brzeska, J; Janeczek, H; Janik, H; Kowalczuk, M; Rutkowska, M

    2015-01-01

    The aim of the present study was to determine the degradability of aliphatic polyurethanes, based on a different amount of synthetic, atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB), in hydrolytic (phosphate buffer) and oxidative (H2O2/CoCl2) solutions. The soft segments were built with atactic poly[(R,S)-3-hydroxybutyrate] and polycaprolactone or polyoxytetramethylenediols, whereas hard segments were the reaction product of 4,4'-methylenedicyclohexyl diisocyanate and 1,4-butanediol.The selected properties - density and morphology of polymer surfaces - which could influence the sensitivity of polymers to degradation processes - were analyzed.The analysis of molecular mass (GPC), thermal properties (DSC) and the sample weight changes were undertaken to estimate the degree of degradability of polymer samples after incubation in environments studied.Investigated polyurethanes were amorphous with the very low amount of crystalline phases of hard segments.The polyurethane synthesized with a poly[(R,S)-3-hydroxybutyrate] and polyoxytetramethylenediol at a molar ratio of NCO:OH=3.7:1 (prepolymer step) appeared as the most sensitive for both degradative solutions. Its weight and molecular mass losses were the highest in comparison to other investigated polyurethanes.It could be expected that playing with the amount of poly[(R,S)-3-hydroxybutyrate] in polyurethane synthesis the rate of polyurethane degradation after immersion in living body would be modeled.

  10. Preparation of well-defined poly(ether-ester) macromers: photogelation and biodegradability.

    PubMed

    Nakayama, Yasuhide; Okuda, Kanna; Takamizawa, Keiichi; Nakayama, Atsuyoshi

    2011-04-01

    Two series of poly(ether-ester)-based bis-functional macromers terminated with acrylate groups and a well-defined number of ester bonds were synthesized. One series had a chain of 1, 3 or 5 ester bonds at both ends of the central poly(ethylene glycol) block (molecular weight, about 1000), while the other had an alternating structure of oligo(ethylene glycol) each of them linked to two ester bonds, in which 6 or 10 ester bonds were incorporated equally in the macromer molecules and the total molecular weight was adjusted by about 1000. Irradiation of all poly(ether-ester) macromers mixed with camphorquinone resulted in the formation of gels. Gel yield increased and hydrophilic properties of the gels produced decreased with irradiation time. The elastic modulus of the gels decreased with the number of ester bonds. Upon incubation in a PBS solution (pH 8.04), all gels were gradually degraded with time. At 3 weeks of incubation, the degradation ratio increased linearly with the number of ester bonds per unit of molecular weight of the macromers. The order of in vivo degradation rates determined from weight loss was similar to that of the in vitro study. Thus, these poly(ether-ester) macromers may be useful for biodegradable biomaterials or tissue engineering scaffolds.

  11. Electrochemical Interrogation of G3-Poly(propylene thiophenoimine) Dendritic Star Polymer in Phenanthrene Sensing

    PubMed Central

    Makelane, Hlamulo R.; Tovide, Oluwakemi; Sunday, Christopher E.; Waryo, Tesfaye; Iwuoha, Emmanuel I.

    2015-01-01

    A novel dendritic star-copolymer, generation 3 poly(propylene thiophenoimine) (G3PPT)-co-poly(3-hexylthiophene) (P3HT) star co-polymer on gold electrode (i.e., Au|G3PPT-co-P3HT) was used as a sensor system for the determination of phenanthrene (PHE). The G3PPT-co-P3HT star co-polymer was synthesized via in situ electrochemical co-polymerization of generation 3 poly (propylene thiophenoimine) and poly (3-hexylthiophene) on gold electrode. 1HNMR spectroscopy was used to determine the regioregularity of the polymer composites, whereas Fourier transform infrared spectroscopy and scanning electron microscopy were used to study their structural and morphological properties. Au|G3PPT-co-P3HT in the absence of PHE, exhibited reversible electrochemistry attributable to the oligo (thiophene) ‘pendants’ of the dendrimer. PHE produced an increase in the voltammetric signals (anodic currents) due to its oxidation on the dendritic material to produce catalytic current, thereby suggesting the suitability of the Au|G3PPT-co-P3HT electrode as a PHE sensor. The electrocatalysis of PHE was made possible by the rigid and planar oligo-P3HT species (formed upon the oxidation of the oligo (thiophene) pendants of the star-copolymer), which allowed the efficient capture (binding) and detection (electrocatalytic oxidation) of PHE molecules. PMID:26404296

  12. Synthesis and fabrication of a degradable poly(N-isopropyl acrylamide) scaffold for tissue engineering applications

    PubMed Central

    Galperin, Anna; Long, Thomas J.; Garty, Shai; Ratner, Buddy D.

    2013-01-01

    Biodegradable poly(N-isopropyl acrylamide) (poly-NIPAM) hydrogels with controlled molecular weight of the parent polymer and its degradation products were synthesized by atom transfer radical polymerization in the presence of a polycaprolactone-based di-chlorinated macroinitiator and polycaprolactone dimethacrylate. The phase transition temperature, swelling, hydrolytic degradability, and mechanical properties at 25 and 37°C were explored. A cytocompatibility study showed good NIH3T3 cell response over 5 days culture on the surface of the hydrogels, demonstrated by a consistent increase in cell proliferation detected by an Alamar Blue assay. MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazo-lium bromide] results suggested that the hydrogels and their degradation products in the concentration range of 1–25 mg/ mL were not cytotoxic to NIH3T3 cells. A sphere-templating technique was utilized to fabricate biodegradable polyNIPAM scaffolds with monodisperse, pore size. Scaffolds with pore diameter of 48 ± 6 μm were loaded with A-10 smooth muscle cells and then warmed to 37°C entrapping cells in pores approximately 40 μm in diameter, a size we have found to be optimal for angiogenesis and biointegration. Due to their degradable nature, tunable molecular weight, highly interconnected morphology, thermally controlled monodisperse pore size, and temperature-induced volume expansion–contraction, the polyNIPAM-based scaffolds developed in this work will be valuable in tissue engineering. PMID:22961921

  13. Poly(ethylene glycol) grafted polylactide based copolymers for the preparation of PLA-based nanocarriers and hybrid hydrogels.

    PubMed

    Riva, Raphaël; Schmeits, Stéphanie; Croisier, Florence; Lecomte, Philippe; Jérôme, Christine

    2015-01-01

    In previous works, poly(D,L-lactide-co-ɛCL-poly(ethylene glycol) (poly(D,L-La-co-αPEGɛCL) amphiphilic graft-copolymers were successfully synthesized according to a copper azide-alkyne cycloaddition (CuAAC) strategy. This paper aims at reporting on the behavior of this amphiphilic copolymer in water, which was not studied in the previous paper. Moreover, the ability of the copolymer to stabilize a PLA nanoparticles aqueous suspension is presented. For this purpose, dynamic light scattering (DLS) and transmission electron microscopy (TEM) are proposed to characterize the nanoparticles in solution. Otherwise, the strategy developed for the synthesis of the amphiphilic copolymers was adapted and extended to the synthesis of PLA-based degradable hydrogel, potentially applicable as drug-loaded degradable polymer implant.

  14. Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles.

    PubMed

    Fortunati, E; Rinaldi, S; Peltzer, M; Bloise, N; Visai, L; Armentano, I; Jiménez, A; Latterini, L; Kenny, J M

    2014-01-30

    Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

  15. Poly(meth)acrylate-based coatings.

    PubMed

    Nollenberger, Kathrin; Albers, Jessica

    2013-12-05

    Poly(meth)acrylate coatings for pharmaceutical applications were introduced in 1955 with the launch of EUDRAGIT(®) L and EUDRAGIT(®) S, two types of anionic polymers. Since then, by introducing various monomers into their polymer chains and thus altering their properties, diverse forms with specific characteristics have become available. Today, poly(meth)acrylates function in different parts of the gastrointestinal tract and/or release the drug in a time-controlled manner. This article reviews the properties of various poly(meth)acrylates and discusses formulation issues as well as application possibilities.

  16. Method and apparatus for synthesizing hydrocarbons

    DOEpatents

    Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

    1985-04-16

    A method and apparatus for synthesizing a mixture of aliphatic alcohols having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further optionally includes Na ions present as substitutional cations in an amount of about 5 to 10 atom %. At a temperature of about 570 to 630/sup 0/K, and at pressures of about 20 to 50 atm, methanol and isobutanol are the predominant products and are produced in amounts of about 90 wt % of the total hydrocarbon mixture. 6 figs.

  17. Synthesizing Biomolecule-based Boolean Logic Gates

    PubMed Central

    Miyamoto, Takafumi; Razavi, Shiva; DeRose, Robert; Inoue, Takanari

    2012-01-01

    One fascinating recent avenue of study in the field of synthetic biology is the creation of biomolecule-based computers. The main components of a computing device consist of an arithmetic logic unit, the control unit, memory, and the input and output devices. Boolean logic gates are at the core of the operational machinery of these parts, hence to make biocomputers a reality, biomolecular logic gates become a necessity. Indeed, with the advent of more sophisticated biological tools, both nucleic acid- and protein-based logic systems have been generated. These devices function in the context of either test tubes or living cells and yield highly specific outputs given a set of inputs. In this review, we discuss various types of biomolecular logic gates that have been synthesized, with particular emphasis on recent developments that promise increased complexity of logic gate circuitry, improved computational speed, and potential clinical applications. PMID:23526588

  18. Intermetallic Nanocrystals: Syntheses and Catalytic Applications.

    PubMed

    Yan, Yucong; Du, Jingshan S; Gilroy, Kyle D; Yang, Deren; Xia, Younan; Zhang, Hui

    2017-02-24

    At the forefront of nanochemistry, there exists a research endeavor centered around intermetallic nanocrystals, which are unique in terms of long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure. In contrast to alloy nanocrystals with no elemental ordering, it is challenging to synthesize intermetallic nanocrystals with a tight control over their size and shape. Here, recent progress in the synthesis of intermetallic nanocrystals with controllable sizes and well-defined shapes is highlighted. A simple analysis and some insights key to the selection of experimental conditions for generating intermetallic nanocrystals are presented, followed by examples to highlight the viable use of intermetallic nanocrystals as electrocatalysts or catalysts for various reactions, with a focus on the enhanced performance relative to their alloy counterparts that lack elemental ordering. Within the conclusion, perspectives on future developments in the context of synthetic control, structure-property relationships, and applications are discussed.

  19. Energy storage materials synthesized from ionic liquids.

    PubMed

    Gebresilassie Eshetu, Gebrekidan; Armand, Michel; Scrosati, Bruno; Passerini, Stefano

    2014-12-01

    The advent of ionic liquids (ILs) as eco-friendly and promising reaction media has opened new frontiers in the field of electrochemical energy storage. Beyond their use as electrolyte components in batteries and supercapacitors, ILs have unique properties that make them suitable as functional advanced materials, media for materials production, and components for preparing highly engineered functional products. Aiming at offering an in-depth review on the newly emerging IL-based green synthesis processes of energy storage materials, this Review provides an overview of the role of ILs in the synthesis of materials for batteries, supercapacitors, and green electrode processing. It is expected that this Review will assess the status quo of the research field and thereby stimulate new thoughts and ideas on the emerging challenges and opportunities of IL-based syntheses of energy materials.

  20. Method and apparatus for synthesizing hydrocarbons

    DOEpatents

    Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

    1983-06-21

    A method and apparatus for synthesizing a mixture of hydrocarbons having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further includes Na present as a substitutional cation in an amount of about 5 to 10 atom %. At a temperature of about 340 to 360/sup 0/C, and at pressures of about 20 to 50 atm, CH/sub 3/OH is produced in an amount of about 90 wt % of the total hydrocarbon mixture, and comprised 1 mole % of the effluent gas.

  1. Molecular scale electronics: syntheses and testing

    NASA Astrophysics Data System (ADS)

    Reinerth, William A.; Jones, LeRoy, II; Burgin, Timothy P.; Zhou, Chong-wu; Muller, C. J.; Deshpande, M. R.; Reed, Mark A.; Tour, James M.

    1998-09-01

    This paper describes four significant breakthroughs in the syntheses and testing of molecular scale electronic devices. The 16-mer of oligo(2-dodecylphenylene ethynylene) was prepared on Merrifields resin using the iterative divergent/convergent approach which significantly streamlines the preparation of this molecular scale wire. The formation of self-assembled monolayers and multilayers on gold surfaces of rigid rod conjugated oligomers that have thiol, 0957-4484/9/3/016/img11-dithiol, thioacetyl, or 0957-4484/9/3/016/img11-dithioacetyl end groups have been studied. The direct observation of charge transport through molecules of benzene-1, 4-dithiol, which have been self-assembled onto two facing gold electrodes, has been achieved. Finally, we report initial studies into what effect varying the molecular alligator clip has on the molecule scale wire's conductivity.

  2. Simplification of Methods for PET Radiopharmaceutical Syntheses

    SciTech Connect

    Kilbourn, Michael, R.

    2011-12-27

    In an attempt to develop simplified methods for radiochemical synthesis of radiopharmaceuticals useful in Positron Emission Tomography (PET), current commercially available automated synthesis apparati were evaluated for use with solid phase synthesis, thin-film techniques, microwave-accelerated chemistry, and click chemistry approaches. Using combinations of these techniques, it was shown that these automated synthesis systems can be simply and effectively used to support the synthesis of a wide variety of carbon-11 and fluorine-18 labeled compounds, representing all of the major types of compounds synthesized and using all of the common radiochemical precursors available. These techniques are available for use to deliver clinically useful amounts of PET radiopharmaceuticals with chemical and radiochemical purities and high specific activities, suitable for human administration.

  3. Syntheses and degradations of fluorinated heterocyclics

    NASA Technical Reports Server (NTRS)

    Paciorek, K. L.; Kratzer, R. H.; Kaufman, J.; Rosser, R. W.

    1975-01-01

    The relative stability of two ring systems, the triazine rings and 1,2,4-oxadiazoles, which offer potential crosslinks useful for curing perfluoroalkyl ether elastomers, has been investigated. Tris (perfluoro-n-heptyl)-s-triazine, the perfluoroether substituted-s-triazine, 1,4-bis/(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl/benzene, its perfluoroalkyl ether substituted analog, and 3,5-bis-(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and subjected to thermal and oxidative degradation at 235 and 325 C and to hydrolytic degradation at 235 C. The perfluoroalkyl ether substituted triazine and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were found to be stable under all conditions investigated.

  4. Methods for synthesizing metal oxide nanowires

    DOEpatents

    Sunkara, Mahendra Kumar; Kumar, Vivekanand; Kim, Jeong H.; Clark, Ezra Lee

    2016-08-09

    A method of synthesizing a metal oxide nanowire includes the steps of: combining an amount of a transition metal or a transition metal oxide with an amount of an alkali metal compound to produce a mixture; activating a plasma discharge reactor to create a plasma discharge; exposing the mixture to the plasma discharge for a first predetermined time period such that transition metal oxide nanowires are formed; contacting the transition metal oxide nanowires with an acid solution such that an alkali metal ion is exchanged for a hydrogen ion on each of the transition metal oxide nanowires; and exposing the transition metal oxide nanowires to the plasma discharge for a second predetermined time period to thermally anneal the transition metal oxide nanowires. Transition metal oxide nanowires produced using the synthesis methods described herein are also provided.

  5. Syntheses and Structure Determinations of Calcium Thiolates.

    PubMed

    Chadwick, Scott; Englich, Ulrich; Noll, Bruce; Ruhlandt-Senge, Karin

    1998-09-07

    The exploration of synthetic methodologies toward heavy alkaline-earth chalcogenolates resulted in the preparation and structural characterization of a family of calcium thiolates, including [Ca(SC(6)F(5))(2)(py)(4)], 1 (py = pyridine), the separated ion-triple [Ca(18-crown-6)(NH(3))(3))][SMes](2).2THF, 2 (Mes = 2,4,6-tBu(3)C(6)H(2)), and the contact triple [Ca(18-crown-6)(SMes)(2)].THF, 3. Compound 1 was prepared by treating [Ca(N(SiMe(3))(2))(2)](2) with 4 equiv of HSC(6)F(5) under addition of pyridine. The thiolates 2 and 3 were synthesized by treatment of calcium metal dissolved in dry, liquid NH(3) under addition of 2 equiv of HSMes and crown ether or, alternatively, by the reduction of MesSSMes with calcium metal in dry, liquid ammonia. We also report two reaction products isolated during attempted calcium thiolate syntheses: [CaBr(4)(THF)(2)(&mgr;(2)-Li)(2)(THF)(4)], 4, isolated as the product of a salt elimination reaction between CaBr(2) and 2 equiv of [Li(THF)(n)()S-2,4,6-(i)()Pr(3)C(6)H(2)](m)(). [(NH(4))(py)(SC(6)F(5))], 5, was obtained as the sole product in the reaction of metallic calcium with HSC(6)F(5) in liquid ammonia under addition of pyridine. All compounds were characterized by single-crystal X-ray crystallography in addition to IR and NMR spectroscopy.

  6. Poly-alpha-glutamic acid synthesis using a novel catalytic activity of RimK from Escherichia coli K-12.

    PubMed

    Kino, Kuniki; Arai, Toshinobu; Arimura, Yasuhiro

    2011-03-01

    Poly-L-α-amino acids have various applications because of their biodegradable properties and biocompatibility. Microorganisms contain several enzymes that catalyze the polymerization of L-amino acids in an ATP-dependent manner, but the products from these reactions contain amide linkages at the side residues of amino acids: e.g., poly-γ-glutamic acid, poly-ε-lysine, and cyanophycin. In this study, we found a novel catalytic activity of RimK, a ribosomal protein S6-modifying enzyme derived from Escherichia coli K-12. This enzyme catalyzed poly-α-glutamic acid synthesis from unprotected L-glutamic acid (Glu) by hydrolyzing ATP to ADP and phosphate. RimK synthesized poly-α-glutamic acid of various lengths; matrix-assisted laser desorption ionization-time of flight-mass spectrometry showed that a 46-mer of Glu (maximum length) was synthesized at pH 9. Interestingly, the lengths of polymers changed with changing pH. RimK also exhibited 86% activity after incubation at 55°C for 15 min, thus showing thermal stability. Furthermore, peptide elongation seemed to be catalyzed at the C terminus in a stepwise manner. Although RimK showed strict substrate specificity toward Glu, it also used, to a small extent, other amino acids as C-terminal substrates and synthesized heteropeptides. In addition, RimK-catalyzed modification of ribosomal protein S6 was confirmed. The number of Glu residues added to the protein varied with pH and was largest at pH 9.5.

  7. New Poly(amide-imide)/Nanocomposites Reinforced Silicate Nanoparticles Based on N-pyromellitimido-L-phenyl Alanine Containing Ether Moieties

    NASA Astrophysics Data System (ADS)

    Faghihi, Khalil; Shabanian, Meisam; Dadfar, Ehsan

    2012-02-01

    A series of Poly(amide-imide)/montmorillonite nanocomposites containing N-pyromellitimido-L-phenyl alanine moiety in the main chain were synthesized by a convenient solution intercalation technique. Poly(amide-imide) (PAI) 5 as a source of polymer matrix was synthesized by the direct polycondensation reaction of N-pyromellitimido-L-phenyl alanine 3 with 4,4'-diamino diphenyl ether 4 in the presence of triphenyl phosphite (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). The resulting nanocomposite films were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results showed that organo-modified clay was dispersed homogeneously in PAI matrix. TGA indicated an enhancement of thermal stability of new nanocomposites compared with the pure polymer.

  8. Functional Aromatic Poly(1,3,4-Oxadiazole-Ether)s with Benzimidazole Pendants: Synthesis, Thermal and Dielectric Studies

    PubMed Central

    Ganesh, Shimoga D.; Pai, Vasantakumar K.; Kariduraganavar, Mahadevappa Y.; Jayanna, Madhu B.

    2014-01-01

    Poly(1,3,4-oxadiazole-ether) with reactive carboxylic acid pendants was synthesized from solution polymerization via nucleophilic displacement polycondensation among 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole (BFPOx) and 4,4′-bis(4-hydroxyphenyl) valeric acid (BHPA). Without altering the polymeric segments, benzimidazole modified poly(1,3,4-oxadiazole-ether)s were prepared by varying stoichiometric ratios of 1,2-phenylenediamine. The molecular structural characterization of these polymers was achieved by, FT-IR, NMR, TGA, elemental analysis, and analytical techniques. The weight-average molecular weight of virgin polymer with carboxylic acid functionality was determined by gel permeation chromatography (GPC) and was found to be 22400 (Mw/Mn = 2.07). All the synthesized polyethers were compressed into pellets and electrical contacts were established to perform dielectric properties. PMID:27437448

  9. The synthesis and in vitro characterization of the mucoadhesion and swelling of poly(acrylic acid) hydrogels.

    PubMed

    Warren, S J; Kellaway, I W

    1998-05-01

    The purpose of this research was to synthesize insoluble, mucoadhesive hydrogels by crosslinking linear poly(acrylic acid) with sucrose and investigate the relationship between hydrogel crosslink density, swelling, and in vitro mucoadhesion. A condensation reaction was employed to synthesize the hydrogels and crosslink density was varied by altering sucrose concentration and cure time. Equilibrium swelling at pH 7.4 was measured both gravimetrically and geometrically. In vitro mucoadhesion was determined by a tensile technique. Equilibrium swelling studies indicated that the crosslink density was proportional to both sucrose concentration and duration of cure time. In vitro mucoadhesive properties of the hydrogels improved as crosslink density increased. This was attributed to an increase in poly(acrylic acid) chain density/unit area of the equilibrium swollen hydrogel, which promoted interaction of the mucoadhesive and glycoprotein polymer chains.

  10. Enhanced surface segregation of poly(methyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate by introduction of a second block.

    PubMed

    Ni, Huagang; Gao, Jie; Li, Xuehua; Hu, Yanyan; Yan, Donghuan; Ye, XiuYun; Wang, Xinping

    2012-01-01

    New fluorinated copolymers of poly(methyl methacrylate)-b-poly(butyl methacrylate) or poly(n-octadecyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (PMMA(x)-b-PBMA(y)-ec-PFMA(z) or PMMA(x)-b-PODMA(y)-ec-PFMA(z)) were synthesized by living atom transfer radical polymerization. Thin films made of PMMA(230)-b-PODMA(y)-ec-PFMA(1) were characterized by differential scanning calorimetry, angle-resolved X-ray photoelectron spectroscopy and X-ray diffraction. These films were found to exhibit robust surface segregation of the end groups. Furthermore, the fluorine enrichment factor at the film surface was found to increase linearly with increasing degree of polymerization of poly(n-octadecyl methacrylate) and its increasing fusion enthalpy in the second block, which enhances the segregation of the fluorinated moieties.

  11. Synthesis and characterization of sulfonated poly(ether sulfone)s containing mesonaphthobifluorene for polymer electrolyte membrane fuel cell.

    PubMed

    Lim, Youngdon; Seo, Dongwan; Lee, Soonho; Hossain, Md Awlad; Lim, Jinseong; Lee, Sangyoung; Hong, Taehoon; Kim, Whangi

    2014-10-01

    The novel sulfonated poly(ether sulfone)s containing mesonaphthobifluorene (MNF) moiety were synthesized and characterized their properties. The prepared polymers have highly conjugated aromatic structure due to the MNF group which is an allotrope of carbon and one atom thick planar sheets of sp2-bonded carbon atoms. Poly(ether sulfone)s bearing tetraphenylethylene on polymer backbone were synthesized by polycondensation and followed intra-cyclization from tetraphenylethylene to form MNF by Friedel-craft reaction with Lewis acid (FeCl3). The sulfonation was performed selectively on MNF units with conc. sulfuric acid. The structural properties of the sulfonated polymers were investigated by 1H-NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, and proton conductivity. The synthesized polymer electrolyte membranes showed better thermal and dimensional stabilities owing to the inducted highly conjugated aromatic structure in the polymer backbone. The water uptake of the synthesized membranes ranged from 23-52%, compared with 32.13% for Nafion 211 at 80 degrees C. The synthesized membranes exhibited proton conductivities (80 degrees C, RH 90%) of 74.6-100.4 mS/cm, compared with 102.7 mS/cm for Nafion 211.

  12. Poly(lactic acid-co-glycolic acid)-poly(ethylene glycol)-poly(lactic acid-co-glycolic acid) thermogel as a novel submucosal cushion for endoscopic submucosal dissection.

    PubMed

    Yu, Lin; Xu, Wei; Shen, Wenjia; Cao, Luping; Liu, Yan; Li, Zhaoshen; Ding, Jiandong

    2014-03-01

    Endoscopic submucosal dissection (ESD) is a clinical therapy for early stage neoplastic lesions in the gastrointestinal tract. It is, however, faced with a crucial problem: the high occurrence of perforation. The formation of a submucosal fluid cushion (SFC) via a fluid injection is the best way to avoid perforation, and thus an appropriate biomaterial is vital for this minimally invasive endoscopic technique. In this study, we introduced an injectable thermogel as a novel submucosal injection substance in ESD. The hydrogel synthesized by us was composed of poly(lactic acid-co-glycolic acid)-poly(ethylene glycol)-poly(lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) triblock copolymers. The polymer/water system was a low-viscosity fluid at room temperature and thus easily injected, and turned into a non-flowing gel at body temperature after injection. The submucosal injection of the thermogel to create SFCs was performed in both resected porcine stomachs and living minipigs. High mucosal elevation with a clear margin was maintained for a long duration. Accurate en bloc resection was achieved with the assistance of the thermogel. The mean procedure time was strikingly reduced. Meanwhile, no obvious bleeding, perforation and tissue damage were observed. The application of the thermogel not only facilitated the ESD procedure, but also increased the efficacy and safety of ESD. Therefore, the PLGA-PEG-PLGA thermogel provides an excellent submucosal injection system, and has great potential to improve the ESD technique significantly.

  13. Synthesis of poly glycidylmethacrylate grafted azobenzene copolymer: Photosensitivity and nonlinear optical properties

    NASA Astrophysics Data System (ADS)

    Sousani, Abbas; Moghadam, Peyman Najafi; Hasanzadeh, Reza; Motiei, Hamideh; Bagheri, Massoumeh

    2016-01-01

    In this work poly glycidylmethacrylate grafted 4-hydroxy-4‧-methoxy-azobenzene (Azo-PGMA) was synthesized. For this propose firstly 4-hydroxy-4‧-methoxy-azobenzene (AZO) was prepared, then poly glycidylmethacrylate was prepared by free radical polymerization of glycidylmethacrylate in the presence of benzoyl peroxide as initiator under inert atmosphere in dry THF. Finally the homopolymer was functionalized by AZO moieties. The characterization of the synthesized copolymer was carried out by 1H NMR, FT-IR, thermal gravimetric analyze (TGA), differential scanning calorimetry (DSC) and optical polarizing microscope (POM) analysis. The UV-vis studies were carried out on Azo-PGMA copolymer and the results showed that the synthesized Azo-PGMA copolymer has ultra-fast response to UV light and has slow relaxation time. Also the third-order nonlinear optical properties of the Azo-PGMA copolymer and AZO were studied by using Z-scan technique. Nonlinear refraction and absorption coefficients of the above mentioned materials were measured by the closed and open aperture Z-scan method using a continuous wave Nd-YAG laser at 532 nm. The positive nonlinear absorption in Azo-PGMA and AZO was investigated at the wavelength of λ = 532 nm, respectively and the measured values of nonlinear refraction in both of the samples were from the order of 10-8 cm2/W.

  14. Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

    2015-08-01

    Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance (1HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF3SO3 show the highest conductivity. The complexation between EMG30 and LiCF3SO3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR).

  15. Controlled release of theophylline from poly(vinyl alcohol) hydrogels/porous silicon nanostructured systems

    NASA Astrophysics Data System (ADS)

    Cervantes-Rincón, N.; Medellín-Rodríguez, F. J.; Escobar-Barrios, V. A.; Palestino, G.

    2013-03-01

    In this research, hybrid hydrogels of poly (vinyl alcohol)/ porous silicon (PSi)/theophylline were synthesized by the freezing and thawing method. We evaluated the influence of the synthesis parameters of the poly (vinyl alcohol) (PVA) hydrogels in relation to their ability to swell and drug released. The parameters studied (using an experimental design developed in Minitab 16) were the polymer concentration, the freezing temperature and the number of freezing/thawing (f/t) cycles. Nanostructured porous silicon particles (NsPSi) and theophylline were added within the polymer matrix to increase the drug charge and the polymer mechanical strength. The hybrid hydrogels were characterized by Infrared Spectroscopy Fourier Transform (FTIR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Differential Scanning Calorimetry (DSC), drug delivery kinetics were engineered according to the desired drug release schedule.

  16. Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

    SciTech Connect

    Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

    2015-08-28

    Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance ({sup 1}HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in {sup 1}HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF{sub 3}SO{sub 3} show the highest conductivity. The complexation between EMG30 and LiCF{sub 3}SO{sub 3} were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)

  17. Thin films from hydrophilic poly(N,N-dimethyl acrylamide) copolymers as optical indicators for humidity

    NASA Astrophysics Data System (ADS)

    Lazarova, K.; Todorova, L.; Christova, D.; Vasileva, M.; Georgiev, R.; Madjarova, V.; Babeva, T.

    2017-01-01

    In the present paper we study thin films from poly(N,N-dimethyl acrylamide)-poly(ethylene oxide) (PDMAA/PEO) copolymers of different composition and structure in order to implement them as sensitive media for optical indicators for humidity. PDMAA/PEO di- and triblock copolymers were synthesized via redox polymerization in aqueous media. Thin films were deposited on silicon substrates by spin coating method using polymers solutions with appropriate concentrations. Refractive index, extinction coefficient and thickness of the films are calculated from reflectance spectra of the films deposited on silicon substrates using non-linear curve fitting method. Sensing properties of the films were tested by films exposure to different humidity levels followed by in-situ monitoring of the changes in the optical properties. The influence of the polymer structure and postdeposition annealing on the optical and sensing properties of the films was investigated. The potential application of selected polymers for optical sensing of humidity were demonstrated and discussed.

  18. Poly(aryl ethers) and related polysiloxane copolymer molecular coatings: Preparation and radiation degradation

    NASA Technical Reports Server (NTRS)

    Mcgrath, J. E.

    1982-01-01

    The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.

  19. Synthesis of photosensitive poly(methyl methacrylate-co-glycidyl methacrylate) for optical waveguide devices

    NASA Astrophysics Data System (ADS)

    Fei, Xu; Shi, Yuan; Cao, Yang

    2010-08-01

    Photosensitive poly(MMA-co-GMA) for optical waveguide was synthesized, and the refractive index of the polymer film was tuned in the range of 1.481-1.588 at 1550 nm by mixing with bis-phenol-A epoxy resin. The film, which was made by spinning coated the poly(MMA-co-GMA) with photo initiator, had good UV light lithograph sensitivity, high glass transition temperature ( T g : 153°C, after crosslinking) and good thermal stabilities ( T d : up to 324°C, after crosslinking). The optical waveguides with very smooth top surface were fabricated from the resulting polymer by direct UV exposure and chemical development. For waveguides with cladding, the propagation losses of the channel waveguides were measured to be below 3 dB/cm at 1550 nm.

  20. Degradation of imidazolium- and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone) anion exchange membranes.

    PubMed

    Chen, Dongyang; Hickner, Michael A

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by ¹H NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 °C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 °C but much lower stability at 80 °C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  1. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    SciTech Connect

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  2. Synthesis of the first poly(diaminosulfide)s and an investigation of their applications as drug delivery vehicles

    PubMed Central

    Yoo, Jun; D’Mello, Sheetal R.; Graf, Tyler; Salem, Aliasger K.; Bowden, Ned B.

    2012-01-01

    This paper reports the first examples of poly(diaminosulfide)s that were synthesized by the reaction of a sulfur transfer reagent and several secondary diamines. The diaminosulfide group has the general structure of R2N-S-NR2 and, although it has been used in the synthesis of small molecules, it has never been utilized in the synthesis of macromolecules until this report. A series of poly(diaminosulfide)s were synthesized at elevated temperatures, and the molecular weights of the polymers were as high as 12,400 g mol−1 with conversions for the polymerization reaction up to 99%. The rate constants for the transamination reactions that lead to the polymers were measured in several solvents to provide an understanding the reaction conditions necessary to polymerize the monomers. The degradation of diaminosulfides were studied in D2O, C6D6, CD3OD, CDCl3, and DMSO-d6/D2O to demonstrate that they were very stable in organic solvents but degraded within hours under aqueous conditions. These results clearly demonstrated that diaminosulfides are very stable in organic solvents under ambient conditions. Poly(diaminosulfide)s have sufficient stabilities to be useful for many applications. The ability of these polymers to function as drug delivery vehicles were studied by the fabrication of nanoparticles of a water-insoluble poly(diaminosulfide) with a dye. The microparticles were readily absorbed into human embryonic 293 cells and possessed no measureable toxicity towards these same cells. PMID:22347726

  3. A Route to Aliphatic Poly(ester)s with Thiol Pendant Groups: From Monomer Design to Editable Porous Scaffolds.

    PubMed

    Fuoco, Tiziana; Finne-Wistrand, Anna; Pappalardo, Daniela

    2016-04-11

    Biodegradable aliphatic polyesters such as poly(lactide) and poly(ε-caprolactone), largely used in tissue engineering applications, lack suitable functional groups and biological cues to enable interactions with cells. Because of the ubiquity of thiol groups in the biological environment and the pliability of thiol chemistry, we aimed to design and synthesize poly(ester) chains bearing pendant thiol-protected groups. To achieve this, 3-methyl-6-(tritylthiomethyl)-1,4-dioxane-2,5-dione, a lactide-type monomer possessing a pendant thiol-protected group, was synthesized. This molecule, when used as a monomer in controlled ring-opening polymerization in combination with lactide and ε-caprolactone, appeared to be a convenient "building block" for the preparation of functionalized aliphatic copolyesters, which were easily modified further. A polymeric sample bearing pyridyl disulfide groups, able to bind a cysteine-containing peptide, was efficiently obtained from a two-step modification reaction. Porous scaffolds were then prepared by blending this latter copolymer sample with poly(L-lactide-co-ε-caprolactone) followed by salt leaching. A further disulfide exchange reaction performed in aqueous medium formed porous scaffolds with covalently linked arginine-glycine-aspartic acid sequences. The scaffolds were characterized by thermal and mechanical tests, and scanning electron microscopy surface images revealed a highly porous morphology. Moreover, a cytotoxicity test indicated good cell viability.

  4. Nanocrystalline nickel ferrite particles synthesized by non-hydrolytic sol-gel method and their composite with biodegradable polymer.

    PubMed

    Yin, H; Casey, P S; Chow, G M

    2012-11-01

    Targeted drug delivery has been one of the most important biomedical applications for magnetic particles. Such applications require magnetic particles to have functionalized surfaces/surface coatings that facilitate their incorporation into a polymer matrix to produce a polymer composite. In this paper, nanocrystalline nickel ferrite particles with an oleic acid surface coating were synthesized using a non-hydrolytic sol-gel method and incorporated into a biodegradable polymer matrix, poly(D,L-lactide) PLA prepared using a double emulsion method. As-synthesized nickel ferrite particles had a multi-crystalline structure with chemically adsorbed oleic acid on their surface. After forming the PLA composite, nickel ferrite particles were encapsulated in PLA microspheres. At low nickel ferrite concentrations, composites showed very similar surface charges to that of PLA. The composites were magnetically responsive and increasing the nickel ferrite concentration was found to increase magnetization of the composite.

  5. Room temperature synthesized rutile TiO(2) nanoparticles induced by laser ablation in liquid and their photocatalytic activity.

    PubMed

    Liu, Peisheng; Cai, Weiping; Fang, Ming; Li, Zhigang; Zeng, Haibo; Hu, Jinlian; Luo, Xiangdong; Jing, Weiping

    2009-07-15

    TiO(2) nanoparticles were prepared by one-step pulsed laser ablation of a titanium target immersed in a poly-(vinylpyrrolidone) solution at room temperature. The products were systematically characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). The results indicated that the rutile TiO(2) nanocrystalline particles were one-step synthesized at room temperature and the mean size in diameter is about 50 nm with a narrow size distribution. A probable formation process was proposed on the basis of the microstructure and the instantaneous plasma plume induced by the laser. Photocatalytic activity was monitored by degradation of a methylene blue solution. The as-prepared rutile TiO(2) nanoparticles demonstrate a good photocatalytic performance. This work shows that pulsed laser ablation in liquid media is a good method to synthesize some nanosized materials which are difficult to produce by other conventional methods.

  6. Direct Synthesis of Poly(dimethylsiloxane) Copolymers with TPE-Properties via CuAAC (Click Chemistry).

    PubMed

    Schmidt, Udo; Zehetmaier, Philip C; Rieger, Bernhard

    2010-03-16

    Poly(dimethylsiloxane) copolymers were synthesized directly from AA/BB monomers employing a CuAAC reaction (click chemistry) in a polyaddition approach. Using organic dialkynes and oligo(siloxane)s end-functionalized with azide moieties it was possible to obtain siloxane-based copolymers with TPE properties by click chemistry for the first time. As seen from DSC experiments, properties were strongly dependent on the incorporated organic comonomer.

  7. Poly(alkylene phosphates): from synthetic models of biomacromolecules and biomembranes toward polymer-inorganic hybrids (mimicking biomineralization).

    PubMed

    Penczek, Stanislaw; Pretula, Julia; Kaluzynski, Krzysztof

    2005-01-01

    Syntheses of poly(alkylene phosphates), with repeating units having two or three methylene groups and phosphoryl groups and mimicking backbones of biomacromolecules, are reviewed. Two major methods elaborated in this laboratory, namely, ring-opening polymerization and transesterification, are described. The resulting polymers were used as carriers of cations (Ca2+ and Mg2+) in membrane processes and in controlling the crystallization of CaCO3, in a process related to biomineralization.

  8. Photoinduced bending behavior of cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone.

    PubMed

    Lv, Jiu-an; Wang, Weiru; Xu, Jixiang; Ikeda, Tomiki; Yu, Yanlei

    2014-07-01

    Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation.

  9. A new synthesis of lamellar-mesostructured silica by using poly(ethylene glycol) distearate as template

    SciTech Connect

    Zhang Huanzhi; Jin Zhengwei; Wang Xiaodong

    2008-11-03

    A lamellar-mesostructured silica has been synthesized by using poly(ethylene glycol) distearate as template in ethanol solution. Highly ordered lamellar mesostructure was confirmed by X-ray diffraction pattern, transmission electronic microscopy, and nitrogen adsorption-desorption isotherm. The material obtained in this work has a large interlayer distance, and good thermal and mechanical stabilities, which can favor the preparation of the in situ polymerized nanocomposites based on intercalation of polymers in the lamellar-mesostructured silica.

  10. Poly(silylene)vinylenes from ethynylhydridosilanes

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina

    1992-11-10

    Catalytic polymerization of dialkyl-, alkylaryl- or diaryldiethynylhydridosilanes cleanly affords soluble poly(silylene)vinylenes which can be shaped as fibers, films and bulk objects and thermally converted to silicon carbide.

  11. Lignin poly(lactic acid) copolymers

    DOEpatents

    Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.

    2017-02-14

    Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

  12. Poly(ADP-ribosyl)ation in carcinogenesis.

    PubMed

    Masutani, Mitsuko; Fujimori, Hiroaki

    2013-12-01

    Cancer develops through diverse genetic, epigenetic and other changes, so-called 'multi-step carcinogenesis', and each cancer harbors different alterations and properties. Here in this article we review how poly(ADP-ribosyl)ation is involved in multi-step and diverse pathways of carcinogenesis. Involvement of poly- and mono-ADP-ribosylation in carcinogenesis has been studied at molecular and cellular levels, and further by animal models and human genetic approaches. PolyADP-ribosylation acts in DNA damage repair response and maintenance mechanisms of genomic stability. Several DNA repair pathways, including base-excision repair and double strand break repair pathways, involve PARP and PARG functions. These care-taker functions of poly(ADP-ribosyl)ation suggest that polyADP-ribosyation may mainly act in a tumor suppressive manner because genomic instability caused by defective DNA repair response could serve as a driving force for tumor progression, leading to invasion, metastasis and relapse of cancer. On the other hand, the new concept of 'synthetic lethality by PARP inhibition' suggests the significance of PARP activities for survival of cancer cells that harbor defects in DNA repair. Accumulating evidence has revealed that some PARP family molecules are involved in various signaling cascades other than DNA repair, including epigenetic and transcriptional regulations, inflammation/immune response and epithelial-mesenchymal transition, suggesting that poly(ADP-ribosyl)ation both promotes and suppresses carcinogenic processes depending on the conditions. Expanding understanding of poly(ADP-ribosyl)ation suggests that strategies to achieve cancer prevention targeting poly(ADP-ribosyl)ation for genome protection against life-long exposure to environmental carcinogens and endogenous carcinogenic stimuli.

  13. Atom transfer radical polymerization to fabricate monodisperse poly[glycidyl methacrylate-co-poly (ethylene glycol) methacrylate] microspheres and its application for protein affinity purification.

    PubMed

    Yu, Ling; Shi, Zhuan Zhuan; Li, Chang Ming

    2015-09-01

    Poly[glycidyl methacrylate-co-poly (ethylene glycol) methacrylate] microspheres for the first time were successfully synthesized by atom transfer radical polymerization (ATRP) method at room temperature. The co-polymerization approach was investigated to delicately control the microsphere morphology and size-distribution by reaction conditions including solvent percentage, monomer loading and rotation speed. The results show that the average size of the microspheres is ∼5.7 μm with coexistence of epoxy, hydroxyl and ether groups, which provide plentiful functional sites for protein anchoring. The mechanism of the microsphere formation is proposed. The microsphere successfully demonstrates its unique application for affinity purification of proteins, in which the functional epoxy group facilitates a simple and efficient protein covalent immobilization to purify immunoglobulin G on the microspheres, while the hydrophilic poly (ethylene glycol) motif can repulse nonspecific protein adsorption for good specificity. This microspheres can be used in broad protein biosensors due to their abundant functional groups and high surface to volume ratio.

  14. In vitro characterization of pH-sensitive azithromycin-loaded methoxy poly (ethylene glycol)-block-poly (aspartic acid-graft-imidazole) micelles.

    PubMed

    Teng, Fangfang; Deng, Peizong; Song, Zhimei; Zhou, Feilong; Feng, Runliang; Liu, Na

    2017-02-09

    In order to improve azithromycin's antibacterial activity in acidic medium, monomethoxy poly (ethylene glycol)-block-poly (aspartic acid-graft-imidazole) copolymer was synthesized through allylation, free radical addition, ring-opening polymerization and amidation reactions with methoxy poly (ethylene glycol) as raw material. Drug loading capacity and encapsulation efficiency of azithromycin-loaded micelles prepared via thin film hydration method were 11.58±0.86% and 96.06±1.93%, respectively. The drug-loaded micelles showed pH-dependent property in the respects of particle size, zeta potential at the range of pH 5.5-7.8. It could control drug in vitro release and demonstrate higher release rate at pH 6.0 than that at pH 7.4. In vitro antibacterial experiment indicated that the activity of azithromycin-loaded micelles against S. aureus was superior to free azithromycin in medium at both pH 6.0 and pH 7.4. Using fluorescein as substitute with pH-dependent fluorescence decrease property, laser confocal fluorescence microscopy analysis confirmed that cellular uptake of micelles was improved due to protonation of copolymer's imidazole groups at pH 6.0. The enhanced cellular uptake and release of drug caused its activity enhancement in acidic medium when compared with free drug. The micellar drug delivery system should be potential application in the field of bacterial infection treatment.

  15. Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

    PubMed

    Feng, Xueling; Zhang, Kaihuan; Chen, Peng; Sui, Xiaofeng; Hempenius, Mark A; Liedberg, Bo; Vancso, G Julius

    2016-12-01

    Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature.

  16. Synthesis of poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABA block copolymers by the combination of quasiliving carbocationic and atom transfer radical polymerizations.

    PubMed

    Szabó, Ákos; Szarka, Györgyi; Iván, Béla

    2015-01-01

    Systematic investigations are carried out on the synthesis of a series of new, unique ABA-type triblock copolymers consisting of the hydrophobic and chemically inert polyisobutylene (PIB) inner and the hydrophilic comb-shaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer as an outer block. Telechelic PIB macroinitiators with narrow molecular weight distributions (MWD) are synthesized by quasiliving carbocationic polymerization of isobutylene with a bifunctional initiator followed by quantitative chain end derivatizations. Atom transfer radical polymerization (ATRP) of PEGMAs with various molecular weights is investigated by using these macroinitiators. It is found that CuBr is an inefficient ATRP catalyst, while CuCl leads to high, nearly complete conversions of the PEGMA macromonomers. Gel permeation chromatography (GPC) analyses reveal slow initiation of PEGMA at relatively high PIB/PEGMA ratios or with PEGMAs of higher molecular weights due to steric hindrance between the macroinitiator and macromonomer. The occurrence of slow initiation, and not permanent termination, is proven by highly efficient ATRP of a low-molecular-weight monomer, methyl methacrylate, with the block copolymers as macroinitiators. Successful synthesis of PPEGMA-PIB-PPEGMA ABA block copolymers is obtained by using either low-molecular-weight PEGMA or relatively low macroinitiator/macromonomer ratios. Differential scanning calorimetry (DSC) indicates phase separation and significant suppression of the crystallinity of the pendant poly(ethylene glycol) (PEG) chains in these new block copolymers.

  17. 2,5-Thiophene-based liquid crystalline poly(amide)s, poly(arylene ether ketone)s, and poly(benzimidazole)s

    SciTech Connect

    Stompel, S.

    1993-01-01

    Poly(p-phenylene terephthalamide) (PPTA or Kevlar[sup TM]) adopts an extended-chain crystal habit in the solid state which derives from the chain parallelism in its liquid crystalline (LC) phase. The objective of this dissertation is to investigate how the deviation from core linearity which is achieved by replacing terephthalic acid, a linear monomer, with 2,5-thiophenedicarboxylic acid, a monomer with a [approximately]148[degrees] bend, affects liquid crystalline properties of aromatic polyamides. The mesogenic properties of the 2,5-thiophene are initially verified for newly synthesized low molar mass diamide model compounds where the characteristic texture of the smectic A phase is observed by polarized optical microscopy. Differential scanning calorimetry (DSC) studies shows that the observed mesophase for the thiophene-based diamide is much narrower and exists at lower temperatures than that observed for the corresponding p-phenylene diamide. Extensions to macromolecules show that if each terephthalamide unit in PPTA is replaced with a 2,5-thiophenylamide unit, high molecular weight polymer can be synthesized and, moreover, such 2,5-thiophene-based aromatic polyamide (PPThA) is stable and exhibits liquid crystalline phases in concentrated sulfuric acid solutions. Preliminary mechanical properties of coarse fibers spun from the liquid crystalline solutions and isotropic solutions in sulfuric acid are compared. PPThA lyotropic solutions are studied using deuterium NMR spectroscopy. LC solutions may be aligned in a magnetic field to yield a [open quotes]single liquid crystal[close quotes]-a macroscopically oriented phase. In such uniaxial solutions, the transition to isotropic state at elevated temperatures may be indirectly monitored by deuterium NMR; quadrupolar interactions of the probe molecule (deuterated sulfuric acid) reflects changes in the macromolecular ordering. Direct monitoring of polymer order is accomplished using deuterium labeled PPThA.

  18. Investigation of anti-corrosive properties of poly(aniline-co-2-pyridylamine-co-2,3-xylidine) and its nanocomposite poly(aniline-co-2-pyridylamine-co-2,3-xylidine)/ZnO on mild steel in 0.1 M HCl

    NASA Astrophysics Data System (ADS)

    Alam, Ruman; Mobin, Mohammad; Aslam, Jeenat

    2016-04-01

    A soluble terpolymer of aniline (AN), 2-pyridylamine (PA) and 2,3-xylidine (XY), poly(AN-co-PA-co-XY) and its nanocomposite with ZnO nanoparticles namely, poly(AN-co-PA-co-XY)/ZnO were synthesized by chemical oxidative polymerization employing ammonium persulfate as an oxidant. Nanocomposites of homopolymers, polyaniline/ZnO, poly(XY)/ZnO and poly(PA)/ZnO were also synthesized by following similar synthesis route. FTIR, XRD and SEM techniques were used to characterize the synthesized compounds. The synthesized compounds were chemically deposited on mild steel specimens by solvent evaporation method using N-methyl-2-pyrrolidone (NMP) as solvent and 10% epoxy resin (by weight) as binder. Anticorrosive properties of homopolymer nanocomposites, terpolymer and its nanocomposite coatings were studied in 0.1 M HCl by subjecting them to various corrosion tests which includes: free corrosion potential measurement (OCP), weight loss measurements, potentiodynamic polarization, and AC impedance technique. The surface morphology of the corroded and uncorroded coated steel specimens was evaluated using SEM. The corrosion protection performance of terpolymer nanocomposite coating was compared to the terpolymer and individual homopolymers nanocomposites coatings after 30 days immersion in corrosive medium.

  19. Prediction of Poly(A) Sites by Poly(A) Read Mapping

    PubMed Central

    Bonfert, Thomas; Friedel, Caroline C.

    2017-01-01

    RNA-seq reads containing part of the poly(A) tail of transcripts (denoted as poly(A) reads) provide the most direct evidence for the position of poly(A) sites in the genome. However, due to reduced coverage of poly(A) tails by reads, poly(A) reads are not routinely identified during RNA-seq mapping. Nevertheless, recent studies for several herpesviruses successfully employed mapping of poly(A) reads to identify herpesvirus poly(A) sites using different strategies and customized programs. To more easily allow such analyses without requiring additional programs, we integrated poly(A) read mapping and prediction of poly(A) sites into our RNA-seq mapping program ContextMap 2. The implemented approach essentially generalizes previously used poly(A) read mapping approaches and combines them with the context-based approach of ContextMap 2 to take into account information provided by other reads aligned to the same location. Poly(A) read mapping using ContextMap 2 was evaluated on real-life data from the ENCODE project and compared against a competing approach based on transcriptome assembly (KLEAT). This showed high positive predictive value for our approach, evidenced also by the presence of poly(A) signals, and considerably lower runtime than KLEAT. Although sensitivity is low for both methods, we show that this is in part due to a high extent of spurious results in the gold standard set derived from RNA-PET data. Sensitivity improves for poly(A) sites of known transcripts or determined with a more specific poly(A) sequencing protocol and increases with read coverage on transcript ends. Finally, we illustrate the usefulness of the approach in a high read coverage scenario by a re-analysis of published data for herpes simplex virus 1. Thus, with current trends towards increasing sequencing depth and read length, poly(A) read mapping will prove to be increasingly useful and can now be performed automatically during RNA-seq mapping with ContextMap 2. PMID:28135292

  20. Adsorption of biopolymers on SWCNT: ordered poly(rC) and disordered poly(rI).

    PubMed

    Karachevtsev, Maksym V; Gladchenko, Galina O; Plokhotnichenko, Alexander M; Leontiev, Victor S; Karachevtsev, Victor A

    2013-03-07

    Polymer adsorption onto single-walled carbon nanotubes (SWCNTs) depends on its rigidity/flexibility. The adsorption properties of two related homopolynucleotides poly(rI) and poly(rC) but of different rigidities were compared, employing absorption spectroscopy and molecular dynamics simulation. It was shown that adsorption of the poor base stacked poly(rI) onto the nanotube is less effective than that of the strong base stacked poly(rC), the chain of which is of higher rigidity. Analysis of UV absorption spectra of polymer:nanotube suspension at heating until 90 °C, which leads to partial nanotube aggregation because of the weakly bound polymer sliding from the tube surface, revealed that the percent of precipitated nanotubes in suspension with poly(rI) is larger than that in suspension with poly(rC) (16% vs 7%). This fact indicates the higher stability of SWCNT:poly(rC) hybrid in comparison with SWCNT:poly(rI). Less effective adsorption of poly(rI) is confirmed with a weaker hypochromic effect of nanotubes covered with poly(rI) than with poly(rC), which originates from π-π stacking of nitrogen bases with the nanotube surface. Spontaneous adsorption of oligomers on the nanotube simulated by the molecular dynamics showed that oligomer r(I)25 has a weaker energy of binding to the carbon nanotube surface than r(C)25. The oligomer with ordered bases has a tendency to form the stretched conformation along the nanotube, which provides a higher binding energy, while more flexible r(I)25 forms the stable loop spaced away from the nanotube surface, the stability of which is strengthened with H-bonding between bases.

  1. Double helix formation of poly(m-phenylene)s bearing achiral oligo(ethylene oxide) pendants and transformation into an excess of one-handed single helix through cholate binding in water.

    PubMed

    Ben, Teng; Furusho, Yoshio; Goto, Hidetoshi; Miwa, Kazuhiro; Yashima, Eiji

    2009-06-21

    A water-soluble poly(m-phenylene) bearing an achiral oligo(ethylene oxide) chain at the 5-position was synthesized by the Ni(0)-mediated homo-coupling polycondensation of a 3,5-dibromophenol monomer. The poly(m-phenylene) adopted a single helical conformation in protic media and self-assembled into a double helix in water through aromatic interaction, while it took a random-coil conformation in chloroform. Upon the addition of sodium cholate in water, the double helical poly(m-phenylene) was transformed into single strands, which bound the cholate molecules to form an excess of one-handed single helix.

  2. Multilayer graphane synthesized under high hydrogen pressure

    DOE PAGES

    Antonov, V. E.; Bashkin, I. O.; Bazhenov, A. V.; ...

    2015-12-19

    A new hydrocarbon – hydrographite – with the composition close to CH is shown to form from graphite and gaseous hydrogen at pressures above 2 GPa and temperatures from 450 to 700 °C. Hydrographite is a black solid thermally stable under ambient conditions. When heated in vacuum, it decomposes into graphite and molecular hydrogen at temperatures from 500 to 650 °C. Powder X-ray diffraction characterizes hydrographite as a multilayer “graphane II” phase predicted by ab initio calculations [Wen X-D et al. PNAS 2011; 108:6833] and consisting of graphane sheets in the chair conformation stacked along the hexagonal c axis inmore » the -ABAB- sequence. The crystal structure of the synthesized phase belongs to the P63mc space group. Moreover, the unit cell parameters are a = 2.53(1) Å and c = 9.54(1) Å and therefore exceed the corresponding parameters of graphite by 2.4(2)% and 42.0(3)%. Stretching vibrations of C–H groups on the surface of the hydrographite particles are examined by infrared spectroscopy.« less

  3. Chemically synthesized FePt nanoclusters

    NASA Astrophysics Data System (ADS)

    Velasco, Victor; Abel, Frank; Hu, Xiaocao; Crespo, Patricia; Hadjipanayis, George

    2014-03-01

    FePt nanoparticles (NPs) are being widely investigated due to their high potential applications in magnetic recording media and biomedicine. These NPs are expected to be ideal candidates due to their excellent magnetic properties, such as high K and high Ms together with a high chemical stability. In this work, the FePt NPs have been synthesized by chemical routes according to the method reported by M. Chen et al.[2] At high temperature, surfactants together with iron pentacarbonyl are added to the solution and thermally decomposed. By controlling the injection temperature and the heating rate, we have been able to obtain homogeneous spherical clusters with an average size of 38 +/- 10 nm formed by 5 nm-FePt NPs. These clusters are found to be superparamagnetic above Tb of 55 K whereas at 5 K exhibit a coercive field of 1.2 kOe. Furthermore, these NPs seem to be highly stable in water after replacing the surfactants by TMAOH. These clusters appear to be good candidates for MRI and hyperthermia applications. This work was supported by NSF DMR-0302544.

  4. Oligodendrocyte Precursor Cells Synthesize Neuromodulatory Factors

    PubMed Central

    Sakry, Dominik; Yigit, Hatice; Dimou, Leda; Trotter, Jacqueline

    2015-01-01

    NG2 protein-expressing oligodendrocyte progenitor cells (OPC) are a persisting and major glial cell population in the adult mammalian brain. Direct synaptic innervation of OPC by neurons throughout the brain together with their ability to sense neuronal network activity raises the question of additional physiological roles of OPC, supplementary to generating myelinating oligodendrocytes. In this study we investigated whether OPC express neuromodulatory factors, typically synthesized by other CNS cell types. Our results show that OPC express two well-characterized neuromodulatory proteins: Prostaglandin D2 synthase (PTGDS) and neuronal Pentraxin 2 (Nptx2/Narp). Expression levels of the enzyme PTGDS are influenced in cultured OPC by the NG2 intracellular region which can be released by cleavage and localizes to glial nuclei upon transfection. Furthermore PTGDS mRNA levels are reduced in OPC from NG2-KO mouse brain compared to WT cells after isolation by cell sorting and direct analysis. These results show that OPC can contribute to the expression of these proteins within the CNS and suggest PTGDS expression as a downstream target of NG2 signaling. PMID:25966014

  5. [Femicides in ethnic and racialized groups: syntheses].

    PubMed

    Meneghel, Stela Nazareth; Lerma, Betty Ruth Lozano

    2017-01-01

    The text entitled "Femicides in ethnic and racialized groups: syntheses" presents some of the discussions that took place during a seminar on this topic in Buenaventura. Buenaventura is the main Colombian port on the Pacific, a region rich in minerals and a corridor for the movement of goods, which makes it a strategic territory and a center for disputes. At the seminar, the social and political determinants of femicide were discussed, understanding it as a tactic of waging war against women. The forum provided a space for academic discussion, but also for grievances over inter-personal violence, the manifestation of feelings and the elaboration of pain and grief through the medium of art. We believe that the dissemination of this experience to the Brazilian public, in a country with ethnic, social and racial vulnerability similar to that in Colombia, will be of value to social and health workers. The scope of this paper is therefore to provide the opinion of its authors on the determinants of femicides and on actions to tackle them, in addition to a synthesis of the discussions and debates that permeated the event.

  6. Multistep sintering to synthesize fast lithium garnets

    NASA Astrophysics Data System (ADS)

    Xu, Biyi; Duan, Huanan; Xia, Wenhao; Guo, Yiping; Kang, Hongmei; Li, Hua; Liu, Hezhou

    2016-01-01

    A multistep sintering schedule is developed to synthesize Li7La3Zr2O12 (LLZO) doped with 0.2 mol% Al3+. The effect of sintering steps on phase, relative density and ionic conductivity of Al-doped LLZO has been evaluated using powder X-Ray diffraction (XRD), scanning electron microscopy (SEM), 27Al magic spinning nuclear magnetic resonance (NMR) spectroscopy and electrochemical impedance spectroscopy (EIS). The results show that by holding the sample at 900 °C for 6 h, the mixture of tetragonal and cubic garnet phases are obtained; by continuously holding at 1100 °C for 6 h, the tetragonal phase completely transforms into cubic phase; by holding at 1200 °C, the relative density increases without decomposition of the cubic phase. The Al-LLZO pellets after multistep sintering exhibit cubic phase, relative density of 94.25% and ionic conductivity of 4.5 × 10-4 S cm-1 at room temperature. Based on the observation, a sintering model is proposed and discussed.

  7. Multilayer graphane synthesized under high hydrogen pressure

    SciTech Connect

    Antonov, V. E.; Bashkin, I. O.; Bazhenov, A. V.; Bulychev, B. M.; Fedotov, V. K.; Fursova, T. N.; Kolesnikov, A. I.; Kulakov, V. I.; Lukashev, R. V.; Matveev, D. V.; Sakharov, M. K.; Shulga, Y. M.

    2015-12-19

    A new hydrocarbon – hydrographite – with the composition close to CH is shown to form from graphite and gaseous hydrogen at pressures above 2 GPa and temperatures from 450 to 700 °C. Hydrographite is a black solid thermally stable under ambient conditions. When heated in vacuum, it decomposes into graphite and molecular hydrogen at temperatures from 500 to 650 °C. Powder X-ray diffraction characterizes hydrographite as a multilayer “graphane II” phase predicted by ab initio calculations [Wen X-D et al. PNAS 2011; 108:6833] and consisting of graphane sheets in the chair conformation stacked along the hexagonal c axis in the -ABAB- sequence. The crystal structure of the synthesized phase belongs to the P63mc space group. Moreover, the unit cell parameters are a = 2.53(1) Å and c = 9.54(1) Å and therefore exceed the corresponding parameters of graphite by 2.4(2)% and 42.0(3)%. Stretching vibrations of C–H groups on the surface of the hydrographite particles are examined by infrared spectroscopy.

  8. Mechanochemically Driven Syntheses of Boride Nanomaterials

    NASA Astrophysics Data System (ADS)

    Blair, Richard G.

    Solid state metathesis reactions have proven to be a viable route to the production of unfunctionalized nanomaterials. However, current implementations of this approach are limited to self-propagating reactions. We have been investigating mechanically driven metathesis reactions. The use of high-energy ball mills allows control of crystallite sizes without the use of a capping group. Reinforcement materials with crystallite sizes on the order of 5-30 nm can be produced in such a manner. Borides are of particular interest due to their strength, high melting point, and electrical conductivity. The ultimate goal of this work is to prepare oxide and capping group-free nanoparticles suitable for incorporation in thermoelectric, polymer, and ceramic composites. Ultimately this work will facilitate the production of improved thermoelectric materials that will provide robust, deployable, power generation modules to supplement or replace fuel cell, Stirling, and battery-derived power sources. It will also result in scalable, bulk syntheses of tough, refractory, conductive nanomaterials for polymer composites with improved electrical properties, ceramic composites with enhanced fracture toughness, and composites with enhanced neutron reflectance and/or absorbance.

  9. Why can't vertebrates synthesize trehalose?

    PubMed

    Argüelles, Juan-Carlos

    2014-10-01

    The non-reducing disaccharide trehalose is a singular molecule, which has been strictly conserved throughout evolution in prokaryotes (bacteria and archaea), lower eukaryotes, plants, and invertebrates, but is absent in vertebrates and-more specifically-in mammals. There are notable differences regarding the pivotal roles played by trehalose among distantly related organisms as well as in the specific metabolic pathways of trehalose biosynthesis and/or hydrolysis, and the regulatory mechanisms that control trehalose expression genes and enzymatic activities. The success of trehalose compared with that of other structurally related molecules is attributed to its exclusive set of physical properties, which account for its physiological roles and have also promoted important biotechnological applications. However, an intriguing question still remains: why are vertebrates in general, and mammals in particular, unable (or have lost the capacity) to synthesize trehalose? The search for annotated genomes of vertebrates reveals the absence of any functional trehalose synthase gene. Indeed, this is also true for the human genome, which contains, however, two genes encoding for isoforms of the hydrolytic activity (trehalase). Although we still lack a convincing answer, this striking difference might reflect the divergent evolutionary lineages followed by invertebrates and vertebrates. Alternatively, some clinical data point to trehalose as a toxic molecule when stored inside the human body.

  10. Surface functionalization of graphene oxide with poly(2-hydroxyethyl methacrylate)- graft-poly(ɛ-caprolactone) and its electrospun nanofibers with gelatin

    NASA Astrophysics Data System (ADS)

    Massoumi, Bakhshali; Ghandomi, Fereshteh; Abbasian, Mojtaba; Eskandani, Morteza; Jaymand, Mehdi

    2016-12-01

    This article describes covalent functionalization of graphene oxide (GO) with poly(2-hydroxyethyl methacrylate)- graft-poly(ɛ-caprolactone) [P(HEMA- g-CL)] via `living' polymerization techniques and preparation of its electrospun nanofibers with gelatin. For this purpose, the GO was synthesized by oxidizing pristine graphite powder and then acetyl chloride was incorporated into the GO to afford an atom transfer radical polymerization (ATRP) macroinitiator (GO-Cl). The synthesized macroinitiator was employed for HEMA polymerization via ATRP technique to produce GO- g-PHEMA. Afterward, CL was graft copolymerized from the hydroxyl groups of the PHEMA via ring-opening polymerization approach to afford GO- g-[P(HEMA- g-CL)] nanocomposite. The solutions of the GO- g-[P(HEMA- g-CL)] and gelatin were electrospun to fabricate uniform, conductive, and biocompatible nanofibers. The morphology, in vitro degradability, biocompatibility, hydrophilicity, and conductivity of the GO- g-[P(HEMA- g-CL)]/gelatin electrospun nanofibers were investigated. It is expected that the prepared nanofibers find application as a scaffolding biomaterial for regenerative medicine, mainly due to their biocompatibility, degradability, and electrical conductivity.

  11. Preparation and characterization of pH-sensitive and antifouling poly(vinylidene fluoride) microfiltration membranes blended with poly(methyl methacrylate-2-hydroxyethyl methacrylate-acrylic acid).

    PubMed

    Ju, Junping; Wang, Chao; Wang, Tingmei; Wang, Qihua

    2014-11-15

    Functional terpolymer of poly(methyl methacrylate-2-hydroxyethyl methacrylate-acrylic acid) (P(MMA-HEMA-AA)) was synthesized via a radical polymerization method. The terpolymer could be directly blended with poly(vinylidene fluoride) (PVDF) to prepare the microfiltration (MF) membranes via phase separate process. The synthesized polymers were characterized by Fourier transform infrared (FTIR), the nuclear magnetic resonance proton spectra ((1)H NMR). The membrane had the typical asymmetric structure and the hydrophilic side chains tended to aggregate on the membrane surface. The surface enrichment of amphiphilic copolymer and morphology of MF membranes were characterized by Fourier transform infrared attenuated total reflection spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM). The contact angle (CA) and water uptake were also tested to assess the hydrophilicity and wetting characteristics of the polymer surface. The water filtration properties were measured. It was found the modified membranes showed excellent pH-sensitivity and pH-reversibility behavior. Furthermore, the hydrophilicity of the blended membranes increased, and the membranes showed good protein antifouling property.

  12. Hydration effects and antifouling properties of poly(vinyl chloride-co-PEGMA) membranes studied using molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Shaikh, Abdul Rajjak; Rajabzadeh, Saeid; Matsuo, Ryuichi; Takaba, Hiromitsu; Matsuyama, Hideto

    2016-04-01

    Polyvinyl chloride (PVC) membranes are widely used in water treatment because of their low cost and chemical stability. However, PVC membranes can become fouled, and this restricts their applications in membrane technology. In order to enhance the antifouling property of PVC membranes, copolymers such as poly(vinyl chloride-co-poly(ethylene glycol)methyl ether methacrylate) (poly(VC-co-PEGMA)) with different PEGMA segment percentages were synthesized in our previous work. Experimentally, it was observed that the poly(VC-co-PEGMA) copolymer has better antifouling properties than those of PVC membranes. Here, we explore effect of the PEGMA segment percentage on the surface hydration properties of poly(VC-co-PEGMA) copolymers. Density functional theory calculations and molecular dynamics simulations were carried out to understand the interactions between PVC and PEGMA. Model structures of these systems were validated by comparing the simulated values of their volumetric properties with the experimental values. MD studies showed that increasing PEGMA percentage in the copolymer increases the interaction with water molecules, leading to improved resistance to fouling. The antifouling mechanism is also discussed with respect to surface hydration and water dynamicity. This study could form a basis for the systematic studies of polymeric membranes as well as their stability from the extent of solvent-polymer, solvent-solvent, and polymer-polymer interactions.

  13. Preparation of superhydrophobic membranes by electrospinning of fluorinated silane functionalized poly(vinylidene fluoride)

    NASA Astrophysics Data System (ADS)

    Chen, Yingbo; Kim, Hern

    2009-05-01

    Fluorinated silane functionalized poly(vinylidene fluoride) (PVDF) is synthesized by graft polymerization of 3-trimethoxylpropyl methylacrylate with PVDF followed by coupling of fluorinated silanes. Flat membrane prepared using this functionalized PVDF has a water contact angle of 140°. Superhydrophobic PVDF membrane with a contact angle larger than 150° is prepared by the electrospinning of the fluorinated silane functionalized PVDF. The morphologies of the membranes are characterized using scanning electron microscopy. The surface composition of the membranes is analyzed using FTIR and the contact angles and water drops on the surface of the membrane are measured using video microscopy.

  14. Preparation of Sulfonated Poly(aryl ether sulfone) Electrospun Mat/Phosphosilicate Composite Proton Exchange Membrane

    NASA Astrophysics Data System (ADS)

    Wang, Limei; Dou, Liyan; Guan, Guoying

    2017-03-01

    Side-chain-type sulfonated poly(aryl ether sulfone) (SPES) was synthesized and then electrospun into mats. Phosphosilicate glass (PS) via in situ sol-gel synthesis was enclosed in the mats to form a new reinforced composite membrane. The SPES/PS composite membranes showed satisfactory dimensional change behavior with varying humidity. Especially, the composite membrane exhibits excellent proton conductivity at harsh measurement conditions of low humidity at 80°C. The composite membrane with outstanding combined properties has potential applications for high temperature polymer electrolyte membrane fuel cells.

  15. Photoelectrical, optical, and transport properties of poly (3-hexylthiophene)-zinc sulfide hybrid nanocomposites

    SciTech Connect

    Singh, Beerandra; Kaur, Amarjeet

    2014-08-14

    We have synthesized nanocomposites of poly (3-hexylthiophene) (P3HT) at 273 K and zinc sulfide (ZnS) nanoparticles at 353 K by the chemical route method. The synthesis of these nanocomposites is confirmed by UV-visible, high resolution transmission electron microscope, and Raman spectroscopy. We have measured photocurrent of P3HT using 50 W tungsten lamp. The photoconductivity increases with concentration of ZnS in P3HT-ZnS composite. Temperature dependent dc conductivity of P3HT and its nanocomposites have been thoroughly investigated in light of Mott's variable range hopping.

  16. Crosslinked carboxymethylchitosan-g-poly(acrylic acid) copolymer as a novel superabsorbent polymer.

    PubMed

    Chen, Yu; Tan, Hui-min

    2006-05-22

    A novel carboxymethylchitosan-g-poly(acrylic acid) (CMCTS-g-PAA) superabsorbent polymer was prepared through graft polymerization of acrylic acid onto the chain of carboxymethylchitosan and subsequent crosslinking. It was demonstrated by FTIR spectroscopy that acrylic acid had been graft polymerized with carboxymethylchitosan. The thermal stability of the polymer was characterized by thermogravimetric analysis. By studying the swelling ratio of the polymer synthesized under different conditions, optimization conditions were found for a polymer with the highest swelling ratio. The rate of water absorption of the polymer was high, and the swelling of the polymer fitted the process of first dynamics. The swelling ratio of the polymer was pH-dependent.

  17. Novel synthesis and DC electrical studies of polyindole/poly(vinyl acetate) composite films

    NASA Astrophysics Data System (ADS)

    Bhagat, D. J.; Dhokane, G. R.

    2015-01-01

    Novel one pot synthesis of polyindole/poly(vinyl acetate) composite films was prepared chemically. The monomer indole was polymerized using oxidant cupric chloride. As-synthesized composites were analyzed by X-ray diffraction, Fourier transform infrared spectroscopy and field emission scanning electron microscope equipped with energy dispersive X-ray spectroscopy. The DC conductivity measurements were done through two probe technique. The DC conductivity value was found to be 8.648 × 10-6 S/cm at 383 K. The transference number measurement shows that ionic conductivity was dominant over electronic conductivity.

  18. Antibacterial properties of novel poly(methyl methacrylate) nanofiber containing silver nanoparticles.

    PubMed

    Kong, Hyeyoung; Jang, Jyongsik

    2008-03-04

    Poly(methyl methacrylate) (PMMA) nanofiber containing silver nanoparticles was synthesized by radical-mediated dispersion polymerization and applied to an antibacterial agent. UV-vis spectroscopic analysis indicated that the silver nanoparticles were continually released from the polymer nanofiber in aqueous solution. The antibacterial properties of silver/PMMA nanofiber against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria were evaluated using minimum inhibitory concentration (MIC), the modified Kirby-Bauer method, and a kinetic test. The MIC test demonstrated that the silver/PMMA nanofiber had enhanced antimicrobial efficacy compared to that of silver sulfadiazine and silver nitrate at the same silver concentration.

  19. Poly(amidoamine) (PAMAM) dendrimers: from biomimicry to drug delivery and biomedical applications.

    PubMed

    Esfand, R; Tomalia, D A.

    2001-04-01

    Poly(amidoamine) (PAMAM) dendrimers are the first complete dendrimer family to be synthesized, characterized and commercialized. Based on this extensive activity, they are recognized as a unique new class of synthetic nanostructures. Dendrimers allow the precise control of size, shape and placement of functional groups that is desirable for many life science applications. From this perspective, this review focuses on crucial properties of biomimetic dendrimers that will broaden the potential for their use as macromolecular vectors in novel drug delivery and biomedical applications.

  20. Preparation of Sulfonated Poly(aryl ether sulfone) Electrospun Mat/Phosphosilicate Composite Proton Exchange Membrane

    NASA Astrophysics Data System (ADS)

    Wang, Limei; Dou, Liyan; Guan, Guoying

    2017-01-01

    Side-chain-type sulfonated poly(aryl ether sulfone) (SPES) was synthesized and then electrospun into mats. Phosphosilicate glass (PS) via in situ sol-gel synthesis was enclosed in the mats to form a new reinforced composite membrane. The SPES/PS composite membranes showed satisfactory dimensional change behavior with varying humidity. Especially, the composite membrane exhibits excellent proton conductivity at harsh measurement conditions of low humidity at 80°C. The composite membrane with outstanding combined properties has potential applications for high temperature polymer electrolyte membrane fuel cells.

  1. Tuning heterogeneous poly(dopamine) structures and mechanics: in silico covalent cross-linking and thin film nanoindentation.

    PubMed

    Lin, Shangchao; Chen, Chun-Teh; Bdikin, Igor; Ball, Vincent; Grácio, José; Buehler, Markus J

    2014-01-21

    Mussel-inspired synthetic poly(dopamine) thin films from dihydroxyphenylalanine (DOPA) and lysine, structurally similar to natural melanin, have drawn extensive interest as a versatile surface functionalization and coating material for use in a broad range of applications. In order to gain a better understanding of its complex and heterogeneous polymeric structure and mechanical properties, we report a computational model of poly(dopamine) by mimicking the polymerization process of the intermediate oxidized product of dopamine, 5,6-dihydroxyindole (DHI), via controlled in silico covalent cross-linking under the two most possible reaction schemes proposed in experiments. To validate our results using experiment, we synthesize poly(dopamine) thin films and perform experimental nanoindentations on the film. We observe an overall linear behavior for Young's modulus as a function of the degree of cross-linking, demonstrating the possibility of enhancing the mechanical robustness of poly(dopamine) materials by increasing the extent of polymerization. At the highest degree of polymerization considered (70%), the model mimics the linear tetrameric model for poly(dopamine) and melanin. At this degree of polymerization, we find a Young's modulus of 4.1-4.4 GPa, in agreement with our nanoindentation results of 4.3-10.5 GPa, previous experiments for natural melanin, as well as simulation results for the cyclic tetrameric melanin model (Chen et al., ACS Nano, 2013). Our results suggest that the non-covalent DHI aggregate model might not be appropriate to represent the structure of poly(dopamine) and melanin-like materials, since it gives a much smaller Young's modulus than the experimental lower bound. Our model not only nicely complements the previous computational work, but also provides new computational tools to study the heterogeneous structural and physicochemical properties of poly(dopamine) and melanin, as well as their formation pathways.

  2. Synthesis and swelling-deswelling kinetics of poly(N-isopropylacrylamide) hydrogels grafted with LCST modulated polymers.

    PubMed

    Kaneko, Y; Nakamura, S; Sakai, K; Kikuchi, A; Aoyagi, T; Sakurai, Y; Okano, T

    1999-01-01

    Two types of thermo-responsive hydrogels are synthesized to obtain comb-type grafted gels with different lower critical solution temperatures (LCSTs) between graft chains and cross-linked backbone networks: these are poly(N-isopropylacrylamide) (PIPAAm) cross-linked hydrogels grafted with poly(N-isopropylacryl amide-co-N,N-dimethylacrylamide) (poly(IPAAm-co-DMAAm)) maintaining a freely mobile end and poly(IPAAm-co-DMAAm) cross-linked hydrogels grafted with PIPAAm chains. The effect of graft chain hydrophilic/hydrophobic balance as well as its mobility on deswelling kinetics of these grafted gels are investigated through the polymer LCST modulation and external temperature changes. The deswelling rate of poly(IPAAm-co-DMAAm)-grafted PIPAAm gel increases with increasing in temperature. This gel shows a discontinuous increase of the deswelling rate when the temperature is applied from below to above the graft chain LCST (37 degrees C). The deswelling rate of PIPAAm-grafted poly(IPAAm-co-DMAAm) gel increases continuously when the temperature is applied from below to above the graft chain LCST (31 degrees C). Due to the strong hydrophilicity of backbone network, the hydrophobic aggregation force weak. In contrast to the graft-type gels, normal-type poly(IPAAm-co-DMAAm) cross-linked gel without graft chains demonstrates the discontinuous decrease for the deswelling rate when the temperature is applied from below to above the polymer LCST (36 degrees C), entrapping water inside the gel due to the formation of an impermeable dense skin layer at the gel surface. These gel deswelling mechanisms are discussed in terms of gel structures.

  3. The poly(A) polymerase GLD2 is required for spermatogenesis in Drosophila melanogaster

    PubMed Central

    Sartain, Caroline V.; Cui, Jun; Meisel, Richard P.; Wolfner, Mariana F.

    2011-01-01

    The DNA of a developing sperm is normally inaccessible for transcription for part of spermatogenesis in many animals. In Drosophila melanogaster, many transcripts needed for late spermatid differentiation are synthesized in pre-meiotic spermatocytes, but are not translated until later stages. Thus, post-transcriptional control mechanisms are required to decouple transcription and translation during spermatogenesis. In the female germline, developing germ cells accomplish similar decoupling through poly(A) tail alterations to ensure that dormant transcripts are not prematurely translated: a transcript with a short poly(A) tail will remain untranslated, whereas elongating the poly(A) tail permits protein production. In Drosophila, the ovary-expressed cytoplasmic poly(A) polymerase WISPY is responsible for stage-specific poly(A) tail extension in the female germline. Here, we examine the possibility that a recently derived testis-expressed WISPY paralog, GLD2, plays a similar role in the Drosophila male germline. We show that knockdown of Gld2 transcripts causes male sterility, as GLD2-deficient males do not produce mature sperm. Spermatogenesis up to and including meiosis appears normal in the absence of GLD2, but post-meiotic spermatid development rapidly becomes abnormal. Nuclear bundling and F-actin assembly are defective in GLD2 knockdown testes and nuclei fail to undergo chromatin reorganization in elongated spermatids. GLD2 also affects the incorporation of protamines and the stability of dynamin and transition protein transcripts. Our results indicate that GLD2 is an important regulator of late spermatogenesis and is the first example of a Gld-2 family member that plays a significant role specifically in male gametogenesis. PMID:21427144

  4. Poly(ethylene glycol)-block-poly(2-methyl-2-benzoxycarbonyl-propylene carbonate) micelles for rapamycin delivery: in vitro characterization and biodistribution.

    PubMed

    Lu, Wenli; Li, Feng; Mahato, Ram I

    2011-06-01

    Our objective was to synthesize an amphiphilic diblock copolymer for micellar delivery of rapamycin. Poly(ethylene glycol)-block-poly(2-methyl-2-benzoxycarbonyl-propylene carbonate) (PEG-b-PBC) with different hydrophobic core lengths were synthesized from methoxy poly(ethylene glycol) and 2-methyl-2-benzoxycarbonyl-propylene carbonate through ring-opening polymerization using 1,8-diazabicycloundec-7-ene as a catalyst. The critical micelle concentration of PEG-b-PBC was around 10(-8) M and depends on the hydrophobic core length. Rapamycin was effectively incorporated into micelles and drug loading increased with increasing hydrophobic core length, with maximal drug loading of 10% (w/w, drug/polymer), drug loading efficiency of about 85%, and mean particle size of around 70 nm. The drug release profile was also dependent on the hydrophobic core length and the drug release from PEG(114) -b-PBC(30) micelles was the slowest. We also determined the toxicity of rapamycin micelles on insulinoma (INS-1E) β-cells and human islets. Encapsulation of rapamycin into PEG-b-PBC micelles reduced its toxicity. Biodistribution of rapamycin-loaded PEG-b-PBC micelles was determined after systemic administration into mice. Rapamycin-loaded PEG-b-PBC micelles showed little difference in pharmacokinetics and biodistribution characteristics in mice compared with rapamycin carrying nanosuspension. In conclusion, rapamycin formulated with PEG-b-PBC micelles showed significantly reduced toxicity on INS-1E β-cells and human islets, but had similar biodistribution profiles as those of nanosuspensions.

  5. TiO2/PCL hybrid materials synthesized via sol-gel technique for biomedical applications.

    PubMed

    Catauro, M; Bollino, F; Papale, F; Marciano, S; Pacifico, S

    2015-02-01

    The aim of the present work has been the synthesis of organic/inorganic hybrid materials based on titanium dioxide and poly(ε-caprolactone) (PCL) to be used in the biomedical field. Several materials have been synthesized using sol-gel methods by adding different amounts of polymer to the inorganic sol. The obtained gels have been characterized using Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The FT-IR data allowed us to hypothesize that the structure formed was that of an interpenetrating network, realized by hydrogen bonds between TiOH groups in the sol-gel intermediate species and carbonyl groups in the polymer repeating units. SEM and AFM analyses highlighted that the obtained materials were nanostructurated hybrids. To evaluate the biological properties of the hybrids, their bioactivity and cytotoxicity were investigated as a function of the PCL amount. The bioactivity of the synthesized systems was proven by the formation of a hydroxyapatite layer on the surface of samples soaked in a fluid simulating human blood plasma (SBF). MTT cytotoxicity tests and Trypan Blue dye exclusion tests were carried out exposing NIH-3T3 mouse embryonic fibroblasts for 24 and 48h to extracts from the investigated hybrid materials. The results showed that all the hybrids had a non-cytotoxic effect on target cells.

  6. [Biosynthesis and accumulation of poly(3-hydroxybutyrate) in Vibrio natriegens].

    PubMed

    Liu, Shuang-Jiang

    2002-09-01

    Accumulation of poly(3-hydroxybutyrate) [poly(3HB)] by V. natriegens was studied. Results indicated that V. natriegens used glucose, gluconate, fructose and molasses as carbon sources for poly(3HB) synthesis. When molasses was used, up to 28.4% of poly(3HB) to cellular dry weight was accumulated. The accumulation of poly(3HB) followed, was not simultaneously to, the cell growth. Analysis of the PHA polymerase, beta-ketothiolase, and acetoacetyl-CoA reductase showed that the poly(3HB) accumulation was correlated to the increase of their activities in cells. Poly(3HB) accumulation was also related to the de novo fatty acid synthesis, as revealed by the results that cerulenin, a specific inhibitor to the de novo fatty acid synthesis, significantly reduced accumulation of poly(3HB). Based on the results from this study, the synthetic pathway of poly(3HB) was proposed.

  7. Endothelial cells synthesize and process apolipoprotein B.

    PubMed

    Sivaram, P; Vanni-Reyes, T; Goldberg, I J

    1996-06-21

    We reported previously that a 116-kDa lipoprotein lipase (LPL)-binding protein from endothelial cells has sequence homology to the amino-terminal region of apolipoprotein (apo) B. We now tested whether endothelial cells synthesize apoB mRNA and protein. Primers were designed to the human apoB cDNA sequence and reverse transcription polymerase chain reaction was performed using total RNA isolated from bovine and human endothelial cells. With primers to the 5' region of the apoB mRNA (amino-terminal region of apoB protein) expected size PCR products were generated from both bovine and human endothelial cells as well as from mouse liver RNA, which was used as a control. Primers designed to the 3' region of apoB mRNA generated PCR products from human endothelial cells and HepG2 cells but not from bovine or mouse cells. These data suggest that endothelial cells contain full-length apoB mRNA and that the 5' or the amino-terminal region of apoB is highly conserved from mouse to human. This was confirmed by direct sequencing of the mouse and bovine PCR products. To test whether apoB protein was produced, bovine endothelial cell proteins were metabolically labeled with [35S]methionine/cysteine or [3H]leucine and immunoprecipitated with anti-human apoB antibodies. Using extracts from cells labeled for 1 h, monoclonal antibody 47, directed to the low density lipoprotein receptor binding region of apoB, precipitated a protein of approximate molecular mass 550,000, the size of full-length apoB. Immunoprecipitation of the 550-kDa protein was abolished in the presence of added unlabeled low density lipoprotein. From cells labeled for 16 h, a 116-kDa protein was immunoprecipitated by polyclonal anti-apoB antibodies. This protein was partly released from cells by heparin treatment. Pulse-chase analysis showed that the 116-kDa fragment appeared at the same time as the full-length apoB began disappearing. The immunoprecipitated 116-kDa fragment also bound labeled LPL on ligand blot

  8. Synthesized Spectra of Optically Thin Emission Lines

    NASA Astrophysics Data System (ADS)

    Olluri, K.; Gudiksen, B. V.; Hansteen, V. H.; De Pontieu, B.

    2015-03-01

    In recent years realistic 3D numerical models of the solar atmosphere have become available. The models attempt to recreate the solar atmosphere and mimic observations in the best way, in order to make it possible to couple complicated observations with physical properties such as the temperatures, densities, velocities, and magnetic fields. We here present a study of synthetic spectra created using the Bifrost code in order to assess how well they fit with previously taken solar data. A study of the synthetic intensity, nonthermal line widths, Doppler shifts, and correlations between any two of these three components of the spectra first assuming statistical equilibrium is made, followed by a report on some of the effects nonequilibrium ionization will have on the synthesized spectra. We find that the synthetic intensities compare well with the observations. The synthetic observations depend on the assumed resolution and point-spread function (PSF) of the instrument, and we find a large effect on the results, especially for intensity and nonthermal line width. The Doppler shifts produce the reported persistent redshifts for the transition region (TR) lines and blueshifts for the upper TR and corona lines. The nonthermal line widths reproduce the well-known turnoff point around (2-3) × 105 K, but with much lower values than those observed. The nonthermal line widths tend to increase with decreasing assumed instrumental resolution, also when nonequilibrium ionization is included. Correlations between the nonthermal line width of any two TR line studies as reported by Chae et al. are reproduced, while the correlations of intensity to line width are reproduced only after applying a PSF to the data. Doppler shift correlations reported by Doschek for the TR lines and correlations of Doppler shift to nonthermal line width of the Fe xii 19.5 line reported by Doschek et al. are reproduced.

  9. Human brain glial cells synthesize thrombospondin.

    PubMed Central

    Asch, A S; Leung, L L; Shapiro, J; Nachman, R L

    1986-01-01

    Thrombospondin, a 450-kDa multinodular glycoprotein with lectin-type activity, is found in human platelets, endothelial cells, fibroblasts, smooth muscle cells, monocytes, and granular pneumocytes. Thrombospondin interacts with heparin, fibrinogen, fibronectin, collagen, histidine-rich glycoprotein, and plasminogen. Recently, thrombospondin synthesis by smooth muscle cells has been reported to be augmented by platelet-derived growth factor. We present evidence that thrombospondin is present within and synthesized by astrocytic neuroglial cells. Heparin-Sepharose affinity chromatography of material derived from a human brain homogenate yielded a protein that, when reduced, had an apparent size of 180 kDa and comigrated with reduced platelet thrombospondin on NaDodSO4/PAGE. Immunoblot analysis with monospecific anti-thrombospondin confirmed the presence of immunoreactive thrombospondin. Indirect immunofluorescence of cultured human glial cells indicated the presence of thrombospondin. Metabolic labeling of glial cell cultures with [35S]methionine followed by immunoprecipitation with monospecific anti-thrombospondin revealed synthesis of a 180-kDa polypeptide that comigrated with platelet thrombospondin on NaDodSO4/PAGE. Cultured human glial cells were incubated for 48 hr in serum-free medium with purified platelet-derived growth factor at concentrations up to 50 ng/ml. Aliquots taken at intervals were analyzed by a quantitative double-antibody ELISA. The growth factor stimulated the release of thrombospondin into the culture medium by as much as 10-fold over control cultures. The presence of thrombospondin within glial cells of the central nervous system and the augmentation of its synthesis by platelet-derived growth factor suggest that thrombospondin may play an important role in regulating cell-cell and cell-matrix interactions during periods of cell division and growth. Images PMID:2939460

  10. Thermodynamics of Polymer Adsorption onto Nanoporous Silica and its Application in the Large Scale Purification of Poly(styrene)-block-Poly(alkyl methacrylate) Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Abdulahad, Asem Irfan

    As a result of unavoidable inconsistencies in their synthesis via controlled radical polymerization techniques, block copolymers inherently have distributions in chemical composition and molecular weight in each block that can have significant impact on their viscoelastic properties as well as their ability to self-assemble into ordered phases. High performance liquid chromatography is routinely utilized for determining the average molecular weight distribution that exist in synthetic polymers and is becoming increasingly popular for the fractionation and purification of chemically diverse complex polymer materials such as diblock copolymers. However, the inability of HPLC fractionation to provide meaningful quantities of purified complex polymers makes this method extremely inefficient and limits the ability to characterize purified fractions further. Overall, this dissertation work can be digested in two distinct parts. In the first part, high performance liquid chromatography was used as a tool for studying the influential parameters affecting the critical adsorption point of poly(styrene) and poly(alkyl methacrylate) homopolymers. The understanding gained in the first portion was depended on for the development of large scale fractionation procedures. In the second part, a chemically diverse variety of poly(alkyl methacrylate)-block-poly(styrene) diblock copolymers synthesized by atom transfer radical polymerization and anionic polymerization were purified by large scale adsorption-based fractionation procedures that included chromatographic filtration and the sequential adsorption/desorption of bulk diblock copolymer materials. The impact of diblock copolymer purification is addressed by comparing the molecular weight distribution, chemical composition distribution, viscoelastic properties, and small-angle X-ray scattering profiles.

  11. Surface chemistry of poly(p-xylylene) and nylon

    NASA Astrophysics Data System (ADS)

    Herrera-Alonso, Margarita

    The interaction of a material with its surroundings occurs at the material-environment interface, therefore, the chemical and physical characteristics of the material's surface plays a fundamental role in determining its properties, such as its biocompatibility, adhesion, and wettability, and ultimately, its technological applicability. This dissertation discusses aspects of the chemical surface modification of two polymers, poly(p-xylylene) and nylon. Chapter 2 focuses on the synthesis and wet-chemistry surface modification of poly(p-xylylene) (PPX) thin films. A series of electrophilic aromatic substitutions were studied including chlorosulfonation, chloroamidomethylation, and Friedel-Crafts catalyzed reactions. It was found that the yields and surface selectivity of the reactions studied were highly dependent on the interaction of the polymer with the reaction medium. Chapter 3 describes the use of vapor deposition polymerization in template-assisted synthesis. Poly(p-xylylene) nanotubes were synthesized by template assisted methods using porous aluminum oxide membranes as the templating material. The pore diameter showed a linear dependence with respect to the deposition time. FESEM analysis showed that PPX was deposited along the pores of the membranes. Exposure of the membranes to a reactive solution resulted in chemical functionalization of the inner walls of the nanotubes, confirmed by XPS. Chapter 4 discusses the chemical reduction of nylon film surfaces by reaction with a borane-tetrahydrofuran complex. It was observed that, while the reaction occurs in high yields, its surface-confinement is highly dependent on the segmental mobility of the polymer. The amine-rich surfaces were further used as templates for the synthesis of composite films by electrostatic adsorption of polyanions. Chapter 5 deals with the synthesis of linear polyalkyleneimines of different hydrocarbon lengths by the surface-mediated reduction of nylons. These polyalkyleneimines were

  12. Synthesis of Poly(4-((phenylimino)methyl)benzene-1,2,3-triol) and Its Application for Improving the Heterostructure Device Characteristics

    NASA Astrophysics Data System (ADS)

    Demir, Haci Okkes; Ozkaya, Suat

    2017-01-01

    A trihydroxy substituted poly(4-((phenylimino)methyl)benzene-1,2,3-triol) abbreviated as poly(2,3,4-PIMB), poly(phenoxy-imine)-type polymer, has been successfully synthesized by oxidative coupling polymerization in an aqueous alkaline medium using sodium hypochlorite. Detailed structural characterization of the phenoxy-imine type monomer and its polymer were investigated by Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H-NMR), ultraviolet-visible (UV-Vis), and gel permeation chromatography spectroscopy techniques. According to these analyses, the synthesized polymer has its backbone made of oxyphenylene linkages only. The solubility, thermal stability, electrochemical, and optic features of the polymer and its monomer were also evaluated. Furthermore, seven Ni/poly(2,3,4-PIMB)/ p-Si/Al heterostructure devices were fabricated, and they showed good rectifying behavior such that the ideality factor and the barrier height values ranged from 1.54 eV to 1.78 eV and from 0.62 eV to 0.67 eV, respectively. The capacitance-voltage measurements of one Ni/poly(2,3,4-PIMB)/ p-Si/Al heterostructure device were also analyzed.

  13. Chitosan grafted methoxy poly(ethylene glycol)-poly(ε-caprolactone) nanosuspension for ocular delivery of hydrophobic diclofenac.

    PubMed

    Shi, Shuai; Zhang, Zhaoliang; Luo, Zichao; Yu, Jing; Liang, Renlong; Li, Xingyi; Chen, Hao

    2015-06-12

    This study aimed to develop a cationic nanosuspension of chitosan (CS) and methoxy poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) for ocular delivery of diclofenac (DIC). MPEG-PCL-CS block polymer was synthesized by covalent coupling of MPEG-PCL with CS. The critical micelle concentration of the MPEG-PCL-CS block polymer was 0.000692 g/L. DIC/MPEG-PCL-CS nanosuspension (mean particle size = 105 nm, zeta potential = 8 mV) was prepared and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry. The nanosuspension was very stable without apparent physical property changes after storage at 4 °C or 25 °C for 20 days, but it was unstable in the aqueous humor solution after 24 h incubation. Sustained release of the encapsulated DIC from the nanosuspension occurred over 8 h. Neither a blank MPEG-PCL-CS nanosuspension nor a 0.1% (mass fraction) DIC/MPEG-PCL-CS nanosuspension caused ocular irritation after 24 h of instillation. Enhanced penetration and retention in corneal tissue was achieved with a Nile red/MPEG-PCL-CS nanosuspension compared with a Nile red aqueous solution. In vivo pharmacokinetics studies showed enhanced pre-corneal retention and penetration of the DIC/MPEG-PCL-CS nanosuspension, which resulted in a higher concentration of DIC (Cmax) in the aqueous humor and better bioavailability compared with commercial DIC eye drops (P < 0.01).

  14. Chitosan grafted methoxy poly(ethylene glycol)-poly(ε-caprolactone) nanosuspension for ocular delivery of hydrophobic diclofenac

    PubMed Central

    Shi, Shuai; Zhang, Zhaoliang; Luo, Zichao; Yu, Jing; Liang, Renlong; Li, Xingyi; Chen, Hao

    2015-01-01

    This study aimed to develop a cationic nanosuspension of chitosan (CS) and methoxy poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) for ocular delivery of diclofenac (DIC). MPEG-PCL-CS block polymer was synthesized by covalent coupling of MPEG-PCL with CS. The critical micelle concentration of the MPEG-PCL-CS block polymer was 0.000692 g/L. DIC/MPEG-PCL-CS nanosuspension (mean particle size = 105 nm, zeta potential = 8 mV) was prepared and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry. The nanosuspension was very stable without apparent physical property changes after storage at 4 °C or 25 °C for 20 days, but it was unstable in the aqueous humor solution after 24 h incubation. Sustained release of the encapsulated DIC from the nanosuspension occurred over 8 h. Neither a blank MPEG-PCL-CS nanosuspension nor a 0.1% (mass fraction) DIC/MPEG-PCL-CS nanosuspension caused ocular irritation after 24 h of instillation. Enhanced penetration and retention in corneal tissue was achieved with a Nile red/MPEG-PCL-CS nanosuspension compared with a Nile red aqueous solution. In vivo pharmacokinetics studies showed enhanced pre-corneal retention and penetration of the DIC/MPEG-PCL-CS nanosuspension, which resulted in a higher concentration of DIC (Cmax) in the aqueous humor and better bioavailability compared with commercial DIC eye drops (P < 0.01). PMID:26067670

  15. Improved thermoelectric behavior of nanotube-filled polymer composites with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate).

    PubMed

    Kim, Dasaroyong; Kim, Yeonseok; Choi, Kyungwho; Grunlan, Jaime C; Yu, Choongho

    2010-01-26

    The thermoelectric properties of carbon nanotube (CNT)-filled polymer composites can be enhanced by modifying junctions between CNTs using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), yielding high electrical conductivities (up to approximately 40000 S/m) without significantly altering thermopower (or Seebeck coefficient). This is because PEDOT:PSS particles are decorated on the surface of CNTs, electrically connecting junctions between CNTs. On the other hand, thermal transport remains comparable to typical polymeric materials due to the dissimilar bonding and vibrational spectra between CNT and PEDOT:PSS. This behavior is very different from that of typical semiconductors whose thermoelectric properties are strongly correlated. The decoupled thermoelectric properties, which is ideal for developing better thermoelectric materials, are believed to be due to thermally disconnected and electrically connected contact junctions between CNTs. Carrier transport at the junction is found to be strongly dependent on the type and concentration of stabilizers. The crucial role of stabilizers was revealed by characterizing transport characteristics of composites synthesized by electrically conducting PEDOT:PSS and insulating gum Arabic (GA) with 1:1-1:4 weight ratios of CNT to stabilizers. The influence of composite synthesis temperature and CNT-type and concentration on thermoelectric properties has also been studied. Single-walled (SW) CNT-filled composites dried at room temperature followed by 80 degrees C exhibited the best thermoelectric performance in this study. The highest thermoelectric figure of merit (ZT) in this study is estimated to be approximately 0.02 at room temperature, which is at least one order of magnitude higher than most polymers and higher than that of bulk Si. Further studies with various polymers and nanoparticles with high thermoelectric performance may result in economical, lightweight, and efficient polymer thermoelectric

  16. Synthesis of mesoporous poly(melamine-formaldehyde) particles by inverse emulsion polymerization.

    PubMed

    Schwarz, Dana; Weber, Jens

    2017-07-15

    Mesoporous poly(melamine-formaldehyde) (MF) particles with surface areas of up to 200m(2)g(-1) were synthesized by an inverse emulsion polymerization using dodecane and Span80® as continuous phase. The finer details of the shape control (using emulsion techniques) and the porosity control (using silica nanoparticles as hard-template) are discussed. The impact of phase-separation processes on the observable porosity of the 20-200µm sized spherical particles is analysed by gas sorption methods and electron microscopy. The high density of amine and triazine functional groups in the porous MF particles make the material a promising adsorber for heavy metal ions and methylene blue. In a preliminary column experiment, the synthesized material exhibited a total capacity of 2.54mmol/g (≙ 812.4mg/g) for the adsorption of methylene blue.

  17. Poly (acrylic acid)-capped lanthanide-doped BaFCl nanocrystals: synthesis and optical properties.

    PubMed

    Ju, Qiang; Luo, Wenqin; Liu, Yongsheng; Zhu, Haomiao; Li, Renfu; Chen, Xueyuan

    2010-07-01

    Water-soluble lanthanide-doped BaFCl nanophosphors with the surface functionalized by a layer of poly (acrylic acid) are synthesized via a facile one-step solvothermal method. Intense long-lived luminescence is realized from visible to near-infrared (NIR) by doping with different lanthanide ions. The emission and excitation spectra of Eu(3+) indicate that the doped lanthanide ions occupy a site close to the surface of the nanoparticles. Strong NIR emissions of Nd(3+) and green luminescence of Tb(3+) using Ce(3+) as sensitizers are also achieved in BaFCl nanoparticles. The synthesized nanoparticles featuring long-lived luminescence in either visible or NIR regions may have potential applications as luminescent labels for biological applications.

  18. Effect of crosslinker length on the elastic and compression modulus of poly(acrylamide) nanocomposite hydrogels

    NASA Astrophysics Data System (ADS)

    Zaragoza, J.; Chang, A.; Asuri, P.

    2017-01-01

    Polymer hydrogelshave shown to exhibit improved properties upon the addition of nanoparticles; however, the mechanical underpinnings behind these enhancements have not been fully elucidated. Moreover, fewer studies have focused on developing an understanding of how polymer parameters affect the nanoparticle-mediated enhancements. In this study, we investigated the elastic properties of silica nanoparticle-reinforced poly(acrylamide) hydrogels synthesized using crosslinkers of various lengths. Crosslinker length positively affected the mechanical properties of hydrogels that were synthesized with or without nanoparticles. However the degree of nanoparticle enhancement was negatively correlated to crosslinker length. Our findings enable the understanding of the respective roles of nanoparticle and polymer properties on nanoparticle-mediated enhancement of hydrogels and thereby the development of next-generation nanocomposite materials.

  19. Syntheses and electronic structures of decamethylmetallocenes

    SciTech Connect

    Robbins, J.L.

    1981-04-01

    The synthesis of decamethylmanganocene ((eta-C/sub 5/(CH/sub 3/)/sub 5/)/sub 2/Mn or (Me/sub 5/Cp)/sub 2/Mn)) is described. Magnetic susceptibility and electron paramagnetic resonance (EPR) studies show that (Me/sub 5/Cp)/sub 2/Mn is a low-spin, 17-electron compound with an orbitally degenerate, /sup 2/E/sub 2g/ (e/sub 2g//sup 3/ a/sub 1g//sup 2/) ground state. An x-ray crystallographic study of (Me/sub 5/Cp)/sub 2/Mn shows that it is a monomeric, D/sub 5d/ decamethylmetallocene with metal to ring carbon distances that are about 0.3 A shorter than those determined for high-spin manganocenes. The syntheses of new (Me/sub 5/Cp)/sub 2/M (M = Mg,V,Cr,Co, and Ni) and ((Me/sub 5/Cp)/sub 2/M)PF/sub 6/ (M = Cr,Co, and Ni) compounds are described. In addition, a preparative route to a novel, dicationic decamethylmetallocene, ((Me/sub 5/Cp)/sub 2/Ni)(PF/sub 6/)/sub 2/ is reported. Infrared, nuclear magnetic resonance, magnetic susceptibility, and/or x-ray crystallographic studies indicate that all the above compounds are D/sub 5d/ or D/sub 5h/ decamethylmetallocenes with low-spin electronic configurations. Cyclic voltammetry studies verify the reversibility and the one-electron nature of the (Me/sub 5/Cp)/sub 2/M ..-->.. ((Me/sub 5/Cp)/sub 2/M)/sup +/ (M = Cr,Mn,Fe,Co,Ni), ((Me/sub 5/Cp)/sub 2/Mn)/sup -/ ..-->.. (Me/sub 5/Cp)/sub 2/Mn and ((Me/sub 5/Cp)/sub 2/Ni)/sup +/ ..-->.. (Me/sub 5/Cp)/sub 2/Ni)/sup 2 +/ redox reactions. These studies reveal that the neutral decamethylmetallocenes are much more easily oxidized than their metallocene counterparts. This result attests to the electron-donating properties of the ten substituent methyl groups. Proton and carbon-13 NMR data are reported for the diamagnetic Mg(II), Mn(I), Fe(II), Co(III), and Ni(IV) decamethylmetallocenes and for ((Me/sub 5/Cp)/sub 2/V(CO)/sub 2/)/sup +/. The uv-visible absorption spectra of the 15-, 18- and 20- electron decamethylmetallocenes are also reported.

  20. Development of frequency synthesizer for fast frequency hopping communication equipment

    NASA Astrophysics Data System (ADS)

    Sekizawa, Shinya; Moriyama, Eimatsu

    1990-06-01

    A frequency synthesizer with rapid operation is necessary for the development of fast frequency hopping communication systems in land mobile radios. On the other hand, accuracy is not so important in the fast frequency hopping systems when envelope detection is employed in a receiver. Currently, there are several types of frequency synthesizers. However, they are not sufficient in terms of switching speed, size and cost. A frequency synthesizer with rapid hopping based on a new operating principle is proposed and developed. It is a small synthesizer, consisting of digital devices, available at a low cost. The experimental results show that the synthesizer has the switching performance necessary for frequency hopping land mobile radios. This paper describes the operating principle and the experimental results of the proposed synthesizer.

  1. Biodegradable block poly(ester-urethane)s based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers.

    PubMed

    Ou, Wenfeng; Qiu, Handi; Chen, Zhifei; Xu, Kaitian

    2011-04-01

    A series of block poly(ester-urethane)s (abbreviated as PU3/4HB) based on biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB) segments were synthesized by a facile way of melting polymerization using 1,6-hexamethylene diisocyanate (HDI) as the coupling agent and stannous octanoate (Sn(Oct)(2)) as catalyst, with different 4HB contents and segment lengths. The chemical structure, molecular weight and distribution were systematically characterized by (1)H nuclear magnetic resonance spectrum (NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The thermal property was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hydrophilicity was investigated by static contact angle of deionized water and CH(2)I(2). DSC curves revealed that the PU3/4HB polyurethanes have their T(g) from -25.6 °C to -4.3 °C, and crystallinity from 2.5% to 25.3%, being almost amorphous to semi-crystalline. The obtained PU3/4HBs are hydrophobic (water contact angle 77.4°-95.9°), and their surface free energy (SFE) were studied. The morphology of platelets adhered on the polyurethane film observed by scanning electron microscope (SEM) showed that platelets were activated on the PU3/4HB films which would lead to blood coagulation. The lactate dehydrogenase (LDH) assay revealed that the PU3/4HBs displayed higher platelet adhesion property than raw materials and biodegradable polymer polylactic acid (PLA) and would be potential hemostatic materials. Crystallinity degree, hydrophobicity, surface free energy and urethane linkage content play important roles in affecting the LDH activity and hence the platelet adhesion. CCK-8 assay showed that the PU3/4HB is non-toxic and well for cell growth and proliferation of mouse fibroblast L929. It showed that the hydrophobicity is an important factor for cell growth while 3HB content of the PU3/4HB is important for the cell proliferation. Through changing the

  2. Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

    NASA Astrophysics Data System (ADS)

    Rosenthal-Kim, Emily Quinn

    The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight

  3. Damage to the protein synthesizing apparatus in mouse liver in vivo by magnetocytolysis in the presence of hepatospecific magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Halbreich, Avraham; Groman, Ernest V.; Raison, Danielle; Bouchaud, Claude; Paturance, Sébastien

    2002-07-01

    In the previous work, we incubated THP1 cells and macrophages in vitro with unsubstituted ferrofluid (FF) and placed them in an alternating magnetic field. This resulted in the destruction of the cells (magnetocytolysis). Cell-specific magnetocytolysis in vitro was achieved in MCF7 human breast cancer cells incubated with tamoxifen-bound FF and treated in an alternating magnetic field. In this work, in a search of a model for magnetocytolysis in vivo, we injected mice intravenously with hepatospecific magnetic nanoparticles (HS-USPIO) and subjected the mice to magnetocytolysis in an alternating magnetic field (1 h at 200 A/m). This treatment resulted in a prolongation of blood coagulation time due to depletion of protein coagulation factors that are synthesized exclusively in the liver. The attendant derangement of liver protein synthesis was characterized in cell-free preparations by an inhibition of the endogenously coded protein synthesis coupled with an enhancement of phenylalanine polymerization directed by polyuridylic acid (Poly U). This indication of polyribosome dispersion was confirmed by electron microscopy. Magnetocytolysis did not cause liver necrosis and was neither accompanied by any increase in body or liver temperature, nor damage to any other tissue. The effects of magnetocytolysis were proportional to the amount of injected HS-USPIO, field strength and its application time. Magnetocytolysis did not occur when non-magnetic PolyGalactoseGold particles were substituted for HS-USPIO. PolyGalactoseGold particles were employed to measure asialoglycoprotein receptor (ASGP-R) activity in liver using neutron activation analysis. Injection of PolyGalactoseGold particles to mice, pre-treated by HS-USPIO driven magnetocytolysis, revealed a transient diminution of hepatic ASGP-R. Liver damage from magnetocytolysis was followed by liver regeneration, manifested by the appearance of thymidylate kinase activity, diminution of ASGP-R and return to normal blood

  4. MM-wave synthesizer has 8-to-15-GHz bandwidth

    NASA Astrophysics Data System (ADS)

    Fortunato, M. P.; Ishikawa, K. Y.

    1982-05-01

    Millimeter-wave sweeper IMPATT diodes are combined with microprocessor control and opamp circuitry to give a fast and accurate W-band synthesizer. The breakthrough in millimeter-wave frequency synthesizer development derives from the ability to lock virtually any millimeter-wave IMPATT. The considerable improvement in SSB phase noise of a phase-locked sweeper IMPATT versus a free-running Gunn, fixed-tuned IMPATT, and free-running sweeper IMPATT is illustrated. The spectra of a free-running and a phase-locked sweeper IMPATT are compared. A block diagram of the complete millimeter-wave synthesizer is included, together with typical W-band synthesizer specifications.

  5. Facile synthesis of brush poly(phosphoamidate)s via one-pot tandem ring-opening metathesis polymerization and atom transfer radical polymerization.

    PubMed

    Ding, Liang; Qiu, Jun; Wei, Jun; Zhu, Zhenshu

    2014-09-01

    Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)-based brush poly(phosphoamidate)s are successfully synthesized by a combination of ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) following either a commutative two-step procedure or a straightforward one-pot process using Grubbs ruthenium-based catalysts for tandem catalysis. Compared with the traditional polymerization method, combining ROMP and ATRP in a one-pot process allows the preparation of brush copolymers characterized by a relatively moderate molecular weight distribution and quantitative conversion of monomer. Moreover, the surface morphologies and aggregation behaviors of these polymers are studied by AFM and TEM measurements.

  6. Tailoring the degradation kinetics of poly(ester-carbonate urethane)urea thermoplastic elastomers for tissue engineering scaffolds

    PubMed Central

    Hong, Yi; Guan, Jianjun; Fujimoto, Kazuro L.; Hashizume, Ryotaro; Pelinescu, Anca L.; Wagner, William R.

    2010-01-01

    Biodegradable elastomeric scaffolds are of increasing interest for applications in soft tissue repair and regeneration, particularly in mechanically active settings. The rate at which such a scaffold should degrade for optimal outcomes, however, is not generally known and the ability to select from similar scaffolds that vary in degradation behavior to allow such optimization is limited. Our objective was to synthesize a family of biodegradable polyurethane elastomers where partial substitution of polyester segments with polycarbonate segments in the polymer backbone would lead to slower degradation behavior. Specifically, we synthesized poly(ester carbonate)urethane ureas (PECUUs) using a blended soft segment of poly(caprolactone) (PCL) and poly(1,6-hexamethylene carbonate) (PHC), a 1,4-diisocyanatobutane hard segment and chain extension with putrescine. Soft segment PCL/PHC molar ratios of 100/0, 75/25, 50/50, 25/75, and 0/100 were investigated. Polymer tensile strengths varied from 14-34 MPa with breaking strains of 660-875%, initial moduli of 8-24 MPa and 100% recovery after 10% strain. Increased PHC content was associated with softer, more distensible films. Scaffolds produced by salt leaching supported smooth muscle cell adhesion and growth in vitro. PECUU in aqueous buffer in vitro and subcutaneous implants in rats of PECUU scaffolds showed degradation slower than comparable poly(ester urethane)urea and faster than poly(carbonate urethane)urea. These slower degrading thermoplastic polyurethanes provide opportunities to investigate the role of relative degradation rates for mechanically supportive scaffolds in a variety of soft tissue repair and reconstructive procedures. PMID:20188411

  7. Ketoprofen-poly(vinylpyrrolidone) physical interaction

    NASA Astrophysics Data System (ADS)

    Di Martino, Piera; Joiris, Etienne; Gobetto, Roberto; Masic, Admir; Palmieri, Giovanni F.; Martelli, Sante

    2004-04-01

    Amorphous solid solutions were obtained in different proportions by dissolving ketoprofen (Ket) and poly(vinylpyrrolidone) (PVP) K30 in methanol and by evaporating them under reduced pressure. Their physical properties were studied by powder X-ray diffraction and by differential scanning calorimetry and compared to that of same physical mixtures (PM). The interaction of Keto and poly(vinylpyrrolidone) K30 in the solid state was then investigated by 13C NMR CPMAS analysis. The results indicated that in the Ket-(PVP) co-precipitates, the ket molecules, interacting with their carboxylic group through hydrogen bonding with the poly(vinylpyrrolidone) moieties, are molecularly and irregularly dispersed within the amorphous solvendum that acts as mechanical substratum for amorphous stabilization. In their simple PM, no evidence exists of the Ket-polymer interaction during the considered time interval.

  8. Pilot-scale synthesis and rheological assessment of poly(methyl methacrylate) polymers: perspectives for medical application.

    PubMed

    Linan, Lamia Zuniga; Nascimento Lima, Nádson M; Filho, Rubens Maciel; Sabino, Marcos A; Kozlowski, Mark T; Manenti, Flavio

    2015-06-01

    This work presents the rheological assessment of poly(methyl methacrylate) (PMMA) polymers synthesized in a dedicated pilot-scale plant. This material is to be used for the construction of scaffolds via Rapid Prototyping (RP). The polymers were prepared to match the physical and biological properties required for medical applications. Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC) measurements verified that the synthesized polymers were atactic, amorphous and linear in chains. Rheological properties such as viscosity, storage and loss modulus, beyond the loss factor, and creep and recovery were measured in a plate-plate sensor within the viscoelastic linear region. The results showed the relevant influence of the molecular weight on the viscosity and elasticity of the material, and how, as the molecular weight increases, the viscoelastic properties are getting closer to those of human bone. This article demonstrates that by using the implemented methodology it is possible to synthesize a polymer, with properties comparable to commercially-available PMMA.

  9. The thermodynamic contribution of the 5-methyl group of thymine in the two- and three-stranded complexes formed by poly(dU) and poly(dT) with poly(dA).

    PubMed

    Ross, Philip D; Howard, Frank B

    2003-02-01

    To assess the thermodynamic contribution of the 5-methyl group of thymine, we have studied the two-stranded helical complexes poly(dA).poly(dU) and poly(dA).poly(dT) and the three-stranded complexes--poly(dA).2poly(dU), poly(dA).poly(dT).poly(dU) and poly(dA).2poly(dT)--by differential scanning calorimetry, and uv optical melting experiments. The thermodynamic quantities associated with the 3 --> 2, 2 --> 1, and 3 --> 1 melting transitions are found to vary with salt concentration and temperature in a more complex manner than commonly believed. The transition temperatures, T(m), are generally not linear in the logarithm of concentration or activity of NaCl. The change in enthalpy and in entropy upon melting varies with salt concentration and temperature, and a change in heat capacity accompanies each transition. The poly(dA).2poly(dU) triple helix is markedly different from poly(dA).2poly(dT) in both its CD spectrum and thermodynamic behavior, while the poly(dA).poly(dT).poly(dU) triple helix resembles poly(dA).2poly(dT) in these properties. In comparing poly(dA).2poly(dT) with either the poly(dA).poly(dT).poly(dU) or the poly(dA).2poly(dU) triplexes, the substitution of thymine for uracil in the third strand results in an enhancement of stability against the 3 --> 2 dissociation of deltadeltaG degrees = -135 +/- 85 cal (mol A)(-1) at 37 degrees C. This represents a doubling of the absolute stability toward dissociation compared to the triplexes with poly(dU) as the third strand. The poly (dA).poly (dT) duplex is more stable than poly(dA).poly(dU) by deltadeltaG degrees = -350 +/- 60 cal (mol base pair)(-1) at 37 degrees C. Poly(dA).poly(dT) has 50% greater stability than poly(dA).poly(dU) as a result of the dT for dU substitution in the duplex.

  10. Soluble non-cross-linked poly(norbornene) supports for peptide synthesis with minimal reagents.

    PubMed

    Naganna, Nimmashetti; Madhavan, Nandita

    2014-12-05

    Solid-phase peptide synthesis has been an attractive method for synthesizing peptides because it is quick and can be automated. The heterogeneous reaction medium in solid-phase peptide synthesis necessitates the use of large equivalents of reagents to drive the reactions to completion. Peptide synthesis using soluble, yet isolable, supports is an attractive alternative to solid-phase peptide synthesis. Reported herein is a soluble poly(norbornene)-derived support containing multiple attachment sites for high loading capacities and solubilizing oligoether/alkyl groups. The Ala-attached support has been used to synthesize tri- to octapeptides in 28 to 97% yields using only 1.2 equiv of amino acids and coupling reagents. The acyclic hexapeptide precursor to natural product segatalin A was synthesized in 41% yield on the support using one-eighth of the equivalents of coupling reagents compared to that in reported procedures. The support could be recovered in up to 98% yield after peptide synthesis, and the recovered support was utilized to synthesize tri- and tetrapeptides that contain amino acids other than Ala at the C-terminus in ca. 80% yields.

  11. Imidazolium-Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer-Supported N-Heterocyclic Carbenes for Organocatalysis.

    PubMed

    Lambert, Romain; Coupillaud, Paul; Wirotius, Anne-Laure; Vignolle, Joan; Taton, Daniel

    2016-07-01

    Statistical copoly(ionic liquid)s (coPILs), namely, poly(styrene)-co-poly(4-vinylbenzylethylimidazolium acetate) are synthesized by free-radical copolymerization in methanolic solution. These coPILs serve to in situ generate polymer-supported N-heterocyclic carbenes (NHCs), referred to as polyNHCs, due to the noninnocent role of the weakly basic acetate counter-anion interacting with the proton in C2-position of pendant imidazolium rings. Formation of polyNHCs is first evidenced through the quantitative formation of NHC-CS2 units by chemical postmodification of acetate-containing coPILs, in the presence of CS2 as electrophilic reagent (= stoichiometric functionalization of polyNHCs). The same coPILs are also employed as masked precursors of polyNHCs in organocatalyzed reactions, including a one-pot two-step sequential reaction involving benzoin condensation followed by addition of methyl acrylate, cyanosilylation, and transesterification reactions. The catalytic activity can be switched on and off successively upon thermal activation, thanks to the deprotonation/reprotonation equilibrium in C2-position. NHC species are thus in situ released upon heating at 80 °C (deprotonation), while regeneration of the coPIL precursor occurs at room temperature (reprotonation), triggering its precipitation in tetrahydrofuran. This also allows recycling the coPIL precatalyst by simple filtration, and reusing it for further catalytic cycles. The different organocatalyzed reactions tested can thus be performed with excellent yields after several cycles.

  12. Synthesis and Properties of Poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] Fiber

    PubMed Central

    Lin, Hong; Huang, Yu-Dong; Wang, Feng

    2008-01-01

    The novel polymer poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] (PBOH) fiber was synthesized in the presence of 2,5-dihydroxyterephthalicacid (DHTA) and 4,6-diamino-1,3-benzenediol in poly(phosphoric acid) (PPA) using typical polycondensation conditions. The crystalline solutions of liquid PBOH in PPA were spun into fibers using dry-jet wet spinning. Furthermore, the thermostability and mechanical properties of PBOH were compared with poly(p-phenylene-2,6-benzoxazole) (PBO) in order to investigate the relationship between the chain structure and properties. The results indicated that the thermal degradation temperature of PBOH was above 750K and the tensile strength of the PBOH fiber was 3.1GPa, which were much lower than those of PBO fiber. The compressive strength of PBOH fiber was 331 M Pa, which was slightly higher than that of PBO fiber. In addition, molecular simulation was employed to explain why the compressive strength of PBOH fiber did not increase significantly compared to PBO fiber. PMID:19330065

  13. Pt silicide/poly-Si Schottky diodes as temperature sensors for bolometers

    SciTech Connect

    Yuryev, V. A. Chizh, K. V.; Chapnin, V. A.; Mironov, S. A.; Dubkov, V. P.; Uvarov, O. V.; Kalinushkin, V. P.; Senkov, V. M.; Nalivaiko, O. Y.; Novikau, A. G.; Gaiduk, P. I.

    2015-05-28

    Platinum silicide Schottky diodes formed on films of polycrystalline Si doped by phosphorus are demonstrated to be efficient and manufacturable CMOS-compatible temperature sensors for microbolometer detectors of radiation. Thin-film platinum silicide/poly-Si diodes have been produced by a CMOS-compatible process on artificial Si{sub 3}N{sub 4}/SiO{sub 2}/Si(001) substrates simulating the bolometer cells. Layer structure and phase composition of the original Pt/poly-Si films and the Pt silicide/poly-Si films synthesized by a low-temperature process have been studied by means of the scanning transmission electron microscopy; they have also been explored by means of the two-wavelength X-ray structural phase analysis and the X-ray photoelectron spectroscopy. Temperature coefficient of voltage for the forward current of a single diode is shown to reach the value of about −2%/ °C in the temperature interval from 25 to 50 °C.

  14. A Low Protein Binding Cationic Poly(2-oxazoline) as Non-Viral Vector

    PubMed Central

    He, Zhijian; Miao, Lei; Jordan, Rainer; S-Manickam, Devika; Luxenhofer, Robert; Kabanov, Alexander V

    2015-01-01

    Developing safe and efficient non-viral gene delivery systems remains a major challenge. We present a new cationic poly(2-oxazoline) (CPOx) block copolymer for gene therapy that was synthesized by sequential polymerization of non-ionic 2-methyl-2-oxazoline and a new 2-oxazoline monomer, 2-(N-methyl, N-Boc-amino)-methyl-2-oxazoline, followed by deprotection of the pendant secondary amine groups. Upon mixing with plasmid DNA (pDNA), CPOx forms small (diameter ≈ 80 nm) and narrowly dispersed polyplexes (PDI < 0.2), which are stable upon dilution in saline and against thermal challenge. These polyplexes exhibited low plasma protein binding and very low cytotoxicity in vitro compared to the polyplexes of pDNA and poly(ethylene glycol)-b-poly(l-lysine) (PEG-b-PLL). CPOx/pDNA polyplexes at N/P = 5 bound considerably less plasma protein compared to polyplexes of PEG-b-PLL at the same N/P ratio. This is a unique aspect of the developed polyplexes emphasizing their potential for systemic delivery in vivo. The transfection efficiency of the polyplexes in B16 murine melanoma cells was low after 4 h but increased significantly for 10 h exposure time, indicative of slow internalization of polyplexes. Addition of Pluronic P85 boosted the transfection using CPOx/pDNA polyplexes considerably. The low protein binding of CPOx/pDNA polyplexes is particularly interesting for the future development of targeted gene delivery. PMID:25846127

  15. Click chemistry grafting of poly(ethylene glycol) brushes to alkyne-functionalized pseudobrushes.

    PubMed

    Ostaci, Roxana-Viorela; Damiron, Denis; Grohens, Yves; Léger, Liliane; Drockenmuller, Eric

    2010-01-19

    A versatile method for the grafting of azide-terminated polymer chains to alkyne-functionalized pseudobrushes by the Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition has been developed. First, poly[(propargyl methacrylate)-r-(glycidyl methacrylate)-r-(methyl methacrylate)] random copolymers with monomer ratios of respectively 27/27/46, 41/31/28, and 45/55/0 were synthesized by RAFT polymerization. Then, dense alkyne-functionalized pseudobrushes were grafted in melt by thermal ring-opening of the glycidyl groups by the silanols from the silicon substrate. Finally, the grafting of tailor-made alpha-methoxy-omega-azido-poly(ethylene glycol)s (M(w) approximately 5000, 20,000, and 50,000 g/mol) by Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition was performed in sealed reactors at 60 degrees C for 72 h using a polymer weight fraction of 10% in tetrahydrofuran and Cu(PPh(3))(3)Br/DIPEA as the catalytic system. Alkyne-functionalized pseudobrushes and poly(ethylene glycol) brushes were characterized by ellipsometry, scanning probe microscopy, and water contact angle measurements. This "grafting-to" approach represents a fast and versatile method to provide thick and homogeneous polymer brushes with a high surface coverage. A major benefit of this strategy is the tunable and versatile tethering of alkyne functionalities to silicon substrates using a straightforward spin-coating procedure.

  16. Does inhibition of poly(ADP-ribose) polymerase prevent energy overconsumption under microgravity?

    NASA Astrophysics Data System (ADS)

    Dobrota, C.; Piso, M. I.; Keul, A.

    When plants are exposed to a stress signal they expend a lot of energy and exhibit enhanced respiration rates This is partially due to a breakdown in the NAD pool caused by the enhanced activity PARP which uses NAD as a substrate to synthesize polymers of ADP-ribose Stress-induced depletion of NAD results in a similar depletion of energy since ATP molecules are required to resynthesize the depleted NAD It seems that plants with lowered poly ADP ribosyl ation activity appear tolerant to multiple stresses Inhibiting PARP activity prevents energy overconsumption under stress allowing normal mitochondrial respiration We intend to study if the microgravity is perceived by plants as a stress factor and if experimental inhibition of poly ADP-ribose polymerase may improve the energetic level of the cells References DeBlock M Verduyn C De Brouwer D and Cornelissen M 2005 Poly ADP-ribose polymerase in plants affects energy homeostasis cell death and stress tolerance The Plant Journal 41 95--106 Huang S Greenway H Colmerm T D and Millar A H 2005 Protein synthesis by rice coleoptiles during prolonged anoxia Implications for glycolysis growth and energy utilization Annals of Botany 96 703--715 Mittler R Vanderauwera S Gollery M and Van Breusegem F 2005 Reactive oxygen gene network of plants Trends in Plant Science 9 10 490-498

  17. Efficient synthesis of poly(2-vinylpyridine)-silica colloidal nanocomposite particles using a cationic azo initiator.

    PubMed

    Dupin, Damien; Schmid, Andreas; Balmer, Jennifer A; Armes, Steven P

    2007-11-06

    Colloidal poly(2-vinylpyridine)-silica nanocomposite particles can be efficiently prepared by emulsion polymerization at 60 degrees C using a commercial 20 nm aqueous silica sol as the sole stabilizing agent. Unlike previously reported colloidal nanocomposite syntheses, transmission electron microscopy studies indicate very high silica aggregation efficiencies (88-99%). The key to success is simply the selection of a suitable cationic azo initiator. In contrast, the use of an anionic persulfate initiator leads to substantial contamination of the nanocomposite particles with excess silica sol. The cationic azo initiator is electrostatically adsorbed onto the anionic silica sol at submonolayer coverage, which suggests that surface polymerization may be important for successful nanocomposite formation. Moreover, the 2-vinylpyridine can be partially replaced with either styrene or methacrylic comonomers to produce a range of copolymer-silica nanocomposite particles. The poly(2-vinylpyridine)-silica nanocomposite particles have a well-defined core-shell morphology, with poly(2-vinylpyridine) cores and silica shells; mean diameters typically vary from 180 to 220 nm, and mean silica contents range from 27 to 35% by mass.

  18. From waste to plastic: synthesis of poly(3-hydroxypropionate) in Shimwellia blattae.

    PubMed

    Heinrich, Daniel; Andreessen, Björn; Madkour, Mohamed H; Al-Ghamdi, Mansour A; Shabbaj, Ibrahim I; Steinbüchel, Alexander

    2013-06-01

    In recent years, glycerol has become an attractive carbon source for microbial processes, as it accumulates massively as a by-product of biodiesel production, also resulting in a decline of its price. A potential use of glycerol in biotechnology is the synthesis of poly(3-hydroxypropionate) [poly(3HP)], a biopolymer with promising properties which is not synthesized by any known wild-type organism. In this study, the genes for 1,3-propanediol dehydrogenase (dhaT) and aldehyde dehydrogenase (aldD) of Pseudomonas putida KT2442, propionate-coenzyme A (propionate-CoA) transferase (pct) of Clostridium propionicum X2, and polyhydroxyalkanoate (PHA) synthase (phaC1) of Ralstonia eutropha H16 were cloned and expressed in the 1,3-propanediol producer Shimwellia blattae. In a two-step cultivation process, recombinant S. blattae cells accumulated up to 9.8% ± 0.4% (wt/wt [cell dry weight]) poly(3HP) with glycerol as the sole carbon source. Furthermore, the engineered strain tolerated the application of crude glycerol derived from biodiesel production, yielding a cell density of 4.05 g cell dry weight/liter in a 2-liter fed-batch fermentation process.

  19. VERO cells harbor a poly-ADP-ribose belt partnering their epithelial adhesion belt.

    PubMed

    Lafon-Hughes, Laura; Vilchez Larrea, Salomé C; Kun, Alejandra; Fernández Villamil, Silvia H

    2014-01-01

    Poly-ADP-ribose (PAR) is a polymer of up to 400 ADP-ribose units synthesized by poly-ADP-ribose-polymerases (PARPs) and degraded by poly-ADP-ribose-glycohydrolase (PARG). Nuclear PAR modulates chromatin compaction, affecting nuclear functions (gene expression, DNA repair). Diverse defined PARP cytoplasmic allocation patterns contrast with the yet still imprecise PAR distribution and still unclear functions. Based on previous evidence from other models, we hypothesized that PAR could be present in epithelial cells where cadherin-based adherens junctions are linked with the actin cytoskeleton (constituting the adhesion belt). In the present work, we have examined through immunofluorescence and confocal microscopy, the subcellular localization of PAR in an epithelial monkey kidney cell line (VERO). PAR was distinguished colocalizing with actin and vinculin in the epithelial belt, a location that has not been previously reported. Actin filaments disruption with cytochalasin D was paralleled by PAR belt disruption. Conversely, PARP inhibitors 3-aminobenzamide, PJ34 or XAV 939, affected PAR belt synthesis, actin distribution, cell shape and adhesion. Extracellular calcium chelation displayed similar effects. Our results demonstrate the existence of PAR in a novel subcellular localization. An initial interpretation of all the available evidence points towards TNKS-1 as the most probable PAR belt architect, although TNKS-2 involvement cannot be discarded. Forthcoming research will test this hypothesis as well as explore the existence of the PAR belt in other epithelial cells and deepen into its functional implications.

  20. VERO cells harbor a poly-ADP-ribose belt partnering their epithelial adhesion belt

    PubMed Central

    Vilchez Larrea, Salomé C.; Kun, Alejandra

    2014-01-01

    Poly-ADP-ribose (PAR) is a polymer of up to 400 ADP-ribose units synthesized by poly-ADP-ribose-polymerases (PARPs) and degraded by poly-ADP-ribose-glycohydrolase (PARG). Nuclear PAR modulates chromatin compaction, affecting nuclear functions (gene expression, DNA repair). Diverse defined PARP cytoplasmic allocation patterns contrast with the yet still imprecise PAR distribution and still unclear functions. Based on previous evidence from other models, we hypothesized that PAR could be present in epithelial cells where cadherin-based adherens junctions are linked with the actin cytoskeleton (constituting the adhesion belt). In the present work, we have examined through immunofluorescence and confocal microscopy, the subcellular localization of PAR in an epithelial monkey kidney cell line (VERO). PAR was distinguished colocalizing with actin and vinculin in the epithelial belt, a location that has not been previously reported. Actin filaments disruption with cytochalasin D was paralleled by PAR belt disruption. Conversely, PARP inhibitors 3-aminobenzamide, PJ34 or XAV 939, affected PAR belt synthesis, actin distribution, cell shape and adhesion. Extracellular calcium chelation displayed similar effects. Our results demonstrate the existence of PAR in a novel subcellular localization. An initial interpretation of all the available evidence points towards TNKS-1 as the most probable PAR belt architect, although TNKS-2 involvement cannot be discarded. Forthcoming research will test this hypothesis as well as explore the existence of the PAR belt in other epithelial cells and deepen into its functional implications. PMID:25332845

  1. Poly(aspartic acid) (PAA) hydrolases and PAA biodegradation: current knowledge and impact on applications.

    PubMed

    Hiraishi, Tomohiro

    2016-02-01

    Thermally synthesized poly(aspartic acid) (tPAA) is a bio-based, biocompatible, biodegradable, and water-soluble polymer that has a high proportion of β-Asp units and equivalent moles of D- and L-Asp units. Poly(aspartic acid) (PAA) hydrolase-1 and hydrolase-2 are tPAA biodegradation enzymes purified from Gram-negative bacteria. PAA hydrolase-1 selectively cleaves amide bonds between β-Asp units via an endo-type process, whereas PAA hydrolase-2 catalyzes the exo-type hydrolysis of the products of tPAA hydrolysis by PAA hydrolase-1. The novel reactivity of PAA hydrolase-1 makes it a good candidate for a biocatalyst in β-peptide synthesis. This mini-review gives an overview of PAA hydrolases with emphasis on their biochemical and functional properties, in particular, PAA hydrolase-1. Functionally related enzymes, such as poly(R-3-hydroxybutyrate) depolymerases and β-aminopeptidases, are compared to PAA hydrolases. This mini-review also provides findings that offer an insight into the catalytic mechanisms of PAA hydrolase-1 from Pedobacter sp. KP-2.

  2. From Waste to Plastic: Synthesis of Poly(3-Hydroxypropionate) in Shimwellia blattae

    PubMed Central

    Heinrich, Daniel; Andreessen, Björn; Madkour, Mohamed H.; Al-Ghamdi, Mansour A.; Shabbaj, Ibrahim I.

    2013-01-01

    In recent years, glycerol has become an attractive carbon source for microbial processes, as it accumulates massively as a by-product of biodiesel production, also resulting in a decline of its price. A potential use of glycerol in biotechnology is the synthesis of poly(3-hydroxypropionate) [poly(3HP)], a biopolymer with promising properties which is not synthesized by any known wild-type organism. In this study, the genes for 1,3-propanediol dehydrogenase (dhaT) and aldehyde dehydrogenase (aldD) of Pseudomonas putida KT2442, propionate-coenzyme A (propionate-CoA) transferase (pct) of Clostridium propionicum X2, and polyhydroxyalkanoate (PHA) synthase (phaC1) of Ralstonia eutropha H16 were cloned and expressed in the 1,3-propanediol producer Shimwellia blattae. In a two-step cultivation process, recombinant S. blattae cells accumulated up to 9.8% ± 0.4% (wt/wt [cell dry weight]) poly(3HP) with glycerol as the sole carbon source. Furthermore, the engineered strain tolerated the application of crude glycerol derived from biodiesel production, yielding a cell density of 4.05 g cell dry weight/liter in a 2-liter fed-batch fermentation process. PMID:23542629

  3. Calcium-activated gene transfection from DNA/poly(amic acid-co-imide) complexes.

    PubMed

    Wu, Szu-Yuan; Chang, Li-Ting; Peng, Sydeny; Tsai, Hsieh-Chih

    2015-01-01

    In this study, we synthesized a water-soluble poly(amic acid-co-imide) (PA-I) from ethylenediaminetetraacetic dianhydride (EDTA) and 2,2'-(ethylenedioxy)bis(ethylamine) that possesses comparable transfection efficiency to that of polyethylenimine (PEI), when prepared in combination with divalent calcium cations. The polycondensation of monomers afforded poly(amic acid) (PA) precursors, and subsequent thermal imidization resulted in the formation of PA-I. At a polymer/DNA ratio (indicated by the molar ratio of nitrogen in the polymer to phosphate in DNA) of 40, complete retardation of the DNA band was observed by gel electrophoresis, indicating the strong association of DNA with PA-I. A zeta potential of -22 mV was recorded for the PA-I polymer solution, and no apparent cytotoxicity was observed at concentrations up to 500 μg·mL(-1). In the presence of divalent Ca(2+), the transfection efficiency of PA-I was higher than that of PA, due to the formation of a copolymer/Ca(2+)/DNA polyplex and the reduction in negative charge due to thermal cyclization. Interestingly, a synergistic effect of Ca(2+) and the synthesized copolymer on DNA transfection was observed. The use of Ca(2+) or copolymer alone resulted in unsatisfactory delivery, whereas the formation of three-component polyplexes synergistically increased DNA transfection. Our findings demonstrated that a PA-I/Ca(2+)/DNA polyplex could serve as a promising candidate for gene delivery.

  4. Poly(methyl methacrylate)-titania hybrid materials by sol-gel processing

    SciTech Connect

    Zhang, J.; Luo, S.; Gui, L.; Tang, Y.

    1996-12-31

    Sol-gel derived Poly(methyl methacrylate)-titania hybrid materials were synthesized by using acrylic acid or allyl acetylacetone (3-allyl-2,4-pentanedione) as coupling agents. Titanium butoxide modified with acrylic acid (or titanium isopropoxide modified with allyl acetylacetone) was hydrolyzed to produce a titania network, and then poly (methyl methacrylate) (PMMA) chains formed in situ through a radical polymerization were chemically bonded to the forming titania network to synthesize a hybrid material. Transparent hybrid materials with different contents of titania were achieved. With the increase of the titania content, the colors of the products changed form yellow to dark red. The synthesis process was investigated step by step by using FTIR spectroscopy, and the experimental results demonstrated that acrylate or acetylacetonato groups bound to titanium remain in the final hybrid materials. The thermal stability of the hybrid materials was considerably improved relative to pure PMMA. Field emission scanning electron microscopy (FE-SEM) analyses showed the hybrid materials are porous and pore diameters vary from 10nm to 100nm. The hybrid materials using allyl acetylacetone as the coupling agent exhibited thermochromic effects that both pure PMMA and titania do not have.

  5. Self-assembled hydrogel nanoparticles composed of dextran and poly(ethylene glycol) macromer.

    PubMed

    Kim, I S; Jeong, Y I; Kim, S H

    2000-09-15

    Biodegradable hydrogel nanoparticles were prepared from glycidyl methacrylate dextran (GMD) and dimethacrylate poly(ethylene glycol) (DMP). GMD was synthesized by coupling of glycidyl methacrylate to dextran in the presence of 4-(N,N-dimethylamino)pyridine (DMAP) using dimethylsulfoxide (DMSO) as an aprotic solvent. DMP was synthesized from poly(ethylene glycol) (PEG) and methacryloyl chloride. GMD/DMP (abbreviated as DP) hydrogel was prepared by radical polymerization of GMD and DMP using ammonium peroxydisulfate (APS) as an initiator and UV curing. DP hydrogel nanoparticles were obtained by diafiltration method using DMSO solution. The GMD and DMP were characterized by fourier transform infrared spectroscopy. Fluorescence probe technique was used to investigate the self-assembly of DP in water using pyrene as a hydrophobic probe. The critical association concentration (CAC) was determined to be 5.6 x 10(-2) g/l. The shape of DP hydrogel nanoparticles was spherical when observed by transmission electron microscope (TEM). The size range of DP hydrogel nanoparticles was about 20 approximately 50 nm. The hydrodynamic size of DP hydrogel nanoparticles was measured by photon correlation spectroscopy (PCS) and gradually increased with time in PBS (0.1 M, pH 7.4). Drug release study was performed using clonazepam (CNZ) as a hydrophobic model drug. In vitro release rate of CNZ from the DP hydrogel nanoparticles was dependent on the existence of dextranase and the pH of the release medium.

  6. Understanding the mechanisms of photodecarbonylation of the photoprecursors of higher poly(acene)s

    NASA Astrophysics Data System (ADS)

    Mondal, Rajib; Okhrimenko, Albert N.; Shah, Bipin K.; Neckers, Douglas C.

    2007-09-01

    Polyacenes, linear poly(benzenoid) hydrocarbons, are significant compounds for various electronic applications. Smaller lower molecular weight members of the series (anthracene, tetracene, and pentacene) have been extensively investigated for their use as semiconductors, as active layers in organic field-effect transistors (OFETs) and in organic light-emitting diodes (OLEDs). Smaller HOMO-LUMO gaps might be achieved by synthesizing even higher poly(acene)s such as hexacene and heptacene. Nevertheless, an increased instability and insolubility associated with the increasing number of fused rings has become a synthetic challenge for chemists. We have recently developed a photochemical route that allows one to easily synthesize heptacene in rigid media from an α-diketone photoprecursor, thus opening a pathway to utilize these compounds in the construction of suitable devices. Photodecarbonylations of α-diketones are unusual reactions. In most instances, dione excited states become electron transfer acceptors. The decarbonylation is driven by the stability of the resulting aromatic hydrocarbon. We have studied the nature of the excited states involved in photodecarbonylation of the α-diketones and the structure of the carbon monoxide fragment(s). Results obtained on the mechanism of photodecarbonylation investigated using nanosecond flash photolysis and ultra-fast pump-probe techniques are discussed.

  7. 1H-NMR characterization of poly(ethylene glycol) and polydimethylsiloxane copolymer

    NASA Astrophysics Data System (ADS)

    Zainuddin, Ain Athirah; Othaman, Rizafizah; Noor, Wan Syaidatul Aqma Wan Mohd; Anuar, Farah Hannan

    2016-11-01

    This paper describes the synthesis and characterization of poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) copolymers. The copolymers were synthesized by reacting hydroxyl group (-OH) of poly(ethylene glycol) (PEG) and polydimetylsiloxane (PDMS) with isocyanate group (R-N=C=O) of 1,6-hexamethylene diisocyanate (HMDI). The reaction was carried out at room temperature. The copolymers were synthesized in three different compositions which differ in molar ratios of PEG to PDMS. The ratios (PEG:PDMS) used were 2:6. 3:5 and 4:4. The formation of the copolymers was characterized by 1H Nuclear Magnetic Resonance (1H-NMR) for structural determination. The presence of proton signal at 4.80 ppm which belongs to the proton of urethane group indicates the formation of urethane links. The formation of urethane links showed that two homopolymers were linked together by HMDI to form longer copolymer chains. It is worth to note that the sequence of PEG and PDMS along the copolymer chain is random.

  8. The Electronic Music Synthesizer and the Physics of Music

    ERIC Educational Resources Information Center

    Hartmann, W. M.

    1975-01-01

    Describes the principal modules of analog electronic music synthesizers and discusses some ways that a synthesizer has been used in demonstrations, in psychophysical experiments, and in an undergraduate laboratory course in the physics of music and acoustics. Considers the synthesis of both steady and transitory auditory phenomena. (Author/MLH)

  9. Functional end-capped conducting poly (3,4-ethylenedioxythiophene)

    NASA Astrophysics Data System (ADS)

    Sabatini, V.; Farina, H.; Ortenzi, Marco A.

    2016-05-01

    Methacrylate-terminated Poly(3,4-Ethylenedioxythiophene) (PEDOT) polymers with controlled degree of polymerization were successfully prepared by direct oxidative polycondensation between Ethylenedioxythiophene (EDOT) and a cross-linkable methacrylate end-capper monomer, obtained via Friedel Crafts acylation starting from EDOT and Methacryloyl chloride. The new polymer was synthesized in order to overcome the well-known technical problems of PEDOT, i.e. difficult processability and patterning, due to its poor solubility in common organic and inorganic solvents. The chemical structure and the degree of polymerization of the end-capped polymers were determined by 1H NMR spectra. A new synthesis of Methacrylate end-capped PEDOT with controlled degree of polymerization, soluble in common organic and chlorinated solvents and with improved conductivity, 210 S/cm, was performed. This method includes: direct oxidative polycondensation of 3,4-Ethylenedioxythiophene (EDOT) in the presence of a cross-linkable end-capper, i.e. Methacrylate end-capped EDOT prepared via Friedel Crafts acylation with Methacryloyl chloride and oxidant species, i.e. ferric sulfate. Furthermore, the oxidative polycondensation of EDOT monomer and Methacrylate end-capped EDOT in the presence of Sulfonated Polyethersulfone (SPES)- characterized by different degree of Sulfonation (DS)- as dopant agent was performed, leading to functional end-capped conducting PEDOT, easy to process and pattern, with conductivity of 210 S/cm, 50 S/cm higher than the one of commercial PEDOT.

  10. Poly(arylene ether)s containing pendent ethynyl groups

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

    1996-01-01

    Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

  11. Role of β-hydroxybutyrate, its polymer poly-β-hydroxybutyrate and inorganic polyphosphate in mammalian health and disease

    PubMed Central

    Dedkova, Elena N.; Blatter, Lothar A.

    2014-01-01

    We provide a comprehensive review of the role of β-hydroxybutyrate (β-OHB), its linear polymer poly-β-hydroxybutyrate (PHB), and inorganic polyphosphate (polyP) in mammalian health and disease. β-OHB is a metabolic intermediate that constitutes 70% of ketone bodies produced during ketosis. Although ketosis has been generally considered as an unfavorable pathological state (e.g., diabetic ketoacidosis in type-1 diabetes mellitus), it has been suggested that induction of mild hyperketonemia may have certain therapeutic benefits. β-OHB is synthesized in the liver from acetyl-CoA by β-OHB dehydrogenase and can be used as alternative energy source. Elevated levels of PHB are associated with pathological states. In humans, short-chain, complexed PHB (cPHB) is found in a wide variety of tissues and in atherosclerotic plaques. Plasma cPHB concentrations correlate strongly with atherogenic lipid profiles, and PHB tissue levels are elevated in type-1 diabetic animals. However, little is known about mechanisms of PHB action especially in the heart. In contrast to β-OHB, PHB is a water-insoluble, amphiphilic polymer that has high intrinsic viscosity and salt-solvating properties. cPHB can form non-specific ion channels in planar lipid bilayers and liposomes. PHB can form complexes with polyP and Ca2+ which increases membrane permeability. The biological roles played by polyP, a ubiquitous phosphate polymer with ATP-like bonds, have been most extensively studied in prokaryotes, however polyP has recently been linked to a variety of functions in mammalian cells, including blood coagulation, regulation of enzyme activity in cancer cells, cell proliferation, apoptosis and mitochondrial ion transport and energy metabolism. Recent evidence suggests that polyP is a potent activator of the mitochondrial permeability transition pore in cardiomyocytes and may represent a hitherto unrecognized key structural and functional component of the mitochondrial membrane system. PMID

  12. Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles

    PubMed Central

    Greene, Anna C.; Zhu, Jiahua; Pochan, Darrin J.; Jia, Xinqiao; Kiick, Kristi L.

    2011-01-01

    In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules. PMID:21552373

  13. Synthesis of poly(ethylene furandicarboxylate) polyester using monomers derived from renewable resources: thermal behavior comparison with PET and PEN.

    PubMed

    Papageorgiou, George Z; Tsanaktsis, Vasilios; Bikiaris, Dimitrios N

    2014-05-07

    Poly(ethylene-2,5-furandicarboxylate) (PEF) is a new alipharomatic polyester that can be prepared from monomers derived from renewable resources like furfural and hydroxymethylfurfural. For this reason it has gained high interest recently. In the present work it was synthesized from the dimethylester of 2,5-furandicarboxylic acid and ethylene glycol by applying the two-stage melt polycondensation method. The thermal behavior of PEF was studied in comparison to its terephthalate and naphthalate homologues poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN), which were also synthesized following the same procedure. The equilibrium melting point of PEF was found to be 265 °C while the heat of fusion for the pure crystalline PEF was estimated to be about 137 J g(-1). The crystallization kinetics was analyzed using various models. PET showed faster crystallization rates than PEN and this in turn showed faster crystallization than PEF, under both isothermal and non-isothermal conditions. The spherulitic morphology of PEF during isothermal crystallization was investigated by polarized light microscopy (PLM). A large nucleation density and a small spherulite size were observed for PEF even at low supercoolings, in contrast to PET or PEN. Thermogravimetric analysis indicated that PEF is thermally stable up to 325 °C and the temperature for the maximum degradation rate was 438 °C. These values were a little lower than those for PET or PEN.

  14. MECHANICAL PROPERTIES OF BLENDS OF PAMAM DENDRIMERS WITH POLY(VINYL CHLORIDE) AND POLY(VINYL ACETATE)

    EPA Science Inventory

    Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonacne ...

  15. A facile strategy to synthesize monodisperse superparamagnetic OA-modified Fe3O4 nanoparticles with PEG assistant

    NASA Astrophysics Data System (ADS)

    Sun, Minmin; Zhu, Aimei; Zhang, Qiugen; Liu, Qinglin

    2014-11-01

    A facile strategy was reported to synthesize monodisperse super-paramagnetic oleic acid (OA) modified Fe3O4 nanoparticles, which the poly ethylene glycol (PEG) was used as the assistant. The influence of the molecular weight and concentration of PEG was investigated in the process of OA-modification. In addition, the mechanism of PEG action in the reaction system was discussed. The morphology and properties of the as-synthesized Fe3O4 magnetic nanoparticles were characterized by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and superconducting quantum interference device (SQUID). The size (12 nm) of the as-prepared Fe3O4 nanoparticles is smaller than the superparamagnetic critical size (25 nm) of Fe3O4 nanoparticles, which endows the OA-modified Fe3O4 nanoparticles with superparamagnetic property. Furthermore, the dispersibility and stability of as-synthesized OA-modified Fe3O4 magnetic nanoparticles were very good. As the stabilizer and dispersant, PEG played a very important role and did not encapsulate the OA-modified Fe3O4 nanoparticles. The condition for OA-modified Fe3O4 nanoparticles preparation was optimized.

  16. Surfactant-free, cationic latices of poly(BMA-co-MMA) using AIBA initiator.

    PubMed

    Lee, Ki-Chang

    2013-09-01

    When polymer particles come into use, especially, for photonic crystal applications, their diameter, dispersivity, and refractive indices become very important. Poly(benzyl methacrylate) is known to be a kind of high refracive materials (n = 1.57) compared to poly(methyl methacrylate) (n = 1.49). Not many work was concerned for surfactant-free emulsion polymerization of benzyl methacrylate or its copolymerization using cationic initiators. Narrowly dispersed cationic poly(BMA-co-MMA) and PBMA latices were synthesized successfully by surfactant-free emulsion polymerization with AIBA. The influences of BMA/MMA ratio, BMA/MMA monomer and initiator concentrations, addition of DVB/EGDMA crosslink agent, and polymerization temperature on the kinetics and on the particle size and molecular weight were studied. Monodisperse cationic charged PBMA and poly(BMA-coMMA) latices with particle diameters varying between 160-494 nm and polymer molecular weights of the order 1.25 x 10(4) to 7.55 x 10(4) g/mol were prepared. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio, AIBA concentration, DVB crosslink agent, and polymerization temperature. The particle diameter increased with BMA concentration in BMA/MMA ratio, AIBA concentration, and BMA/MMA monomer concentration. The molecular weight increased with BMA concentration in BMA/MMA ratio and BMA/MMA monomer concentration. The glass transition temperature of the latex copolymers decreased with increasing amount of BMA from 375 K for PMMA to 321 K for PBMA. It was, thus, found that the particle diameter and rate of polymerization as well as the polymer molecular weight for surfactant-free emulsion polymerization of BMA and MMA can be controlled easily by controlling the BMA/MMA ratio, BMA/MMA monomer concentration, AIBA concentration, and polymerization temperature.

  17. Improvement of device performance of polymer organic light-emitting diodes on smooth transparent sheet with graphene films synthesized by plasma treatment

    NASA Astrophysics Data System (ADS)

    Okigawa, Yuki; Mizutani, Wataru; Suzuki, Kenkichi; Ishihara, Masatou; Yamada, Takatoshi; Hasegawa, Masataka

    2015-09-01

    Because graphene films have one-atom thickness, the morphology of the transparent sheets could have a greater effect on the performance of organic light-emitting diode (OLED) devices with graphene films than on that with indium tin oxide (ITO). In this study, we have evaluated the polymer OLED devices with graphene films synthesized by plasma treatment on poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) sheets having high flatness. The results imply that the surface roughness of the transparent sheets predominantly affects the luminescence of polymer OLED devices with graphene films. The suppression of leakage current and a luminescence higher than 8000 cd/m2 at 15 V were attained for the devices on the transparent sheet with higher flatness in spite of the presence of large sharp spikes.

  18. Distribution of protein poly(ADP-ribosyl)ation systems across all domains of life

    PubMed Central

    Perina, Dragutin; Mikoč, Andreja; Ahel, Josip; Ćetković, Helena; Žaja, Roko; Ahel, Ivan

    2014-01-01

    Poly(ADP-ribosyl)ation is a post-translational modification of proteins involved in regulation of many cellular pathways. Poly(ADP-ribose) (PAR) consists of chains of repeating ADP-ribose nucleotide units and is synthesized by the family of enzymes called poly(ADP-ribose) polymerases (PARPs). This modification can be removed by the hydrolytic action of poly(ADP-ribose) glycohydrolase (PARG) and ADP-ribosylhydrolase 3 (ARH3). Hydrolytic activity of macrodomain proteins (MacroD1, MacroD2 and TARG1) is responsible for the removal of terminal ADP-ribose unit and for complete reversion of protein ADP-ribosylation. Poly(ADP-ribosyl)ation is widely utilized in eukaryotes and PARPs are present in representatives from all six major eukaryotic supergroups, with only a small number of eukaryotic species that do not possess PARP genes. The last common ancestor of all eukaryotes possessed at least five types of PARP proteins that include both mono and poly(ADP-ribosyl) transferases. Distribution of PARGs strictly follows the distribution of PARP proteins in eukaryotic species. At least one of the macrodomain proteins that hydrolyse terminal ADP-ribose is also always present. Therefore, we can presume that the last common ancestor of all eukaryotes possessed a fully functional and reversible PAR metabolism and that PAR signalling provided the conditions essential for survival of the ancestral eukaryote in its ancient environment. PARP proteins are far less prevalent in bacteria and were probably gained through horizontal gene transfer. Only eleven bacterial species possess all proteins essential for a functional PAR metabolism, although it is not known whether PAR metabolism is truly functional in bacteria. Several dsDNA viruses also possess PARP homologues, while no PARP proteins have been identified in any archaeal genome. Our analysis of the distribution of enzymes involved in PAR metabolism provides insight into the evolution of these important signalling systems, as well as

  19. Enhanced gene delivery using biodegradable poly(ester amine)s (PEAs) based on low-molecular-weight polyethylenimine and poly(epsilon-caprolactone)-pluronic-poly(epsilon-caprolactone).

    PubMed

    Liu, Tingting; Yu, Xiujun; Kan, Bing; Guo, Qingfa; Wang, Xiuhong; Shi, Shuai; Guo, Gang; Luo, Feng; Zhao, Xia; Wei, Yuquan; Qian, Zhiyong

    2010-08-01

    In this paper, the poly(ester amine)s (PEAs) were successfully prepared from low-molecular-weight PEI (Mn = 2000) and Poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCFC) copolymers using isophorone diisocyanate (IPDI) as cross-linker. The obtained PEAs copolymers are biodegradable and water-soluble. The PEAs/DNA complexes showed effective and stable DNA condensation with the particle size < or = 200 nm and zeta potential > or =10 mV, indicating its potential for intracellular delivery. Compared to the unmodified low-molecular-weight PEI, PEAs displayed similarly low cytotoxicity in all two cell lines (293T: Human kidney carcinoma, HUVEC: Human umbilical vein Endothelial cell) and revealed much higher transfection efficiency in 293T cell lines. Therefore these PEAs might be a novel safe and efficient polymeric gene delivery vectors.

  20. DNA-Cu(II) poly(amine) complex membrane as novel catalytic layer for highly sensitive amperometric determination of hydrogen peroxide.

    PubMed

    Gu, Tingting; Hasebe, Yasushi

    2006-05-15

    A novel hydrogen peroxide biosensor was fabricated by using a DNA-Cu(II) complex as a novel electrocatalyst for the reduction of hydrogen peroxide (H2O2). A polyion complex (PIC) membrane composed of DNA and poly(allylamine) (PAA) functioned as a support matrix for immobilization of electrocatalytic element-copper ion. The circular dichroism (CD) spectrum of the DNA-Cu(II)/PAA membrane in wet state showed that the DNA exists in B-like form within the membrane. Electrochemical measurements of the DNA-Cu(II)/PAA membrane-modified glassy carbon (GC) electrode revealed that the copper ion embedded in the DNA/PAA layer exhibits good electrochemical behaviors, and the electrochemical rate constant between the immobilized copper ion and the GC electrode surface was estimated to be 26.4 s(-1). The resulting DNA-Cu(II)/PAA/GC electrode showed an excellent electrocatalytic activity for the H2O2 reduction. The sensitivity of the sensor for the determination of H2O2 was affected by the amount of each component, such as copper ion, DNA and PAA in the DNA-Cu(II)/PAA membrane. Effects of applied potential, pH, temperature, ionic strength and buffer concentrations upon the response currents of the sensor were also investigated for an optimum analytical performance. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid (response time, less than 5 s) response to H2O2. The steady-state cathodic current responses of the sensor obtained at -0.2 V versus Ag/AgCl in air-saturated 50 mM phosphate buffer (pH 5.0) increased linearly up to 135 microM with the detection limit of 50 nM. Interference by ascorbic acid and uric acid due to the reduction of Cu(II) was effectively cancelled by further modification of outermost layer of polyion complex film. In addition, the sensor exhibited good reproducibility and stability.

  1. Complementary use of flow and sedimentation field-flow fractionation techniques for size characterizing biodegradable poly(lactic acid) nanospheres

    PubMed Central

    Contado, Catia; Dalpiaz, Alessandro; Leo, Eliana; Zborowski, Maciej; Williams, P. Stephen

    2009-01-01

    Poly(lactic acid) nanoparticles were synthesized using a modified evaporation method, testing two different surfactants (sodium cholate and Pluronic F68) for the process. During their formulation the prodrug 5′-octanoyl-CPA (Oct-CPA) of the antiischemic N6-cyclopentyladenosine (CPA) was encapsulated. Three different purification methods were compared with respect to the influence of surfactant on the size characteristics of the final nanoparticle product. Flow and sedimentation field-flow fractionation techniques (FlFFF and SdFFF, respectively) were used to size characterize the five poly(lactic acid) particle samples. Two different combinations of carrier solution (mobile phase) were employed in the FlFFF analyses, while a solution of poly(vinyl alcohol) was used as mobile phase for the SdFFF runs. The separation performances of the two techniques were compared and the particle size distributions, derived from the fractograms, were interpreted with the support of observations by scanning electron microscopy. Some critical aspects, such as the carrier choice and the channel thickness determination for the FlFFF, have been investigated. This is the first comprehensive comparison of the two FFF techniques for characterizing non standard particulate materials. The two FFF techniques proved to be complementary and gave good, congruent and very useful information on the size distributions of the five poly(lactic acid) particle samples. PMID:17482199

  2. High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film.

    PubMed

    Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

    2017-01-05

    Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA=1:1), tributylphosphate(TBP, 0.05mL) and PtOEP (5μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I=1.003+2.663[O2] (R(2)=0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples.

  3. High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film

    NASA Astrophysics Data System (ADS)

    Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

    2017-01-01

    Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA = 1:1), tributylphosphate(TBP, 0.05 mL) and PtOEP (5 μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I = 1.003 + 2.663[O2] (R2 = 0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples.

  4. Electrocatalytic oxidation of ascorbic acid using a poly(aniline-co-m-ferrocenylaniline) modified glassy carbon electrode.

    PubMed

    Chairam, Sanoe; Sriraksa, Worawit; Amatatongchai, Maliwan; Somsook, Ekasith

    2011-01-01

    A poly(aniline-co-m-ferrocenylaniline) was successfully synthesized on a glassy carbon electrode (GCE) by electrochemical copolymerization using a scan potential range from -0.3 to +0.9 V (vs. Ag/AgCl) in 0.5 M H2SO4 containing 30% acetonitrile (ACN), 0.1 M aniline (Ani) and 0.005 M m-ferrocenyaniline (m-FcAni). The field emission scanning electron microscope (FESEM) and electrochemical methods were used to characterize the poly(Ani-co-m-FcAni) modified electrode. The poly(Ani-co-m-FcAni)/GCE exhibited excellent electrocatalytic oxidation of ascorbic acid (AA) in citrate buffer solution (CBS, pH 5.0). The anodic peak potential of AA was shifted from +0.55 V at the bare GCE to +0.25 V at the poly(Ani-co-m-FcAni)/GCE with higher current responses than those seen on the bare GCE. The scan number at the 10th cycle was selected as the maximum scan cycle in electrochemical polymerization. The limit of detection (LOD) was estimated to be 2.0 μM based on the signal-to-noise ratio (S/N = 3). The amperometric responses demonstrated an excellent selectivity for AA determination over glucose (Glu) and dopamine (DA).

  5. Modification of HTPB-based polyurethane with temperature-sensitive poly(N-isopropyl acrylamide) for biomaterial usage.

    PubMed

    Yang, Jen Ming; Yang, Shu Jyuan; Lin, Hao Tzu; Chen, Jan Kan

    2007-01-01

    Hydroxyl-terminated polybutadiene (HTPB)-based polyurethane with dimethyol propionic acid (DPA) as chain extender was synthesized by solution polymerization. The HTPB-based polyurethane was modified by UV radiation with N-isopropyl acrylamide monomer to get poly(N-isopropyl acrylamide)-modified polyurethane (PUDPANIPAAm). The cohesive energy (E(coh)), molar volume (V), solubility parameter (delta), molecular weight (W(M)), volume per gram (V(g)), and the density (1/V(g)) of PUDPANIPAAm were calculated by group contribution methods. To evaluate the application of PUDPANIPAAm for wound dressing and transplantation of cell sheet, the measurement of water content, water vapor transmission rate, and gas permeation on the PUDPANIPAAm membrane was evaluated. The biocompatibility of these membranes, cell adhesion, and proliferation assay were conducted in the cell culture. The effect of thermosensitivity of poly(N-isopropyl acrylamide) on cell detachment was also evaluated in the primary study. The results showed that these PUDPANIPAAm membranes are thermosensitive. The modification of PU with poly(N-isopropyl acrylamide) reduced the water vapor transmission rate and permeability of gas through PUDPANIPAAm membrane. PUDPANIPAAm membranes could support cell adhesion and growth. Owing to the thermosensitive nature of poly(N-isopropyl acrylamide), the relative cell numbers detached from PUDPANIPAAm membranes were larger than those detached from the polystyrene dish.

  6. Surface modification with poly(sulfobetaine methacrylate-co-acrylic acid) to reduce fibrinogen adsorption, platelet adhesion, and plasma coagulation.

    PubMed

    Kuo, Wei-Hsuan; Wang, Meng-Jiy; Chien, Hsiu-Wen; Wei, Ta-Chin; Lee, Chiapyng; Tsai, Wei-Bor

    2011-12-12

    Zwitterionic sulfobetaine methacrylate (SBMA) polymers were known to possess excellent antifouling properties due to high hydration capacity and neutral charge surface. In this study, copolymers of SBMA and acrylic acid (AA) with a variety of compositions were synthesized and were immobilized onto polymeric substrates with layer-by-layer polyelectrolyte films via electrostatic interaction. The amounts of platelet adhesion and fibrinogen adsorption were determined to evaluate hemocompatibility of poly(SBMA-co-AA)-modified substrates. Among various deposition conditions by modulating SBMA ratio in the copolymers and pH of the deposition solution, poly(SBMA(56)-co-AA(44)) deposited at pH 3.0 possessed the best hemocompatibility. This work demonstrated that poly(SBMA-co-AA) copolymers adsorbed on polyelectrolyte-base films via electrostatic interaction improve hemocompatibility effectively and are applicable for various substrates including TCPS, PU, and PDMS. Furthermore, poly(SBMA-co-AA)-coated substrate possesses great durability under rigorous conditions. The preliminary hemocompatibility tests regarding platelet adhesion, fibrinogen adsorption, and plasma coagulation suggest the potential of this technique for the application to blood-contacting biomedical devices.

  7. Electrocatalytic Oxidation of Ascorbic Acid Using a Poly(aniline-co-m-ferrocenylaniline) Modified Glassy Carbon Electrode

    PubMed Central

    Chairam, Sanoe; Sriraksa, Worawit; Amatatongchai, Maliwan; Somsook, Ekasith

    2011-01-01

    A poly(aniline-co-m-ferrocenylaniline) was successfully synthesized on a glassy carbon electrode (GCE) by electrochemical copolymerization using a scan potential range from −0.3 to +0.9 V (vs. Ag/AgCl) in 0.5 M H2SO4 containing 30% acetonitrile (ACN), 0.1 M aniline (Ani) and 0.005 M m-ferrocenyaniline (m-FcAni). The field emission scanning electron microscope (FESEM) and electrochemical methods were used to characterize the poly(Ani-co-m-FcAni) modified electrode. The poly(Ani-co-m-FcAni)/GCE exhibited excellent electrocatalytic oxidation of ascorbic acid (AA) in citrate buffer solution (CBS, pH 5.0). The anodic peak potential of AA was shifted from +0.55 V at the bare GCE to +0.25 V at the poly(Ani-co-m-FcAni)/GCE with higher current responses than those seen on the bare GCE. The scan number at the 10th cycle was selected as the maximum scan cycle in electrochemical polymerization. The limit of detection (LOD) was estimated to be 2.0 μM based on the signal-to-noise ratio (S/N = 3). The amperometric responses demonstrated an excellent selectivity for AA determination over glucose (Glu) and dopamine (DA). PMID:22346636

  8. pH-Responsive Polyethylene Glycol Monomethyl Ether-ε-Polylysine-G-Poly (Lactic Acid)-Based Nanoparticles as Protein Delivery Systems

    PubMed Central

    Liu, Huiqin; Li, Yijia; Yang, Rui; Gao, Xiujun; Ying, Guoguang

    2016-01-01

    The application of poly(lactic acid) for sustained protein delivery is restricted by the harsh pH inside carriers. In this study, we synthesized a pH-responsive comb-shaped block copolymer, polyethylene glycol monomethyl ether-ε-polylysine-g-poly (lactic acid) (PEP)to deliver protein (bovine serum albumin (BSA)). The PEP nanoparticles could automatically adjust the internal pH to a milder level, as shown by the quantitative ratio metric results. The circular dichroism spectra showed that proteins from the PEP nanoparticles were more stable than those from poly(lactic acid) nanoparticles. PEP nanoparticles could achieve sustained BSA release in both in vitro and in vivo experiments. Cytotoxicity results in HL-7702 cells suggested good cell compatibility of PEP carriers. Acute toxicity results showed that the PEP nanoparticles induced no toxic response in Kunming mice. Thus, PEP nanoparticles hold potential as efficient carriers for sustained protein release. PMID:27467072

  9. pH-Responsive Polyethylene Glycol Monomethyl Ether-ε-Polylysine-G-Poly (Lactic Acid)-Based Nanoparticles as Protein Delivery Systems.

    PubMed

    Liu, Huiqin; Li, Yijia; Yang, Rui; Gao, Xiujun; Ying, Guoguang

    2016-01-01

    The application of poly(lactic acid) for sustained protein delivery is restricted by the harsh pH inside carriers. In this study, we synthesized a pH-responsive comb-shaped block copolymer, polyethylene glycol monomethyl ether-ε-polylysine-g-poly (lactic acid) (PEP)to deliver protein (bovine serum albumin (BSA)). The PEP nanoparticles could automatically adjust the internal pH to a milder level, as shown by the quantitative ratio metric results. The circular dichroism spectra showed that proteins from the PEP nanoparticles were more stable than those from poly(lactic acid) nanoparticles. PEP nanoparticles could achieve sustained BSA release in both in vitro and in vivo experiments. Cytotoxicity results in HL-7702 cells suggested good cell compatibility of PEP carriers. Acute toxicity results showed that the PEP nanoparticles induced no toxic response in Kunming mice. Thus, PEP nanoparticles hold potential as efficient carriers for sustained protein release.

  10. Method For Synthesizing Extremely High-Temperature Melting Materials

    DOEpatents

    Saboungi, Marie-Louise; Glorieux, Benoit

    2005-11-22

    The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

  11. Method for synthesizing extremely high-temperature melting materials

    DOEpatents

    Saboungi, Marie-Louise; Glorieux, Benoit

    2007-11-06

    The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as carbides and transition-metal, lanthanide and actinide oxides, using an aerodynamic levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

  12. Method for Synthesizing Extremeley High Temperature Melting Materials

    DOEpatents

    Saboungi, Marie-Louise and Glorieux, Benoit

    2005-11-22

    The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

  13. Fabrication and characterization of chitosan-crosslinked-poly(alginic acid) nanohydrogel for adsorptive removal of Cr(VI) metal ion from aqueous medium.

    PubMed

    Sharma, Gaurav; Naushad, Mu; Al-Muhtaseb, Ala'a H; Kumar, Amit; Khan, Mohammad Rizwan; Kalia, Susheel; Shweta; Bala, Manju; Sharma, Arush

    2017-02-01

    In this study, chitosan-crosslinked-poly (alginic acid) nanohydrogel (CN-cl-PL(AA)NHG) was synthesized by co-polymerization method. It was used an effective adsorbent for the exclusion of Cr(VI) metal ion from aqueous medium. The synthesized nanohydrogel was characterized by FTIR, SEM and TEM. The TEM images clearly indicated the appearance of smooth surface with average size of particles ranging from 30 to 80nm. The effect of different adsorption parameters like agitation time, temperature, initial metal ion concentration and adsorbent dosage was studied and optimized. The results demonstrated that the prepared chitosan-crosslinked-poly (alginic acid) nanohydrogel had high adsorption tendency for the removal of Cr(VI) from the aqueous solution. The pseudo-second-order equation represented the better adsorption kinetics for the adsorption process. The thermodynamic studies showed the adsorption of Cr(VI) onto CN-cl-PL(AA)NHG was spontaneous and chemical in nature.

  14. Raman spectroscopy of Z-form poly[d(A-T)].poly[d(A-T)].

    PubMed

    Ridoux, J P; Liquier, J; Taillandier, E

    1988-05-17

    Helical structures of double-stranded poly[d(A-T)] in solution have been studied by Raman spectroscopy. While the classical right-handed conformation B-type spectra are obtained in the case of sodium chloride solutions, a Z-form Raman spectrum is observed by addition of nickel ions at high sodium concentration, conditions in which the inversion of the circular dichroic spectrum of poly[d(A-T)] is detected, similar to that observed for high-salt poly[d(G-C)] solutions [Bourtayre, P., Liquier, J., Pizzorni, L., & Taillandier, E. (1987) J. Biomol. Struct. Dyn. 5, 97-104]. The characterization of the Z-form spectrum of poly[d(A-T)] is proposed by comparison with previously obtained characteristic Raman lines of Z-form poly[d(G-C)] and poly[d(A-C)].poly[d(G-T)] solutions and of d(CG)3 and d(CGCATGCG) crystals [Thamann, T. J., Lord, R. C., Wang, A. H.-J., & Rich, A. (1981) Nucleic Acids Res. 9, 5443-5457; Benevides, J. M., Wang, A. H.-J., van der Marel, G. A., van Boom, J. H., Rich, A., & Thomas, G. J., Jr. (1984) Nucleic Acids Res. 14, 5913-5925]. Detailed spectroscopic data are presented reflecting the reorientation of the purine-deoxyribose entities (C2'-endo/anti----C3'-endo/syn), the modification of the phosphodiester chain, and the adenosine lines in the 1300-cm-1 region. The role played by the hydrated nickel ions in the B----Z transition is discussed.

  15. Association of poly-purine/poly-pyrimidine sequences with meiotic recombination hot spots

    PubMed Central

    Bagshaw, Andrew TM; Pitt, Joel PW; Gemmell, Neil J

    2006-01-01

    Background Meiotic recombination events have been found to concentrate in 1–2.5 kilo base regions, but these recombination hot spots do not share a consensus sequence and why they occur at specific sites is not fully understood. Some previous evidence suggests that poly-purine/poly-pyrimidine (poly-pu/py) tracts (PPTs), a class of sequence with distinctive biochemical properties, could be involved in recombination, but no general association of PPTs with meiotic recombination hot spots has previously been reported. Results We used computational methods to investigate in detail the relationship between PPTs and hot spots. We show statistical associations of PPT frequency with hot spots of meiotic recombination initiating lesions, double-strand breaks, in the genome of the yeast S. cerevisiae and with experimentally well characterized human meiotic recombination hot spots. Supporting a possible role of poly-pu/py-rich sequences in hot spot recombination, we also found that all three single nucleotide polymorphisms previously shown to be associated with human hot spot activity changes occur within sequence contexts of 14 bp or longer that are 85% or more poly-pu/py and at least 70% G/C. These polymorphisms are all close to the hot spot mid points. Comparing the sequences of experimentally characterized human hot spots with the orthologous regions of the chimpanzee genome previously shown not to contain hot spots, we found that in all five cases in which comparisons for the hot spot central regions are possible with publicly available sequence data, there are differences near the human hot spot mid points within sequences 14 bp or longer consisting of more than 80% poly-pu/py and at least 50% G/C. Conclusion Our results, along with previous evidence for the unique biochemical properties and recombination-stimulating potential of poly-pu/py-rich sequences, suggest that the possible functional involvement of this type of sequence in meiotic recombination hot spots

  16. Surface activity of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

    SciTech Connect

    Alexandridis, P.; Athanassiou, V.; Fukuda, Shinya; Hatton, T.A. )

    1994-08-01

    The surface tension of aqueous solutions of seven poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) Pluronic copolymers, covering a wide range of molecular weights (3400-14600) and PPO/PEO ratios (0.19-1.79), was determined over the 10[sup [minus]5]-10% w/v concentration range, at two temperatures (25 and 35[degree]C). Two breaks (changes in slope) were observed in the surface tension vs log concentration curve for most of the copolymers. The low-concentration break, occurring at bulk copolymer concentrations of approximately 10[sup [minus]3]%, is believed to originate from rearrangement of the copolymer molecules on the surface at complete coverage of the air/water interface. The breaks at the high-concentration part of the surface tension curve occurred at concentrations that correspond to the critical micellization concentration values as determined by a dye solubilization technique. The surface area per copolymer molecule, A, increased as a function of the number of EO segments, N[sub EO], obeying a scaling law (A [approx] N[sub EO][sup 1/2]) similar to that of lower molecular weight C[sub i]E[sub j] nonionic surfactants. 56 refs., 6 figs., 2 tabs.

  17. Stability of triple-helical poly(dT)-poly(dA)-poly(dT) DNA with counterions.

    PubMed Central

    Dadarlat, V M; Saxena, V K

    1998-01-01

    Structural conformation of triple-helical poly(dT)-poly(dA)-poly(dT) has been a very controversial issue recently. Earlier investigations, based on fiber diffraction data and molecular modeling, indicated an A-form conformation with C'3-endo sugar pucker. On the other hand, Raman, solution infrared spectral, and NMR studies show a B-form structure with C'2-endo sugars. In accordance with these experimental results, a theoretical model with B-form, C'2-endo sugars was proposed in 1993. In the present work we investigate the dynamics and stability of the two conformations within the effective local field approach applied to the normal mode calculations for the system. The presence of counterions was explicitly taken into account. Stable equilibrium positions for the counterions were calculated by analyzing the normal mode dynamics and free energy of the system. The breathing modes of the triple helix are shifted to higher frequencies over those of the double helix by 4-16 cm-1. The characteristic marker band for the B conformation at 835 cm-1 is split up into two marker bands at 830 and 835 cm-1. A detailed comparison of the normal modes and the free energies indicates that the B-form structure, with C'2-endo sugar pucker, is more stable than the A-form structure. The normal modes and the corresponding dipole moments are found to be in close agreement with recent spectroscopic findings. PMID:9649369

  18. Adsorption of poly(rA) on the carbon nanotube surface and its hybridization with poly(rU).

    PubMed

    Karachevtsev, Victor A; Gladchenko, Galyna O; Karachevtsev, Maksym V; Valeev, Vladimir A; Leontiev, Victor S; Lytvyn, Oksana S

    2008-10-06

    Adsorption of poly(rA) on a single-walled carbon nanotube surface in aqueous suspension and the subsequent hybridization of this polymer with free poly(rU) is studied. A comparison of the temperature dependence of the absorbance of free poly(rA) and poly(rA) adsorbed on the nanotube surface [poly(rA)(NT)] at nu(max)= 38,500 cm(-1) shows that the thermostability of the adsorbed polymer is higher. Molecular dynamics simulations demonstrate that more than half of the adenines are not stacked on the tube surface and some of them undergo self-stacking. After addition of a complementary poly(rU) to the poly(rA)(NT) suspension, a double-stranded polymer is formed as confirmed by the characteristic S-like form of its melting curve. However, the melting temperature of this polymer is lower than that of the free poly(rA)poly(rU) duplex. This result indicates that poly(rU) hybridization with poly(rA)(NT) occurs with defects along the whole length of the polymer because of pi-pi stacking between nitrogen bases and the nanotube surface, which hinders the usual hybridization process. Computer modeling demonstrates different possible structures of hybridized polymers on the nanotube surface.

  19. An analysis of the kinetics of oxidation of ascorbate at poly(aniline)-poly(styrene sulfonate) modified microelectrodes.

    PubMed

    Bonastre, A M; Sosna, M; Bartlett, P N

    2011-03-28

    A detailed kinetic study is provided for the oxidation of ascorbate at poly(aniline)-poly(styrene sulfonate) coated microelectrodes. Flat films with a low degree of polymer spillover and a thickness much lower than the microelectrode radius were produced by controlled potentiodynamic electrodeposition. The currents for ascorbate oxidation are found to be independent of the polymer thickness, indicating that the reaction occurs at the outer surface of the polymer film. At low ascorbate concentrations, below around 40 mM, the currents are found to be mass transport limited. At higher ascorbate concentrations the currents became kinetically limited. The experimental data for measurements at a range of potentials are fitted to a consistent kinetic model and the results summarized in a case diagram. The results obtained for the poly(aniline)-(polystyrene sulfonate) coated microelectrode are compared to those for a poly(aniline)-poly(vinyl sulfonate) coated microelectrode and to the results of an earlier study of the reaction at poly(aniline)-poly(vinyl sulfonate) coated rotating disc electrodes. For poly(aniline)-poly(styrene sulfonate) the oxidation of ascorbate is found to proceed by one electron reaction whereas for poly(aniline)-poly(vinyl sulfonate) the reaction is found to be a two electron oxidation.

  20. Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces

    NASA Astrophysics Data System (ADS)

    Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M. D.; Pike, Andrew R.; Horrocks, Benjamin R.; Fulton, David A.; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A.

    2017-01-01

    Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ˜ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

  1. A novel magnetic poly(aniline-naphthylamine)-based nanocomposite for micro solid phase extraction of rhodamine B.

    PubMed

    Bagheri, Habib; Daliri, Rasoul; Roostaie, Ali

    2013-09-10

    A novel Fe3O4-poly(aniline-naphthylamine)-based nanocomposite was synthesized by chemical oxidative polymerization process as a magnetic sorbent for micro solid phase extraction. The scanning electron microscopy images of the synthesized nanocomposite revealed that the copolymer posses a porous structure with diameters less than 50nm. The extraction efficiency of this sorbent was examined by isolation of rhodamine B, a mutagenic and carcinogenic dye, from aquatic media in dispersion mode. Among different synthesized polymers, Fe3O4/poly(aniline-naphthylamine) nanocomposite showed a prominent efficiency. Parameters including the desorption solvent, amount of sorbent, desorption time, sample pH, ionic strength, extraction time and stirring rate were optimized. Under the optimum condition, a linear spiked calibration curve in the range of 0.35-5.00μgL(-1) with R(2)=0.9991 was obtained. The limits of detection (3Sb) and limits of quantification (10Sb) of the method were 0.10μgL(-1) and 0.35μgL(-1) (n=3), respectively. The relative standard deviation for water sample with 0.5μgL(-1) of RhB was 4.2% (n=5) and the absolute recovery was 92%. The method was applied for the determination of rhodamine B in dishwashing foam, dishwashing liquid, shampoo, pencil, matches tips and eye shadows samples and the relative recovery percentage were in the range of 94-99%.

  2. Preparation, characterization, and antibacterial activity studies of silver-loaded poly(styrene-co-acrylic acid) nanocomposites.

    PubMed

    Song, Cunfeng; Chang, Ying; Cheng, Ling; Xu, Yiting; Chen, Xiaoling; Zhang, Long; Zhong, Lina; Dai, Lizong

    2014-03-01

    A simple method for preparing a new type of stable antibacterial agent was presented. Monodisperse poly(styrene-co-acrylic acid) (PSA) nanospheres, serving as matrices, were synthesized via soap-free emulsion polymerization. Field-emission scanning electron microscopy micrographs indicated that PSA nanospheres have interesting surface microstructures and well-controlled particle size distributions. Silver-loaded poly(styrene-co-acrylic acid) (PSA/Ag-NPs) nanocomposites were prepared in situ through interfacial reduction of silver nitrate with sodium borohydride, and further characterized by transmission electron microscopy and X-ray diffraction. Their effects on antibacterial activity including inhibition zone, minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), and bactericidal kinetics were evaluated. In the tests, PSA/Ag-NPs nanocomposites showed excellent antibacterial activity against both gram-positive Staphylococcus aureus and gram-negative Escherichia coli. These nanocomposites are considered to have potential application in antibacterial coatings on biomedical devices to reduce nosocomial infection rates.

  3. Synthesis, characterization and biological evaluation of poly [LA-co-(Glc-alt-Lys)] for nerve regeneration scaffold

    NASA Astrophysics Data System (ADS)

    Yin, Yi-Xia; Yi, Ji-Ling; Xie, Li-Juan; Yan, Qiong-Jiao; Dai, Hong-Lian; Li, Shi-Pu

    2014-03-01

    A novel nerve repairing material poly [LA-co-(Glc-alt-Lys)] (PLGL) was synthesized. The viability and growth of Schwann cells (SCs) co-cultured with poly (D, Llactic acid) (PDLLA) films (control group) and PLGL films were evaluated by MTTassay and SEM observation. Then, contact angle measurement, histological assessment and enzyme-linked immunosorbent assay (ELISA) testing on inflammatory-related cytokines such as IL-10 and TGF-β1 were performed. The results showed that, compared with PDLLA, PLGL films possesses better hydrophilicity, biocompatibility, degradation property and less inflammatory reaction. The present study indicated that PLGL scaffolds would meet the requirements of artificial nerve scaffold and have a potential application in the fields of nerve regeneration.

  4. Biodegradable Multiblock Poly[N-(2-hydroxypropyl)methacrylamide] via Reversible Addition-Fragmentation Chain Transfer Polymerization and Click Chemistry.

    PubMed

    Luo, Kui; Yang, Jiyuan; Kopečková, Pavla; Kopeček, Jindřich

    2011-04-26

    A new bifunctional chain transfer agent (CTA) containing alkyne end groups was designed, synthesized and used for direct synthesis of clickable telechelic polymers. Good control of reversible addition-fragmentation chain transfer (RAFT) polymerization of N-(2-hydroxypropyl)methacrylamide (HPMA) was achieved by using the new CTA, as indicated by a linear increase of number average molecular weight (Mn) with conversion and low polydispersity (PDI) (<1.1). In particular, enzymatically degradable multiblock HPMA polymers were readily prepared by subsequent reaction with αω, -diazido oligopeptide (GFLG) sequence via Cu(I) catalyzed alkyne-azide cycloaddition. Upon exposure of high molecular weight fractions of multiblock polyHPMA to papain or cathepsin B, the polymer was degraded into segments of molecular weight and narrow polydispersity similar to those of the initial telechelic polyHPMA.

  5. A simple sonochemical method for fabricating poly(methyl methacrylate)/stearic acid phase change energy storage nanocapsules.

    PubMed

    Wang, Guxia; Xu, Weibing; Hou, Qian; Guo, Shengwei

    2015-11-01

    In this study, stearic acid suitable for thermal energy storage applications was nanoencapsulated in a poly(methyl methacrylate) shell. The nanocapsules were prepared using a simple ultrasonically initiated in situ polymerization method. The morphology and particle size of the poly(methyl methacrylate)/stearic acid phase change energy storage nanocapsules (PMS-PCESNs) were analyzed using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering. The latent heat storage capacities of stearic acid and the PMS-PCESNs were determined using differential scanning calorimetry. The chemical composition of the nanocapsules was characterized using Fourier transform infrared spectroscopy. All of the results show that the PMS-PCESNs were synthesized successfully and that the latent heat storage capacity and encapsulation efficiency were 155.6 J/g and 83.0%, respectively, and the diameter of each nanocapsule was 80-90 nm.

  6. Synthesis of carboxylated poly(NIPAAm) oligomers and their application to form thermo-reversible polymer-enzyme conjugates.

    PubMed

    Chen, G; Hoffman, A S

    1994-01-01

    A thermo-reversible poly(N-isopropylacrylamide) poly(NIPAAm) oligomer with a carboxyl functional end group has been synthesized by radical polymerization using beta-mercaptopropionic acid as a chain transfer reagent. This polymer has been conjugated to an enzyme, beta-D-glucosidase, to form a thermo-reversible water soluble-insoluble polymer-enzyme conjugate. This conjugate can be used for separation, recovery and recycle of an enzyme simply by applying small temperature changes to the reaction medium. In contrast to the random polymer-enzyme conjugates reported in the literature, in this study the enzyme is coupled to each polymer chain by a single end attachment. These preliminary studies show that the conjugated enzyme exhibits very high retention of activity (> 90%) compared to the native enzyme and shows improved thermal stability.

  7. Poly(ionic liquid)-Mediated Morphogenesis of Bismuth Sulfide with a Tunable Band Gap and Enhanced Electrocatalytic Properties.

    PubMed

    Gao, Min-Rui; Yu, Shu-Hong; Yuan, Jiayin; Zhang, Weiyi; Antonietti, Markus

    2016-10-04

    Conventional polymer additives have a substantial impact on synthetic inorganic chemistry, but critical shortcomings remain; for example, low solubility in organic solvents and potential thermodynamic aggregates. Poly(ionic liquid)s have now been used as efficient additives that enable a high level control of bismuth sulfide crystals with significant size and morphological diversities. The bismuth sulfides exhibit tunable band structure as a result of the quantum size effects. Moreover, poly(ionic liquid)s are able to couple with as-synthesized bismuth sulfides chemically and endow a modified surface electronic structure, which allows resultant products to possess outstanding electrocatalytic performance for water oxidation, although its commercial counterpart is catalytically inert.

  8. Synthesis and characterization of injectable, water-soluble copolymers of tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates.

    PubMed

    Anderson, Brian C; Mallapragada, Surya K

    2002-11-01

    Several homopolymers and copolymers of 2-(diethylamino)ethyl methacrylate (DEAEM) and poly(ethylene glycol) methyl ether methacrylate (PEGMEM) were synthesized using anionic polymerization initiated by potassium t-butoxide. The polymers were characterized by average molecular weight, polydispersity and monomeric unit composition. A very narrow molecular weight distribution was achieved with a well-controlled composition. The glass transition temperatures and compositions of the copolymers followed a Gordon-Taylor relationship. The water solubility and biocompatibility of the copolymers was compared to their parent homopolymers to determine if the addition of a poly(ethylene glycol) group was sufficient to solubilize the polymers in aqueous buffer solutions and to increase the biocompatibility of the polymers. These water-soluble, injectable cationic copolymers have potential applications in gene delivery as well as other biomaterial applications.

  9. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

    Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

    1991-01-01

    Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

  10. Organic syntheses employing supercritical carbon dioxide as a reaction solvent

    NASA Technical Reports Server (NTRS)

    Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

    1993-01-01

    Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

  11. SYNTHESIZING ORGANIC COMPOUNDS USING LIGHT-ACTIVATED TIO2

    EPA Science Inventory

    High-value organic compounds have been synthesized successfully from linear and cyclic hydrocarbons, by photocatalytic oxidation using a semiconductor material, titanium dioxide (TiO2). Various hydrocarbons were partially oxgenated in both liquid and gaseous phase reactors usi...

  12. Synthesizing SoTL Institutional Initiatives toward National Impact

    ERIC Educational Resources Information Center

    Simmons, Nicola

    2016-01-01

    This chapter draws on other authors' ideas in this issue, describing parallels and outlining distinctions toward a synthesized model for the development of SoTL initiatives at the institutional level and beyond.

  13. Biologically synthesized fluorescent CdS NPs encapsulated by PHB.

    PubMed

    Pandian, Sureshbabu Ram Kumar; Deepak, Venkataraman; Kalishwaralal, Kalimuthu; Gurunathan, Sangiliyandi

    2011-04-07

    Here an attempt was made to biologically synthesize fluorescent cadmium sulfide nanoparticles and to immobilize the synthesized nanoparticles in PHB nanoparticles. The present study uses Brevibacterium casei SRKP2 as a potential producer for the green synthesis of CdS nanoparticles. Biologically synthesized nanoparticles were characterized and confirmed using electron microscopy and XRD. The size distribution of the nanoparticles was found to be 10-30 nm followed by which the consequence of time, growth of the organism, pH, concentration of CdCl(2) and Na(2)S on the synthesis of nanoparticles were checked. Enhanced synthesis and fluorescence emission of CdS nanoparticles were achieved at pH 9. The synthesized CdS NPs were immobilized with PHB and were characterized. The fluorescent intensity of the CdS nanoparticles remained unaffected even after immobilization within PHB nanoparticles.

  14. A Simple and Universal Gel Permeation Chromatography Technique for Precise Molecular Weight Characterization of Well-Defined Poly(ionic liquid)s

    SciTech Connect

    He, Hongkun; Zhong, Mingjiang; Adzima, Brian; Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof

    2013-03-20

    Poly(ionic liquid)s (PILs) are an important class of technologically relevant materials. However, characterization of well-defined polyionic materials remains a challenge. Herein, we have developed a simple and versatile gel permeation chromatography (GPC) methodology for molecular weight (MW) characterization of PILs with a variety of anions. PILs with narrow MW distributions were synthesized via atom transfer radical polymerization, and the MWs obtained from GPC were further confirmed via nuclear magnetic resonance end group analysis.

  15. Electrospun poly(ester-Urethane)- and poly(ester-Urethane-Urea) fleeces as promising tissue engineering scaffolds for adipose-derived stem cells.

    PubMed

    Gugerell, Alfred; Kober, Johanna; Laube, Thorsten; Walter, Torsten; Nürnberger, Sylvia; Grönniger, Elke; Brönneke, Simone; Wyrwa, Ralf; Schnabelrauch, Matthias; Keck, Maike

    2014-01-01

    An irreversible loss of subcutaneous adipose tissue in patients after tumor removal or deep dermal burns makes soft tissue engineering one of the most important challenges in biomedical research. The ideal scaffold for adipose tissue engineering has yet not been identified though biodegradable polymers gained an increasing interest during the last years. In the present study we synthesized two novel biodegradable polymers, poly(ε-caprolactone-co-urethane-co-urea) (PEUU) and poly[(L-lactide-co-ε-caprolactone)-co-(L-lysine ethyl ester diisocyanate)-block-oligo(ethylene glycol)-urethane] (PEU), containing different types of hydrolytically cleavable bondings. Solutions of the polymers at appropriate concentrations were used to fabricate fleeces by electrospinning. Ultrastructure, tensile properties, and degradation of the produced fleeces were evaluated. Adipose-derived stem cells (ASCs) were seeded on fleeces and morphology, viability, proliferation and differentiation were assessed. The biomaterials show fine micro- and nanostructures composed of fibers with diameters of about 0.5 to 1.3 µm. PEUU fleeces were more elastic, which might be favourable in soft tissue engineering, and degraded significantly slower compared to PEU. ASCs were able to adhere, proliferate and differentiate on both scaffolds. Morphology of the cells was slightly better on PEUU than on PEU showing a more physiological appearance. ASCs differentiated into the adipogenic lineage. Gene analysis of differentiated ASCs showed typical expression of adipogenetic markers such as PPARgamma and FABP4. Based on these results, PEUU and PEU meshes show a promising potential as scaffold materials in adipose tissue engineering.

  16. Room temperature aqueous self-assembly of poly(ethylene glycol)-poly(4-vinyl pyridine) block copolymers: From spherical to worm-like micelles.

    PubMed

    Rodrigues, Daniela P; Costa, João R C; Rocha, Nuno; Góis, Joana R; Serra, Arménio C; Coelho, Jorge F J

    2016-09-01

    The solution self-assembly and the formation, at room temperature, of a wide range of nanostructures based on monomethyl ether poly(ethylene glycol)-b-poly(4-vinyl pyridine) (mPEG-b-P4VP) block copolymer is reported. Copolymers with different compositions and molecular weights were synthesized through Atom Transfer Radical Polymerization (ATRP) method. The solution self-assembly of the block copolymers was studied by transmission electron microscopy (TEM) for different solution pHs. It was found that the formation of non-spherical nanostructures, such as rod- and worm-like micelles can be easily achieved, at room temperature, by simply varying the molecular weight of the different segments as well as the mPEG to P4VP ratio in the block copolymer structure. Because P4VP segments are known to form strong complexes with metals, the nanostructures prepared in this manuscript can find innovative applications in the biomedical field and be used as nano-templates for inorganic materials.

  17. Improved small molecule drug release from in situ forming poly(lactic-co-glycolic acid) scaffolds incorporating poly(β-amino ester) and hydroxyapatite microparticles.

    PubMed

    Fisher, Paul D; Palomino, Pablo; Milbrandt, Todd A; Hilt, J Zach; Puleo, David A

    2014-01-01

    In situ forming implants are an attractive choice for controlled drug release into a fixed location. Currently, rapidly solidifying solvent exchange systems suffer from a high initial burst, and sustained release behavior is tied to polymer precipitation and degradation rate. The present studies investigated addition of hydroxyapatite (HA) and drug-loaded poly(β-amino ester) (PBAE) microparticles to in situ forming poly(lactic-co-glycolic acid) (PLGA)-based systems to prolong release and reduce burst. PBAEs were synthesized, imbibed with simvastatin (osteogenic) or clodronate (anti-resorptive), and then ground into microparticles. Microparticles were mixed with or without HA into a PLGA solution, and the mixture was injected into buffer, leading to precipitation and creating solid scaffolds with embedded HA and PBAE microparticles. Simvastatin release was prolonged through 30 days, and burst release was reduced from 81 to 39% when loaded into PBAE microparticles. Clodronate burst was reduced from 49 to 32% after addition of HA filler, but release kinetics were unaffected after loading into PBAE microparticles. Scaffold dry mass remained unchanged through day 15, with a pronounced increase in degradation rate after day 30, while wet scaffolds experienced a mass increase through day 25 due to swelling. Porosity and pore size changed throughout degradation, likely due to a combination of swelling and degradation. The system offers improved release kinetics, multiple release profiles, and rapid solidification compared to traditional in situ forming implants.

  18. Improved small molecule drug release from in situ forming poly(lactic-co-glycolic acid) scaffolds incorporating poly(β-amino ester) and hydroxyapatite microparticles

    PubMed Central

    Fisher, Paul D.; Palomino, Pablo; Milbrandt, Todd A.; Hilt, J. Zach; Puleo, David A.

    2014-01-01

    In situ forming implants are an attractive choice for controlled drug release into a fixed location. Currently, rapidly solidifying solvent exchange systems suffer from a high initial burst, and sustained release behavior is tied to polymer precipitation and degradation rate. The present studies investigated addition of hydroxyapatite (HA) and drug-loaded poly(β-amino ester) (PBAE) microparticles to in situ forming poly(lactic-co-glycolic acid) (PLGA)–based systems to prolong release and reduce burst. PBAEs were synthesized, imbibed with simvastatin (osteogenic) or clodronate (anti-resorptive), and then ground into microparticles. Microparticles were mixed with or without HA into a PLGA solution, and the mixture was injected into buffer, leading to precipitation and creating solid scaffolds with embedded HA and PBAE microparticles. Simvastatin release was prolonged through 30 days, and burst release was reduced from 81% to 39% when loaded into PBAE microparticles. Clodronate burst was reduced from 49% to 32% after addition of HA filler, but release kinetics were unaffected after loading into PBAE microparticles. Scaffold dry mass remained unchanged through day 15, with a pronounced increase in degradation rate after day 30, while wet scaffolds experienced a mass increase through day 25 due to swelling. Porosity and pore size changed throughout degradation, likely due to a combination of swelling and degradation. The system offers improved release kinetics, multiple release profiles, and rapid solidification compared to traditional in situ forming implants. PMID:24903524

  19. Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly(ɛ-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

    NASA Astrophysics Data System (ADS)

    Feng, Runliang; Zhu, Wenxia; Song, Zhimei; Zhao, Liyan; Zhai, Guangxi

    2013-06-01

    To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly(ɛ-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and ɛ-caprolactone as raw materials. The structure of the novel copolymer was characterized by 1H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 ± 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 × 105 times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

  20. Artificial extracellular matrix for biomedical applications: biocompatible and biodegradable poly (tetramethylene ether) glycol/poly (ε-caprolactone diol)-based polyurethanes.

    PubMed

    Shahrousvand, Mohsen; Mir Mohamad Sadeghi, Gity; Salimi, Ali

    2016-12-01

    The cells as a tissue component need to viscoelastic, biocompatible, biodegradable, and wettable extracellular matrix for their biological activity. In this study, in order to prepare biomedical polyurethane elastomers with good mechanical behavior and biodegradability, a series of novel polyester-polyether- based polyurethanes (PUs) were synthesized using a two-step bulk reaction by melting pre-polymer method, taking 1,4-Butanediol (BDO) as chain extender, hexamethylene diisocyanate as the hard segment, and poly (tetramethylene ether) glycol (PTMEG) and poly (ε-caprolactone diol) (PCL-Diol) as the soft segment without a catalyst. The soft to the hard segment ratio was kept constant in all samples. Polyurethane characteristics such as thermal and mechanical properties, wettability and water adsorption, biodegradability, and cellular behavior were changed by changing the ratio of polyether diol to polyester diol composition in the soft segment. Our present work provides a new procedure for the preparation of engineered polyurethanes in surface properties and biodegradability, which could be a good candidate for bone, cartilage, and skin tissue engineering.

  1. Rhodium-coordinated poly(arylene-ethynylene)-alt-poly(arylene-vinylene) copolymer acting as photocatalyst for visible-light-powered NAD⁺/NADH reduction.

    PubMed

    Oppelt, Kerstin T; Gasiorowski, Jacek; Egbe, Daniel Ayuk Mbi; Kollender, Jan Philipp; Himmelsbach, Markus; Hassel, Achim Walter; Sariciftci, Niyazi Serdar; Knör, Günther

    2014-09-10

    A 2,2'-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD(+)/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390-650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD(+). With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled.

  2. The heat-chill method for preparation of self-assembled amphiphilic poly(ε-caprolactone)-poly(ethylene glycol) block copolymer based micellar nanoparticles for drug delivery.

    PubMed

    Payyappilly, Sanal Sebastian; Dhara, Santanu; Chattopadhyay, Santanu

    2014-04-07

    A new method is developed for preparation of amphiphilic block copolymer micellar nanoparticles and investigated as a delivery system for celecoxib, a hydrophobic model drug. Biodegradable block copolymers of poly(ethylene glycol) (PEG) and poly(ε-caprolactone) (PCL) were synthesized by ring opening copolymerization and characterized thoroughly using FTIR, (1)H NMR and GPC. The block copolymer was dispersed in distilled water at 60 °C and then it was chilled in an ice bath for the preparation of the micellar nanoparticles. Polymers self-assembled to form micellar nanoparticles (<50 nm) owing to their amphiphilic nature. The prepared micellar nanoparticles were analyzed using HR-TEM, DLS and DSC. The cytotoxicity of the polymer micellar nanoparticles was investigated against HaCaT cell lines. The study of celecoxib release from the micellar nanoparticles was carried out to assess their suitability as a drug delivery vehicle. Addition of the drug to the system at low temperature is an added advantage of this method compared to the other temperature assisted nanoparticle preparation techniques. In a nutshell, polymer micellar nanoparticles prepared using the heat-chill method are believed to be promising for the controlled drug release system of labile drugs, which degrade in toxic organic solvents and at higher temperatures.

  3. Ultrasonic-assisted synthesis of phosphorus graphene oxide/poly (vinyl alcohol) polymer and surface resistivity research of phosphorus graphene oxide/poly (vinyl alcohol) film.

    PubMed

    Li, Jihui; Li, Yongshen; Niu, Shuai; Li, Ning

    2017-05-01

    In this paper, phosphorus graphene oxide/poly (vinyl alcohol) polymer (PGO/PVA polymer) was synthesized by PGO and PVA via the esterification in the case of faint acidity and the ultrasound irradiation and characterized; moreover, phosphorus graphene oxide/poly (vinyl alcohol) film (PGO/PVA film) was prepared by PGO/PVA polymer and characterized; also, the surface resistivity of PGO/PVA film was investigated in the case of the different amount of PGO. Based on those, it had been found that PGO reacted with PVA to produce PGO/PVA polymer via the esterification under the ultrasonic-assisted condition, and PGO/PVA polymer was structured by 2D lattice of PGO and the chain of PVA connected in the form of six-member lactone ring and phosphonic ester, and PGO/PVA film was constituted by PGO/PVA polymer, and surface resistivity of 0.00, 0.75, 1.50, 2.25 and 3.00wt% of PGO/PVA film were 6.85×10(8), 2.98×10(8), 1.42×10(6), 7.66×10(4) and 1.29×10(5)Ω/sq, respectively.

  4. Thermo-Responsive Complexes of c-Myc Antisense Oligonucleotide with Block Copolymer of Poly(OEGMA) and Quaternized Poly(4-Vinylpyridine).

    PubMed

    Topuzogullari, Murat; Elalmis, Yeliz Basaran; Isoglu, Sevil Dincer

    2017-04-01

    Solution behavior of thermo-responsive polymers and their complexes with biological macromolecules may be affected by environmental conditions, such as the concentration of macromolecular components, pH, ion concentration, etc. Therefore, a thermo-responsive polymer and its complexes should be characterized in detail to observe their responses against possible environments under physiological conditions before biological applications. To briefly indicate this important issue, thermo-responsive block copolymer of quaternized poly(4-vinylpyridine) and poly(oligoethyleneglycol methyl ether methacrylate) as a potential nonviral vector has been synthesized. Polyelectrolyte complexes of this copolymer with the antisense oligonucleotide of c-Myc oncogene are also thermo-responsive but, have lower LCST (lower critical solution temperature) values compared to individual copolymer. LCST values of complexes decrease with molar ratio of macromolecular components and presence of salt. Dilution of solutions also affects solution behavior of complexes and causes a significant decrease in size and an increase in LCST, which indicates possible effects of severe dilutions in the blood stream.

  5. The effect of hydrophilic chain length and iRGD on drug delivery from poly(ε-caprolactone)-poly(N-vinylpyrrolidone) nanoparticles.

    PubMed

    Zhu, Zhenshu; Xie, Chen; Liu, Qin; Zhen, Xu; Zheng, Xianchuang; Wu, Wei; Li, Rutian; Ding, Yin; Jiang, Xiqun; Liu, Baorui

    2011-12-01

    Poly(ε-caprolactone)-b-Poly(N-vinylpyrrolidone) (PCL-b-PVP) copolymers with different PVP block length were synthesized by xanthate-mediated reverse addition fragment transfer polymerization (RAFT) and the xanthate chain transfer agent on chain end was readily translated to hydroxy or aldehyde for conjugating various functional moieties, such as fluorescent dye, biotin hydrazine and tumor homing peptide iRGD. Thus, PCL-PVP nanoparticles were prepared by these functionalized PCL-b-PVP copolymers. Furthermore, paclitaxel-loaded PCL-PVP nanoparticles with satisfactory drug loading content (15%) and encapsulation efficiency (>90%) were obtained and used in vitro and in vivo antitumor examination. It was demonstrated that the length of PVP block had a significant influence on cytotoxicity, anti-BSA adsorption, circulation time, stealth behavior, biodistribution and antitumor activity for the nanoparticles. iRGD on PCL-PVP nanoparticle surface facilitated the nanoparticles to accumulate in tumor site and enhanced their penetration in tumor tissues, both of which improved the efficacy of paclitaxel-loaded nanoparticles in impeding tumor growth and prolonging the life time of H22 tumor-bearing mice.

  6. Synthesis, characterization and properties of a physically and chemically gelling polymer system using poly(NIPAAm-co-HEMA-acrylate) and poly(NIPAAm-co-cysteamine).

    PubMed

    Bearat, Hanin H; Lee, Bae Hoon; Valdez, Jorge; Vernon, Brent L

    2011-01-01

    The aim of this work was to develop a simultaneous physically and chemically gelling system using NIPAAm co-polymers. The in situ polymer gel was obtained by synthesizing poly(NIPAAm-co-HEMAacrylate) and poly(NIPAAm-co-cysteamine) through free radical polymerization and further nucleophilic substitution. The purpose of the dual gelation is that physical gelation would take place at higher temperatures as the NIPAAm chains associate, while chemical gelation would occur through a Michael-type addition reaction, resulting in a cross-link forming through a nucleophilic attack of the thiolate on the acrylate. The structure of each co-polymer was then verified using (1)H-NMR and FT-IR spectroscopy. The corresponding lower critical solution temperature and phase transition behavior of each co-polymer was analyzed through cloud point and DSC, while mechanical properties were investigated through rheology. Swelling behavior was also monitored at different temperatures. The resulting polymer system demonstrated properties compatible with physiological conditions, forming a gel at pH 7.4 and at temperatures near body temperature. The hydrogel also showed reduced viscoelastic flow at low frequency stress, and increased strength than purely physical or chemical gels. Swelling behavior was determined to be temperature-dependent; however, no difference was observed in swelling percent beyond 48 h. Having the ability to alter these co-polymers through various synthesis parameters and techniques, this hydrogel can potentially be used as an injectable, waterborne gelling material for biomedical applications such as endovascular embolization.

  7. Synthesis and Characterization of Silicate Ester Prodrugs and Poly(ethylene glycol)-b-poly(lactic-co-glycolic acid) Block Copolymers for Formulation into Prodrug-Loaded Nanoparticles

    NASA Astrophysics Data System (ADS)

    Wohl, Adam Richard

    Fine control of the physical and chemical properties of customized materials is a field that is rapidly advancing. This is especially critical in pursuits to develop and optimize novel nanoparticle drug delivery. Specifically, I aim to apply chemistry concepts to test the hypothesis "Silicate ester prodrugs of paclitaxel, customized to have the proper hydrophobicity and hydrolytic lability, can be formulated with well-defined, biocompatible, amphiphilic block copolymers into nanoparticles that are effective drugs." Chapter 1 briefly describes the context and motivation of the scientific pursuits described in this thesis. In Chapter 2, a family of model silicate esters is synthesized, the hydrolysis rate of each compound is benchmarked, and trends are established based upon the steric bulk and leaving group ability of the silicate substituents. These trends are then applied to the synthesis of labile silicate ester prodrugs in Chapter 3. The bulk of this chapter focuses on the synthesis, hydrolysis, and cytotoxicity of prodrugs based on paclitaxel, a widely used chemotherapeutic agent. In Chapter 4, a new methodology for the synthesis of narrowly dispersed, "random" poly(lactic-co-glycolic acid) polymers by a constant infusion of the glycolide monomer is detailed. Using poly(ethylene glycol) as a macroinitiator, amphiphilic block copolymers were synthesized. Co-formulating a paclitaxel silicate and an amphiphilic block copolymer via flash nanoprecipitation led to highly prodrug-loaded, kinetically trapped nanoparticles. Studies to determine the structure, morphology, behavior, and efficacy of these nanoparticles are described in Chapter 5. Efforts to develop a general strategy for the selective end-functionalization of the polyether block of these amphiphilic block copolymers are discussed in Chapter 6. Examples of this strategy include functionalization of the polyether with an azide or a maleimide. Finally, Chapter 7 provides an outlook for future development of

  8. Vanadium oxide electrode synthesized by electroless deposition for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Wu, Haoran; Lian, Keryn

    2014-12-01

    A thin film vanadium oxide electrode was synthesized by a simple electroless deposition method. Surface and structural analyses revealed that the deposited oxide is a mixture of amorphous V2O5 and VO2. Electrochemical characterizations of the synthesized vanadium oxide showed capacitive behavior with good cycle life. The electroless deposition of vanadium oxide is inexpensive, easy to process, and environmentally benign, offering a promising route for electrode development for electrochemical capacitors.

  9. Poly-Alizarin red S/multiwalled carbon nanotube modified glassy carbon electrode for the boost up of electrocatalytic activity towards the investigation of dopamine and simultaneous resolution in the presence of 5-HT: A voltammetric study.

    PubMed

    Reddaiah, K; Madhusudana Reddy, T; Venkata Ramana, D K; Subba Rao, Y

    2016-05-01

    Poly-Alizarin red S/multiwalled carbon nanotube film on the surface of glassy carbon electrode (poly-AzrS/MWCNT/GCE) was synthesized by electrochemical process and was used for the sensitive and selective determination of dopamine (DA) by employing voltammetric techniques. The electrocatalytic response of the modified electrode was found to exhibit admirable activity. The simultaneous determination of dopamine in the presence of serotonin (5-HT) was found to exhibit very good response at poly-AzrS/MWCNTs/GCE. The effect of pH, scan rate, accumulation time and concentration of dopamine was studied at the developed poly-AzrS/MWCNTs/GCE. The poly-AzrS/MWCNTs/GCE exhibited an efficient electron mediating behavior together with well resolved peaks for dopamine, in 0.1 mol/dm(3) phosphate buffer (PBS) solution of pH 7.0. The limit of detection (LOD) and limit of quantification (LOQ) were found to be as 1.89 × 10(-7) mol/dm(3) and 6.312 × 10(-7) mol/dm(3) respectively with a dynamic range from 1 × 10(-6) to 1.8 × 10(-5) mol/dm(3). The interfacial electron transfer behavior of DA was studied by electrochemical impedance spectroscopy (EIS); the studies showed that the charge transfer rate was enhanced at poly-AzrS/MWCNTs/GCE when compared with bare GCE and poly-AzrS/GCE.

  10. Degradation of methylene blue using biologically synthesized silver nanoparticles.

    PubMed

    Vanaja, M; Paulkumar, K; Baburaja, M; Rajeshkumar, S; Gnanajobitha, G; Malarkodi, C; Sivakavinesan, M; Annadurai, G

    2014-01-01

    Nowadays plant mediated synthesis of nanoparticles has great interest and achievement due to its eco-benign and low time consuming properties. In this study silver nanoparticles were successfully synthesized by using Morinda tinctoria leaf extract under different pH. The aqueous leaf extract was added to silver nitrate solution; the color of the reaction medium was changed from pale yellow to brown and that indicates reduction of silver ions to silver nanoparticles. Thus synthesized silver nanoparticles were characterized by UV-Vis spectrophotometer. Dispersity and morphology was characterized by scanning electron microscope (SEM); crystalline nature and purity of synthesized silver nanoparticles were revealed by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). FTIR spectrum was examined to identify the effective functional molecules responsible for the reduction and stabilization of silver nanoparticles synthesized by leaf extract. The photocatalytic activity of the synthesized silver nanoparticles was examined by degradation of methylene blue under sunlight irradiation. Green synthesized silver nanoparticles were effectively degrading the dye nearly 95% at 72 h of exposure time.

  11. Degradation of Methylene Blue Using Biologically Synthesized Silver Nanoparticles

    PubMed Central

    Vanaja, M.; Paulkumar, K.; Baburaja, M.; Rajeshkumar, S.; Gnanajobitha, G.; Malarkodi, C.; Sivakavinesan, M.; Annadurai, G.

    2014-01-01

    Nowadays plant mediated synthesis of nanoparticles has great interest and achievement due to its eco-benign and low time consuming properties. In this study silver nanoparticles were successfully synthesized by using Morinda tinctoria leaf extract under different pH. The aqueous leaf extract was added to silver nitrate solution; the color of the reaction medium was changed from pale yellow to brown and that indicates reduction of silver ions to silver nanoparticles. Thus synthesized silver nanoparticles were characterized by UV-Vis spectrophotometer. Dispersity and morphology was characterized by scanning electron microscope (SEM); crystalline nature and purity of synthesized silver nanoparticles were revealed by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). FTIR spectrum was examined to identify the effective functional molecules responsible for the reduction and stabilization of silver nanoparticles synthesized by leaf extract. The photocatalytic activity of the synthesized silver nanoparticles was examined by degradation of methylene blue under sunlight irradiation. Green synthesized silver nanoparticles were effectively degrading the dye nearly 95% at 72 h of exposure time. PMID:24772055

  12. Compositions containing poly ([gamma]glutamylcysteinyl)glycines

    DOEpatents

    Jackson, P.J.; Delhaize, E.; Robinson, N.J.; Unkefer, C.J.; Furlong, C.

    1992-02-18

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting the removal, and the apparatus used in effecting the removal are described. One or more of the polypeptides, poly ([gamma]glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly ([gamma]glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form. 1 figs.

  13. Compositions containing poly (.gamma.-glutamylcysteinyl)glycines

    DOEpatents

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1992-01-01

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  14. Thermal Decomposition of Poly(methylphenylsilane)

    NASA Astrophysics Data System (ADS)

    Pan, Lujun; Zhang, Mei; Nakayama, Yoshikazu

    2000-03-01

    The thermal decomposition of poly(methylphenylsilane) was performed at constant heating rates and isothermal conditions. The evolved gases were studied by ionization-threshold mass spectroscopy. Pyrolysis under isothermal conditions reveals that the decomposition of poly(methylphenylsilane) is a type of depolymerization that has a first-order reaction. Kinetic analysis of the evolution spectra of CH3-Si-C6H5 radicals, phenyl and methyl substituents reveals the mechanism and activation energies of the decomposition reactions in main chains and substituents. It is found that the decomposition of main chains is a dominant reaction and results in the weight loss of approximately 90%. The effusion of phenyl and methyl substituents occurs in the two processes of rearrangement of main chains and the formation of stable Si-C containing residuals.

  15. Acetone transport in poly(ethylene terephthalate)

    NASA Astrophysics Data System (ADS)

    Ouyang, Hao; Chen, Che-Chen

    1997-05-01

    Organic solvents like acetone can penetrate into poly(ethylene terephthalate) (PET). The model of case I (Fickian) and case II (swelling) is employed to study the phenomenon of mass transport. This model is successful in explaining the behavior of mass transport in an amorphous polymer, for example, poly(methyl methacrylate) (PMMA). The characteristic parameters, diffusivity D and velocity v, can be obtained from the analysis of experimental data. The mass transport in PET is different from that in PMMA. It is accompanied by a large-scale structural rearrangement, which leads to induced crystallization of the original amorphous state. This is the so-called "solvent-induced crystallization." Acetone-induced crystallization was confirmed by x-ray diffraction. The differential scanning calorimetry thermograms of acetone-treated PET show that the crystallization peak disappears and the glass transition temperature decreases.

  16. Enzymatic hydrolysis of poly(ethylene furanoate).

    PubMed

    Pellis, Alessandro; Haernvall, Karolina; Pichler, Christian M; Ghazaryan, Gagik; Breinbauer, Rolf; Guebitz, Georg M

    2016-10-10

    The urgency of producing new environmentally-friendly polyesters strongly enhanced the development of bio-based poly(ethylene furanoate) (PEF) as an alternative to plastics like poly(ethylene terephthalate) (PET) for applications that include food packaging, personal and home care containers and thermoforming equipment. In this study, PEF powders of various molecular weights (6, 10 and 40kDa) were synthetized and their susceptibility to enzymatic hydrolysis was investigated for the first time. According to LC/TOF-MS analysis, cutinase 1 from Thermobifida cellulosilytica liberated both 2,5-furandicarboxylic acid and oligomers of up to DP4. The enzyme preferentially hydrolyzed PEF with higher molecular weights but was active on all tested substrates. Mild enzymatic hydrolysis of PEF has a potential both for surface functionalization and monomers recycling.

  17. In vitro investigation on poly(lactide)-Tween 80 copolymer nanoparticles fabricated by dialysis method for chemotherapy.

    PubMed

    Zhang, Zhiping; Feng, Si-Shen

    2006-04-01

    Polysorbate 80 (Tween 80) has been widely used as an emulsifier with excellent effects in nanoparticles technology for biomedical applications. This work was thus triggered to synthesize poly(lactide)/Tween 80 copolymers with various copolymer blend ratio, which were synthesized by ring-opening polymerization and characterized by 1H NMR and TGA. Nanoparticles of poly(lactide)/Tween 80 copolymers were prepared by the dialysis method without surfactants/emulsifiers involved. Paclitaxel was chosen as a prototype anticancer drug due to its excellent therapeutic effects against a wide spectrum of cancers. The drug-loaded nanoparticles of poly(lactide)/Tween 80 copolymers were then characterized by various state-of-the-art techniques, including laser light scattering for particles size and size distribution, field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) for surface morphology; laser Doppler anemometry for zeta potential; differential scanning calorimetry (DSC) for the physical status of the drug encapsulated in the polymeric matrix; X-ray photoelectron spectrometer (XPS) for surface chemistry; high performance liquid chromatography (HPLC) for drug encapsulation efficiency; and in vitro drug release kinetics. HT-29 cells and Glioma C6 cells were used as an in vitro model of the GI barrier for oral chemotherapy and a brain cancer model to evaluate in vitro cytotoxicity of the paclitaxel-loaded nanoparticles. The viability of C6 cells was decreased from 37.4 +/- 4.0% for poly(D,L-lactide-co-glycolic acid) (PLGA) nanoparticles to 17.8 +/- 4.2% for PLA-Tween 80-10 and 12.0 +/- 5.4% for PLA-Tween 80-20 copolymer nanoparticles, which was comparable with that for Taxol at the same 50 microg/mL drug concentration.

  18. Dexamethasone-loaded poly(D, L-lactic acid) microspheres/poly(ethylene glycol)-poly(epsilon-caprolactone)-poly(ethylene glycol) micelles composite for skin augmentation.

    PubMed

    Fan, Min; Liao, Jinfeng; Guo, Gang; Ding, Qiuxia; Yang, Yi; Luo, Feng; Qian, Zhiyong

    2014-04-01

    Soft tissue augmentation using various injectable fillers has gained popularity as more patients seek esthetic improvement through minimally invasive procedures requiring little or no recovery time. The currently available injectable skin fillers can be divided into three categories. With careful assessment, stimulatory fillers are the most ideal fillers. In this study, dexamethasone-loaded poly(D, L-lactic acid) (PLA) microspheres of approximately 90 micro m suspended in poly(ethylene glycol)-poly(epsilon-caprolactone)-poly(ethylene glycol) (PEG-PCL-PEG, PECE) micelles were prepared as stimulatory filler for skin augmentation. The biodegradable PECE copolymer can form nano-sized micelles in water, which instantly turns into a non-flowing gel at body temperature due to micellar aggregation. The PECE micelles (making up 90% of composite) served as vehicle for subcutaneous injection were metabolized within 44 days. At the same time, the dexamethasone-loaded PLA microspheres (10% of composite) merely served as stimulus for connective tissue formation. Dexamethasone-loaded PLA microspheres/PECE micelles composite presented great hemocompatibility in vitro. It was demonstrated in the in vive study that the composite was biodegradable, biocompatible, nontoxic and nonmigratory. Histopathological studies indicated that the composite could stimulate collagen regeneration. Furthermore, granuloma, the main complication of the stimulatory fillers, did not appear when the composite was injected into the back of SD rats, because of the dexamethasone controlled release from the composite. All results suggested that dexamethasone-loaded PLA microspheres/PECE micelles composite may be an efficient and promising biomaterial for skin augmentation.

  19. Final Report for the PolyHANAA

    SciTech Connect

    Richards, J.B.; Stratton, P.L.; Benett, W.J.; Koopman, R.P.; Milanovich, F.P.

    2001-04-30

    The PolyHanaa is a 24 chamber thermal cycling instrument designed to perform rapid, real-time optical detection of biological agents using the Polymerase Chain Reaction (PCR) process with TaqMan{trademark} reagents. Liquid samples are pipetted into small, disposable polypropylene tubes that are then inserted into the chambers. The 24 duplex chambers are divided into 6 independent groups and run information is presented simultaneously, in real time, for all groups.

  20. Solid state synthesis of poly(dichlorophosphazene)

    DOEpatents

    Allen, Christopher W.; Hneihen, Azzam S.; Peterson, Eric S.

    2001-01-01

    A method for making poly(dichlorophosphazene) using solid state reactants is disclosed and described. The present invention improves upon previous methods by removing the need for chlorinated hydrocarbon solvents, eliminating complicated equipment and simplifying the overall process by providing a "single pot" two step reaction sequence. This may be accomplished by the condensation reaction of raw materials in the melt phase of the reactants and in the absence of an environmentally damaging solvent.