Browsing by Subject "Polymerization"

Now showing 1 - 20 of 20

Open Access
Catalytic self-threading: a new route for the synthesis of polyrotaxanes
(American Chemical Society, 2004) Tuncel, D.; Steinke, J. H. G.
Main chain and branched polyrotaxanes have been synthesized in which polymerization and rotaxane formation occur simultaneously, due to the presence of the catalytically active self-threading macrocycle cucurbit[6]uril. Using monomers that contain stopper groups to prevent the catalytic macrocycle from noncatalytic threading, it was possible to prepare polyrotaxanes in high yields with molecular weights up to 39000. These polyrotaxanes are structurally perfect in the sense that exactly two macrocyles are threaded onto each structural repeat unit. Investigations into the polymerization mechanism have demonstrated that the catalyst cucurbit[6]uril is highly sensitive toward the structure of the monomers employed and a poorly designed monomer may result in complete inactivity. Features of the mechanism are discussed in some detail.
Open Access
Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons
(Academic Press Inc., 2017) Topuz, F.; Uyar, T.
Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitous environmental contaminants, and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65 mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon.
Open Access
Density profile of a Bose-Einstein condensate inside a pancake-shaped trap: Observational consequences of the dimensional cross-over in the scattering properties
(Elsevier Science B.V., 2002) Tanatar, Bilal; Minguzzi, A.; Vignolo, P.; Tosi, M. P.
It is theoretically well known that two-dimensionality of the scattering events in a Bose-Einstein condensate introduces a logarithmic dependence on density in the coupling constant entering a mean-field theory of the equilibrium density profile, which becomes dominant as the s-wave scattering length gets larger than the condensate thickness. We trace the regions of experimentally accessible system parameters for which the cross-over between different dimensionality behaviors in the scattering properties may become observable through in situ imaging of the condensed cloud with varying trap anisotropy and scattering length.
Open Access
The effect of anions of transition metal salts on the structure of modified mesostructured silica films and monoliths
(Elsevier, 2007) Demirörs, A. F.; Arslan, M.; Dag, Ö.
The structure of the preformed LC mesophase of water:transition metal salt ([M(H2O)6]X2):acid (HX):oligo(ethylene oxide) (or Pluronics):tetramethylorthosilicate (TMOS) mixture during hydrolysis and partial polymerization of the silica source is maintained upon further polymerization and condensation of the silica species in the solid state. The liquid mixture in early stage of the silica polymerization could be casted or dip coated to a surface of a glass or silicon wafer to produce mesostructured silica monoliths and films, respectively. The silica species and ions (metal ions and anions) influence the structure of the LC mesophases (as a result, the structure of silica) and the hydrophilic and hydrophobic balance in the reaction media. The silica structure can be changed from hexagonal to cubic by increasing, for example, the nitrate salt concentration in the nitrate salt systems. A similar transformation takes place in the presence of very low perchlorate salt concentration. The salt concentration in the mesostructured silica can be increased up to 1.1/1.0 salt/SiO2 w/w ratio, in mesostructured silica materials by maintaining its lamella structure in P123 and cubic in the CnEOm systems. However, the materials obtained from the P123 systems undergo transformation from lamella to 2D hexagonal upon calcinations. The method developed in this work can be used to modify the internal surface of the pores with various transition metal ions and metal oxides that may find application in catalysis. © 2006 Elsevier Inc. All rights reserved.
Open Access
Electroinitiated polymerization of 2-chloroethylvinyl ether
(1998) Kalaycioglu, E.; Toppare L.; Yagci, Y.
The electroinitiated polymerization of 2-chloroethylvinyl ether via controlled potential conditions has been achieved. The kinetics of the polymerization were determined by cyclic voltammetry at different temperatures in dichloromethane (DM) and acetonitrile (AN). The post-polymerization kinetics were followed with a similar technique. It was found that polymerization was twice as fast in DM as in AN. In DM, both the polymerization and the post-polymerization rates increased with decreasing temperature, whereas in AN the reverse behavior was observed.
Open Access
Fabrication of polymer micro needles for transdermal drug delivery system using DLP based projection stereo-lithography
(Elsevier, 2016) Ali, Z.; Türeyen, E. Buğra; Karpat, Yiğit; Çakmakcı, Melih
Fabrication of micro needles, which reduce pain during insertion and lessen tissue injury, has recently attracted great interest. Different manufacturing systems have been utilized for the advancement of micro needles such as two-photon photo polymerization, bulk lithography, droplet-borne air blowing and injection molding [1]. This paper proposes a micro fabrication process for polymer micro needles, using DLP based projection-based stereo lithography that is capable of fabricating micro-needles using biocompatible polymers. The fabrication in the experimental setup is performed with continuous movement of the platform in the vertical direction hence good surface quality is obtained. The influence of polymerization time, light intensity of DLP projector and chemical composition of the resins on the production speed and the geometrical accuracy of the micro needles have been studied. The length and the tip diameter of the micro needle are shown to be controlled through these factors. The length and tip diameter of the fabricated micro needles were observed using SEM and optical microscope and measured to be around 520 μm and 40 μm, respectively. The results indicate that polymer micro needles with appropriate geometry can be fabricated using this technique. © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license.
Open Access
Immobilization of invertase in conducting polymer matrices
(Elsevier, 1997-10) Selampinar, F.; Akbulut, U.; Özden, M. Y.; Toppare, L.
This paper reports a novel approach in the electrode immobilization of an enzyme, invertase, by electrochemical polymerization of pyrrole in the presence of enzyme. The polypyrrolelinvertase and polyamide/polypyrrole/invertase electrodes were constructed by the entrapment of enzyme in conducting matrices during electrochemical polymerization of pyrrole. This study involves the preparation and characterization of polypyrrole/invertase and polyamidelpolypyrrolelinvertase electrodes under conditions compatible with the enzyme. It demonstrates the effects of pH and temperature on the properties of enzyme electrode. Enzyme leakage tests were carried out during reuse number studies. The preparation of enzyme electrodes was done in two different electrolyte/ solvent systems. The enzyme serves as a sucrose electrode and retains its activity for several months. (c) 1997 Elsevier Science Limited. All rights reserved
Open Access
A near IR di-styryl BODIPY-based ratiometric fluorescent chemosensor for Hg(II)
(Elsevier, 2010) Atilgan, S.; Kutuk, I.; Ozdemir, T.
A novel BODIPY-based near-IR emitting probe as a selective and sensitive fluorophore for Hg(II) is synthesized. This versatile BODIPY fluorophore is functionalized for long wavelength emission at the 3 and 5 positions via a condensation reaction in which two dithiodioxomonoaza-based crown-containing phenyl units are conjugated to the BODIPY core as a chelating unit. This designed fluorophore, employing an ICT sensor can be used effectively to detect Hg(II) cations by way of a hypsochromic shift (∼90 nm) in both the absorption and emission spectra. © 2009 Elsevier Ltd. All rights reserved.
Open Access
Novel molecular building blocks based on the boradiazaindacene chromophore: applications in fluorescent metallosupramolecular coordination polymers
(2009) Bozdemir, Ö. A.; Büyükcakir, O.; Akkaya, E. U.
We designed and synthesized novel boradiazaindacene (Bodipy) derivatives that are appropriately functionalized for metal-ion-mediated supramolecular polymerization. Thus, ligands for 2-terpyridyl-, 2,6-terpyridyl-, and bipyridyl-functionalized Bodipy dyes were synthesized through Sonogashira couplings. These fluorescent building blocks are responsive to metal ions in a stoichiometry-dependent manner. Octahedral coordinating metal ions such as Zn II result in polymerization at a stoichiometry corresponding to two terpyridyl ligands to one Zn II ion. However, at increased metal ion concentrations, the dynamic equilibria are re-established in such a way that the monomeric metal complex dominates. The position of equilibria can easily be monitored by 1H NMR and fluorescence spectroscopies. As expected, although open-shell Fe II ions form similar complex structures, these cations quench the fluorescence emission of all four functionalized Bodipy ligands. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
Open Access
Oligomerization of ethylene in a slurry reactor using a nickel/sulfated alumina catalyst
(American Chemical Society, 1997) Zhang, Q.; Kantcheva, M.; Dalla Lana, I. G.
During the oligomerization of ethylene over heterogeneous catalysts, the production of α-olefins may be lowered because of an accompanying deactivation of catalyst resulting from strong adsorption of products, by isomerization or by a tendency to copolymerize into branched products. The oligomerization of ethylene was studied using Ni(II)/sulfated alumina catalysts prepared with a nonporous fumed alumina (ALON) support. The influences of methods of catalyst preparation and activation upon oligomerization activity were screened using a gas - solid microreactor. On the basis of the test results obtained in the microreactor, a modified form of the superior catalyst was prepared and its performance was examined in more detail using a well-agitated gas - liquid - solid slurry reactor. This catalyst exhibited very good oligomerization activity with no apparent deactivation in the slurry reactor at temperatures at or below 298 K and at near-atmospheric pressure. Complete conversion of the ethylene with the production of mainly two oligomers, 1-butene and 1-hexene, was attained. After 34 h in the slurry, formation of a significant amount of two branched C6 isomers was observed.
Open Access
Organization of bridging organics in periodic mesoporous organosilicas (PMOs)-polarization micro-raman spectroscopy
(Wiley, 2001) Dag, Ö.; Ozin, G. A.
The organization of bridging organics in oriented periodic mesoporous organosilica film (OPMOF) was demonstrated using the polarization micro-Raman spectroscopy (PMRS) in conjunction with powder x-ray diffraction (PXRD) and polarization optical microscopy (POM). The synthesis and the structural characterization of hexagonal symmetry OPMOF containing bridge-bonded ethane, ethene inside the silica channel walls were described. The mesoscale channels were found to run parallel to the surface of the underlying glass substrates as demonstrated by the PXRD measurements. A hexagonal array of channels with glassy silica organosilica walls was the best description of the structure shown by the PMRS measurements of OPMOF.
Open Access
Pd nanocube decoration onto flexible nanofibrous mats of core-shell polymer-ZnO nanofibers for visible light photocatalysis
(Royal Society of Chemistry, 2017) Arslan, O.; Topuz, F.; Eren, H.; Bıyıklı, Necmi; Uyar, Tamer
Plasmonic enhancement for electron-hole separation efficiency and visible light photocatalysis was achieved by Pd nanocube decoration on a ZnO nanolayer coated onto electrospun polymeric (polyacrylonitrile (PAN)) nanofibers. Since exciton formation and sustainable electron-hole separation have a vital importance for realizing better solar energy in photovoltaic and photocatalytic devices, we achieved visible light photocatalysis by Pd nanocube decoration onto well designed core-shell nanofibers of ZnO@PAN-NF. By controlling the cubic Pd nanoparticle size and the thickness of the crystalline ZnO nanolayer deposited onto electrospun PAN nanofibers via atomic layer deposition (ALD), defect mediated visible light photocatalysis efficiency can be increased. By utilizing nanofabrication techniques such as thermal decomposition, electrospinning and ALD, this fabricated template became an efficient, defect mediated, Pd nanocube plasmon enhanced photocatalytic system. Due to the enhanced contact features of the Pd nanocubes, an increase was observed for the visible light photocatalytic activity of the flexible and nanofibrous mat of Pd@ZnO@PAN-NF.
Open Access
Silver nitrate/oligo(ethylene oxide) surfactant/mesoporous silica nanocomposite films and monoliths
(Academic Press, 2001) Samarskaya, O.; Dag, Ö.
A lyotropic, liquid crystalline (LC) phase of a silver nitrate/oligo(ethylene oxide), water, and acid mixture was used for one-pot synthesis of mesoporous silica materials in which Ag+ ions are uniformly distributed. We established that the AgNO3-to-surfactant mole ratio is very important in a 50 wt% surfactant/water system to preserve the hexagonal LC phase before and after the addition of the silica source. Below a 0.6 AgNO3-to-surfactant mole ratio, the mixture is liquid crystalline and serves as a template for silica polymerization. However, between 0.6 and 0.8 AgNO3-to-surfactant mole ratios, one must control the composition of the mixture during the polymerization processes. Above a 0.8 mole ratio, Ag+ ions undergo phase separation from the reaction mixture by complexing with the surfactant molecules. The resulting silica materials obtained from AgNO3/surfactant ratio above 0.8 have anisotropy but without a hexagonal mesophase. Here, we establish a AgNO3 concentration range in which the LC phase is preserved to template the synthesis of mesoporous silica, and we discuss the structural behavior of the mixtures at AgNO3/surfactant mole ratios of 0.00-2.00, using POM, PXRD, FTIR, and UV-Vis absorption spectroscopy. © 2001 Academic Press.
Open Access
Surface-modified bacterial nanofibrillar PHB scaffolds for bladder tissue repair
(Taylor and Francis Ltd., 2016) Karahaliloǧlu, Z.; Demirbilek, M.; Şam, M.; Saǧlam, N.; Mizrak, A. K.; Denkbaş, E. B.
The aim of the study is in vitro investigation of the feasibility of surface-modified bacterial nanofibrous poly [(R)-3-hydroxybutyrate] (PHB) graft for bladder reconstruction. In this study, the surface of electrospun bacterial PHB was modified with PEG- or EDA via radio frequency glow discharge method. After plasma modification, contact angle of EDA-modified PHB scaffolds decreased from 110 ï¿½ 1.50 to 23 ï¿½ 0.5 degree. Interestingly, less calcium oxalate stone deposition was observed on modified PHB scaffolds compared to that of non-modified group. Results of this study show that surface-modified scaffolds not only inhibited calcium oxalate growth but also enhanced the uroepithelial cell viability and proliferation.
Open Access
Synthesis of solid solutions of Cd1-xZnxS nanocrystals in the channels of mesostructured silica films
(Royal Society of Chemistry, 2006) Akdoğan, Y.; Üzüm, Ç.; Dag, O.; Coombs, N.
In this contribution, we introduce the use of metal ion (Cd(ii) and Zn(ii)) modified mesostructured silica as a reaction medium, to produce a solid solution of Cd1-xZnxS nanocrystals as a thin film. With this approach, a true liquid crystalline templating (TLCT) and liquid crystalline mesophase of transition metal salt oligo(ethylene oxide) non-ionic surfactant (((1 - x)[Cd(H2O)4](NO3)2 + x[Zn(H2O)6](NO3)2) CH 3(CH2)11(OCH2CH2) 10OH, (MLC)), systems were collectively used to synthesise mesostructured silica films. The film samples were reacted at room temperature (RT) in an H2S atmosphere to produce zinc blend Cd 1-xZnxS nanocrystals in the channels of mesostructured silica. The initial Zn(ii) and Cd(ii) ion concentrations in the reaction media determine the final composition and band gap of the Cd1-xZn xS nanocrystals. The growth process of the Cd1-xZn xS nanocrystals in the pores is influenced by the silica walls. If the walls are rigid (well polymerized, obtained by aging the samples before H2S treatment), then the Cd1-xZnxS nanoparticles are smaller in size and more uniform in size distribution. © The Royal Society of Chemistry 2006.
Open Access
Synthesis, characterization and thermal properties of Alkyl-functional naphthoxazines
(Wiley, 2013-02-15) Uyar, Tamer; Hacaloglu, J.; Ishida, H.
A series of alkyl-functional naphthoxazine resins having various alkyl chain lengths from C1 to C18 are synthesized with a high yield and high purity by the reactions of 1,5-dihydroxynaphthalene, formaldehyde, and aliphatic amines. The proposed chemical structures of the naphthoxazines are confirmed by high-resolution mass spectrometry, H-1 nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and pyrolysis mass spectrometry studies. The alkyl-functional naphthoxazines have shown low polymerization temperature characteristics where polymerization of these monomers is achieved in the range of 150-170 degrees C yielding cross-linked polynaphthoxazines. The low-temperature polymerization characteristics and the associated thermal degradation behaviors are studied. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 3114-3123, 2013
Open Access
Temperature dependence of the energy of a vortex in a two-dimensional Bose gas
(Elsevier, 2004) Rajagopal, K. K.; Tanatar, Bilal; Vignolo, P.; Tosi, M. P.
We evaluate the thermodynamic critical angular velocity Ωc(T) for creation of a vortex of lowest quantized angular momentum in a strictly two-dimensional Bose gas at temperature T, using a mean-field two-fluid model for the condensate and the thermal cloud. Our results show that (i) a Thomas-Fermi description of the condensate badly fails in predicting the particle density profiles and the energy of the vortex as functions of T; and (ii) an extrapolation of a simple Thomas-Fermi formula for Ωc(0) is nevertheless approximately useful up to T≃0.5Tc.
Open Access
Theoretical analysis of substituent effects on building blocks of conducting polymers: 3, 4'-substituted bithiophenes
(American Chemical Society, 1999) Salzner, U.; Kızıltepe, T.
Substituents are widely used to modify the properties of conducting polymers. To study substituent effects on energy levels and energy gaps systematically, CH3-, OH-, NH2-, CN-, and CCH-substituted bithiophenes were examined with density functional theory and NBO analysis. Total charges and :r-electron densities were analyzed separately to examine π- and σ-effects. Second-order perturbation theory was used to quantify conjugation in terms of orbital interactions. NBO orbital energies were employed to investigate the effect of alternating donor-acceptor substitution. Substituents in 3- and 4- positions shift HOMO and LUMO levels in parallel and hardly influence HOMO- LUMO gaps. For level shifting the π-donating and π-accepting abilities are most important; electronegativity mainly influences the σ-orbitals and is less crucial in determining energy gaps. Alternating donor-acceptor substitution leads to HOMO and LUMO energies that are average between those of the parent systems and has little effect on energy gaps.
Open Access
Towards mechanochemical generation of singlet oxygen
(2018-12) Aydonat, Simay
Singlet oxygen is a short-lived reactive species which is involved a number of biochemical processes and implicated as the primary photo-generated cytotoxic agent in photodynamic therapy (PDT) of cancer. Precise chemical control of singlet oxygen generation and or storage is therefore of immense interest. In this particular study, the possibility of mechanochemical release of singlet oxygen in cross-linked polymers carrying anthracene 9,10-endoperoxides was explored. 9,10-Diphenylanthracenes are stable at room temperature but undergo thermal cycloreversion when heated to produce singlet oxygen. Thus, a cross-linked polyacrylate was synthesized, incorporating anthracene-endoperoxide modules with chain extensions at the 9,10-positions. Previously in our lab, thermal lability of the anthracene endoperoxides were shown when attached to gold nanorods. In this work, it was demonstrated that on mechanical agitation in a cryogenic ball mill, fluorescence emission due to anthracene units in the polymer is enhanced, with a concomitant generation of singlet oxygen as proved by detection with a selective probe, SOSG. Also, a cross-linked polyacrylate and a PDMS elastomer incorporating anthracene-endoperoxide modules with chain extensions at the 9,10-positions were synthesized as the polymeric matrix for a better manifestation of mechanochemical process.
Open Access
Transition metals for the synthesis of glycopolymers and glycopolypeptides
(Wiley-VCH Verlag, 2015) Islam, M.; Shaikh, A. Y.; Hotha, S.
Glycopolymers and glycopolypeptides are an important class of molecules, which can self-assemble to various interesting biohybrid materials. It is envisaged that the glycans impart good immunological response, and the aliphatic or polypeptide backbone can give tertiary structure for the resulting glycopolymers. The major bottleneck in the synthesis of glycopolymers or glycopolypeptides is the access to suitable building blocks and polymerization methods. This review describes methods that have recently been explored for the successful synthesis of many useful glycomonomers that could be polymerized to afford glycopolymers and/or glycopolypeptides.