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Sample records for linear functional copolymers

  1. Responsive linear-dendritic block copolymers.

    Blasco, Eva; Piñol, Milagros; Oriol, Luis

    2014-06-01

    The combination of dendritic and linear polymeric structures in the same macromolecule opens up new possibilities for the design of block copolymers and for applications of functional polymers that have self-assembly properties. There are three main strategies for the synthesis of linear-dendritic block copolymers (LDBCs) and, in particular, the emergence of click chemistry has made the coupling of preformed blocks one of the most efficient ways of obtaining libraries of LDBCs. In these materials, the periphery of the dendron can be precisely functionalised to obtain functional LDBCs with self-assembly properties of interest in different technological areas. The incorporation of stimuli-responsive moieties gives rise to smart materials that are generally processed as self-assemblies of amphiphilic LDBCs with a morphology that can be controlled by an external stimulus. Particular emphasis is placed on light-responsive LDBCs. Furthermore, a brief review of the biomedical or materials science applications of LDBCs is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Thin Films of Novel Linear-Dendritic Diblock Copolymers

    Iyer, Jyotsna; Hammond, Paula

    1998-03-01

    A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

  3. Functional Nanoporous Polymers from Block Copolymer Precursors

    Guo, Fengxiao

    Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed......, where living anionic polymerization and atom transfer radical polymerization (ATRP) are combined to synthesize a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer precursor. By using either anhydrous hydrogen fluoride or trifluoroacetic acid, PtBA block...

  4. Functionalization of Block Copolymer Vesicle Surfaces

    Wolfgang Meier

    2011-01-01

    Full Text Available In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted.

  5. Linear optical absorption response of poly(vinylidene fluoride - trifluoroethylene) copolymers to high gamma dose

    Medeiros, Adriana S.

    2009-01-01

    Poly(vinylidene fluoride) [PVDF] is a semicrystalline linear homopolymer composed by the repetition of CH 2 - CF 2 monomers. The Poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] is a copolymer which is obtained with the random introduction of fluorinated CHF-CF 2 monomers in the PVDF main chain. PVDF, and also its copolymers with TrFE contents ranging from 18 to 63 wt. %, have long been studied for their striking ferroelectric properties and their applications in actuators, transducers and ferroelectric memory. Recent research work around the world have demonstrated that, for TrFE contents ranging from with 30 to 50 wt. %, the copolymer can have its ferroelectric properties modified by high doses of ionizing radiation, with the appearing of radio-induced relaxor ferroelectric features. These studies have lead us to investigate the possible use of these copolymers as high dose dosemeters, once the reported amount of induced C=C conjugated bonds after X-ray, UV and gamma irradiation seems to be a function of the delivered radiation dose. In a first investigation for doses ranging from 0.1 to 100 kGy we found out a linear relation between the gamma radiation dose and the absorption peak intensities in the UV region of the spectrum, i.e., at 223 and 274 nm. The absorption peak at 223 nm is the most sensitive to gamma rays and can be used for detecting gamma doses ranging from 0.3 to 75 kGy. Simultaneously, the absorption peak at 274 nm can be used for doses ranging from 1 to 100 kGy. Now, in the present work, we extended the investigation to gamma doses up to 3 MGy. Particularly, this study is focused in the optical absorption peak at 274 nm, corresponding to the radio-induction of triplets of conjugated C=C double bonds. The investigation revealed a linear correlation between the gamma dose and peak intensity at 274 nm for gamma doses ranging from 0.1 to more than 750 KGy, with a huge extension of the original usable dose range. Calorimetric data revealed a

  6. Linear low density polyethylene/cycloolefin copolymer blends

    Dorigato, A.; Pegoretti, A.; Fambri, L.; Lonardi, C.; Šlouf, Miroslav; Kolařík, Jan

    2011-01-01

    Roč. 5, č. 1 (2011), s. 23-37 ISSN 1788-618X R&D Projects: GA ČR GA106/09/1348 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer blends * cycloolefin copolymer * creep Subject RIV: JI - Composite Materials Impact factor: 1.769, year: 2011

  7. TiO2 nanorods/PMMA copolymer-based nanocomposites: highly homogeneous linear and nonlinear optical material

    Sciancalepore, C; Agostiano, A; Cassano, T; Valentini, A; Curri, M L; Striccoli, M; Mecerreyes, D; Tommasi, R

    2008-01-01

    Original nanocomposites have been obtained by direct incorporation of pre-synthesized oleic acid capped TiO 2 nanorods into properly functionalized poly(methyl methacrylate) copolymers, carrying carboxylic acid groups on the repeating polymer unit. The presence of carboxylic groups on the alkyl chain of the host functionalized copolymer allows an highly homogeneous dispersion of the nanorods in the organic matrix. The prepared TiO 2 /PMMA-co-MA nanocomposites show high optical transparency in the visible region, even at high TiO 2 nanorod content, and tunable linear refractive index depending on the nanoparticle concentration. Finally measurements of nonlinear optical properties of TiO 2 polymer nanocomposites demonstrate a negligible two-photon absorption and a negative value of nonlinear refractive index, highlighting the potential of the nanocomposite for efficient optical devices operating in the visible region

  8. TiO2 nanorods/PMMA copolymer-based nanocomposites: highly homogeneous linear and nonlinear optical material

    Sciancalepore, C.; Cassano, T.; Curri, M. L.; Mecerreyes, D.; Valentini, A.; Agostiano, A.; Tommasi, R.; Striccoli, M.

    2008-05-01

    Original nanocomposites have been obtained by direct incorporation of pre-synthesized oleic acid capped TiO2 nanorods into properly functionalized poly(methyl methacrylate) copolymers, carrying carboxylic acid groups on the repeating polymer unit. The presence of carboxylic groups on the alkyl chain of the host functionalized copolymer allows an highly homogeneous dispersion of the nanorods in the organic matrix. The prepared TiO2/PMMA-co-MA nanocomposites show high optical transparency in the visible region, even at high TiO2 nanorod content, and tunable linear refractive index depending on the nanoparticle concentration. Finally measurements of nonlinear optical properties of TiO2 polymer nanocomposites demonstrate a negligible two-photon absorption and a negative value of nonlinear refractive index, highlighting the potential of the nanocomposite for efficient optical devices operating in the visible region.

  9. Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

    Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

    2013-07-11

    In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

  10. Assessment of ethylene vinyl-acetate copolymer samples exposed to γ-rays via linearity analyses

    Oliveira, Lucas N. de; Nascimento, Eriberto O. do; Schimidt, Fernando [Instituto Federal de Educação, Ciência e Tecnologia de Goiás (IFG), Goiânia, GO (Brazil); Antonio, Patrícia L.; Caldas, Linda V.E., E-mail: lcaldas@ipen.br [Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil)

    2017-07-01

    Materials with the potential to become dosimeters are of interest in radiation physics. In this research, the materials were analyzed and compared in relation to their linearity ranges. Samples of ethylene vinyl-acetate copolymer (EVA) were irradiated with doses from 10 Gy to 10 kGy using a {sup 60}Co Gamma-Cell system 220 and evaluated with the FTIR technique. The linearity analyses were applied through two methodologies, searching for linear regions in their response. The results show that both applied analyses indicate linear regions in defined dose interval. The radiation detectors EVA can be useful for radiation dosimetry in intermediate and high doses. (author)

  11. Functional (co)polymers from carbenes: scope, mechanism & polymer properties

    Franssen, N.M.G.

    2012-01-01

    Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

  12. Coding and decoding libraries of sequence-defined functional copolymers synthesized via photoligation.

    Zydziak, Nicolas; Konrad, Waldemar; Feist, Florian; Afonin, Sergii; Weidner, Steffen; Barner-Kowollik, Christopher

    2016-11-30

    Designing artificial macromolecules with absolute sequence order represents a considerable challenge. Here we report an advanced light-induced avenue to monodisperse sequence-defined functional linear macromolecules up to decamers via a unique photochemical approach. The versatility of the synthetic strategy-combining sequential and modular concepts-enables the synthesis of perfect macromolecules varying in chemical constitution and topology. Specific functions are placed at arbitrary positions along the chain via the successive addition of monomer units and blocks, leading to a library of functional homopolymers, alternating copolymers and block copolymers. The in-depth characterization of each sequence-defined chain confirms the precision nature of the macromolecules. Decoding of the functional information contained in the molecular structure is achieved via tandem mass spectrometry without recourse to their synthetic history, showing that the sequence information can be read. We submit that the presented photochemical strategy is a viable and advanced concept for coding individual monomer units along a macromolecular chain.

  13. Super toughened biodegradable polylactide blends with non-linear copolymer interfacial architecture obtained via facile in-situ reactive compatibilization

    Ojijo, Vincent O

    2015-12-01

    Full Text Available to the formation of non-linear copolymer architecture at the interface. Scanning electron microscopy showed a drastic reduction of the dispersed phase size upon compatibilization, even at very low quantities of the chain extender. Rheological probing...

  14. Reorganizing Neural Network System for Two Spirals and Linear Low-Density Polyethylene Copolymer Problems

    G. M. Behery

    2009-01-01

    Full Text Available This paper presents an automatic system of neural networks (NNs that has the ability to simulate and predict many of applied problems. The system architectures are automatically reorganized and the experimental process starts again, if the required performance is not reached. This processing is continued until the performance obtained. This system is first applied and tested on the two spiral problem; it shows that excellent generalization performance obtained by classifying all points of the two-spirals correctly. After that, it is applied and tested on the shear stress and the pressure drop problem across the short orifice die as a function of shear rate at different mean pressures for linear low-density polyethylene copolymer (LLDPE at 190∘C. The system shows a better agreement with an experimental data of the two cases: shear stress and pressure drop. The proposed system has been also designed to simulate other distributions not presented in the training set (predicted and matched them effectively.

  15. Anhydric maleic functionalization and polyethylene glycol grafting of lactide-co-trimethylene carbonate copolymers

    Díaz, A.; Valle, L.; Franco, L. del [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Sarasua, J.R. [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain); Estrany, F. [Departament d' Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Puiggalí, J., E-mail: Jordi.Puiggali@upc.es [Department of Mining-Metallurgy Engineering and Materials Science, University of the Basque Country (UPV/EHU), Bilbao (Spain)

    2014-09-01

    Lactide and trimethylene carbonate copolymers were successfully grafted with polyethylene glycol via previous functionalization with maleic anhydride and using N,N′-diisopropylcarbodiimide as condensing agent. Maleinization led to moderate polymer degradation. Specifically, the weight average molecular weight decreased from 36,200 to 30,200 g/mol for the copolymer having 20 mol% of trimethylene carbonate units. Copolymers were characterized by differential scanning calorimetry, thermogravimetry and X-ray diffraction. Morphology of spherulites and lamellar crystals was evaluated with optical and atomic force microscopies, respectively. The studied copolymers were able to crystallize despite the randomness caused by the trimethylene carbonate units and the lateral groups. Contact angle measurements indicated that PEG grafted copolymers were more hydrophilic than parent copolymers. This feature justified that enzymatic degradation in lipase medium and proliferation of both epithelial-like and fibroblast-like cells were enhanced. Grafted copolymers were appropriate to prepare regular drug loaded microspheres by the oil-in-water emulsion method. Triclosan release from loaded microspheres was evaluated in two media. - Highlights: • Pegylated copolymers of lactide and trimethylene carbonate have been synthesized. • Grafting with polyethylene glycol was able via maleic anhydride functionalization. • Drug-loaded microspheres could be prepared from new pegylated copolymers. • Hydrophilicity of lactide/trimethylene carbonate copolymers increased by pegylation. • New pegylated copolymers supported cell adhesion and proliferation.

  16. Functionalized linear and cyclic polyolefins

    Tuba, Robert; Grubbs, Robert H.

    2018-02-13

    This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

  17. Analysis of the static properties of cluster formations in symmetric linear multiblock copolymers

    Fytas, N G; Theodorakis, P E

    2011-01-01

    We use molecular dynamics simulations to study the static properties of a single linear multiblock copolymer chain under poor solvent conditions varying the block length N, the number of blocks n, and the solvent quality by variation of the temperature T. We study the most symmetrical case, where the number of blocks of monomers of type A, n A , equals that of monomers B, n B (n A = n B = n/2), the length of all blocks is the same irrespective of their type, and the potential parameters are also chosen symmetrically, as for a standard Lennard-Jones fluid. Under poor solvent conditions the chains collapse and blocks with monomers of the same type form clusters, which are phase separated from the clusters with monomers of the other type. We study the dependence of the size of the clusters formed on n, N and T. Furthermore, we discuss our results with respect to recent simulation data on the phase behaviour of such macromolecules, providing a complete picture for the cluster formations in single multiblock copolymer chains under poor solvent conditions.

  18. The Preparation and Characterization of Tourmaline-Containing Functional Copolymer p (VST/MMA/BA

    Yingmo Hu

    2018-01-01

    Full Text Available Tourmaline was modified with vinyl triethoxysilane containing double bond to prepare the polymerizable organic vinylsiliconoxyl tourmaline (VST and then copolymerized with methyl methacrylate (MMA and butyl acrylate (BA to produce the tourmaline-containing functional copolymer p (VST/MMA/BA. The structures and morphologies of VST and p (VST/MMA/BA copolymer were characterized by IR, SEM, and EDX. The experimental results indicated that tourmaline was introduced into the copolymer via surface modification and the tourmaline-containing functional copolymer was obtained by a copolymerization process with MMA and BA. The prepared p (VST/MMA/BA copolymer displayed excellent storage stabilities, high far-infrared radiation and negative ion releasing performances, and good mechanical properties.

  19. A series of poly(butylimidazolium) ionic liquid functionalized copolymers for anion exchange membranes

    Ouadah, Amina; Xu, Hulin; Luo, Tianwei; Gao, Shuitao; Wang, Xing; Fang, Zhou; Jing, Chaojun; Zhu, Changjin

    2017-12-01

    A new series of ionic liquid functionalized copolymers for anion exchange membranes (AEM) is prepared. Poly(butylvinylimidazolium)(b-VIB) is copolymerized with para-methyl styrene (p-MS) by the radical polymerization formed block copolymers b-VIB/p-MS, which is crosslinked with poly(diphenylether bibenzimidazole) (DPEBI) providing the desired materials b-VIB/p-MS/DPEBI. Structures are characterized via H1NMR, FTIR spectra and elemental analysis. The b-VIB blocks offer the anion conduction function while DPEBI moieties contribute to enhancing other properties. The prepared membranes display chloride conductivity as high as 19.5 mS/cm at 25 °C and 69.2 mS/cm at 100 °C-higher than that of the commercial membrane tokuyuama A201-. Their hydroxide conductivity reaches 35.7 Scm-1 at 25 °C and 73.1 Scm-1 at 100 °C. The membranes showed a linear Arrhenius behavior in the anion conduction, low activation energies and distinguished nanophase separation of hydrophilic/hydrophobic regions by the transmission electron microscopy (TEM) studies. Thermal investigations using TGA and DSC confirm that the membranes are stable up to 250 °C. Particularly, drastically alkaline stability due to no decrease in the hydroxide conductivity after 168 h of treatment with 2M KOH.

  20. Functionalized isothianaphthene monomers that promote quinoidal character in donor-acceptor copolymers for organic photovoltaics

    Douglas, Jessica D.

    2012-05-22

    A series of low band gap isothianaphthene-based (ITN) polymers with various electron-withdrawing substituents and intrinsic quinoidal character were synthesized, characterized, and tested in organic photovoltaic (OPV) devices. The three investigated ITN cores contained either ester, imide, or nitrile functionalities and were each synthesized in only four linear steps. The relative electron-withdrawing strength of the three substituents on the ITN moiety was evaluated and correlated to the optical and electronic properties of ITN-based copolymers. The ester- and imide-containing p-type polymers reached device efficiencies as high as 3% in bulk heterojunction blends with phenyl C 61-butyric acid methyl ester (PC 61BM), while the significantly electron-deficient nitrile-functionalized polymer behaved as an n-type material with an efficiency of 0.3% in bilayer devices with poly(3-(4-n-octyl)phenylthiophene) (POPT). © 2012 American Chemical Society.

  1. Meromorphic functions and linear algebra

    Nevanlinna, Olavi

    2003-01-01

    This volume describes for the first time in monograph form important applications in numerical methods of linear algebra. The author presents new material and extended results from recent papers in a very readable style. The main goal of the book is to study the behavior of the resolvent of a matrix under the perturbation by low rank matrices. Whereas the eigenvalues (the poles of the resolvent) and the pseudospectra (the sets where the resolvent takes large values) can move dramatically under such perturbations, the growth of the resolvent as a matrix-valued meromorphic function remains essen

  2. Synthesis and Functionalization of Poly(ethylene oxide-b-ethyloxazoline) Diblock Copolymers with Phosphonate Ions

    Chen, Alfred Yuen-Wei

    2013-01-01

    Poly(ethylene oxide) (PEO) and poly(2-ethyl-2-oxazoline) (PEOX) are biocompatible polymers that act as hydrophilic "stealth" drug carriers. As block copolymers, the PEOX group offers a wider variety of functionalization. The goal of this project was to synthesize a poly(ethylene oxide)-b-poly(2-ethyl-2-oxazoline) (PEO-b-PEOX) block copolymer and functionalize pendent groups of PEOX with phosphonic acid. This was achieved through cationic ring opening polymerization (CROP) of 2-...

  3. Characterization of Functionalized Acrylic acid /4- Vinyl Pyridine Graft Copolymers

    Kamal, H.; Mahmoud, Gh.A.; Hegazy, D.E.

    2009-01-01

    Properties and characterization of the membranes prepared by radiation grafting of acrylic acid (AAc) or/ and 4-vinyl pyridine (4VP) onto low density polyethylene (LDPE) and polypropylene (PP) films were carried out. The FTIR spectra for the grafted membranes were studied to evaluate the structure change as a result of grafting. The swelling behaviour of the graft copolymer in methanol was studied. It was found that the grafting of AAc and/ or 4- VP onto LDPE and PP resulted in introducing good hydrophilic properties to such polymer substrates. The hydrophilic properties were directly proportional to the amount of functional groups. The mechanical properties (Young's modulus, elongation percent and tensile strength) of the grafted membranes also, have been investigated. As the grafting degree increases, the modulus also increases. Increasing the hydrophilicity of the membranes by chemical treatment enhances its mechanical properties. The thermal parameters of the grafted membranes such as δH m1 . δH m2 , and T rc have been also studied by using DSC

  4. A Trivial Linear Discriminant Function

    Shuichi Shinmura

    2015-11-01

    Full Text Available In this paper, we focus on the new model selection procedure of the discriminant analysis. Combining re-sampling technique with k-fold cross validation, we develop a k-fold cross validation for small sample method. By this breakthrough, we obtain the mean error rate in the validation samples (M2 and the 95\\% confidence interval (CI of discriminant coefficient. Moreover, we propose the model  selection  procedure  in  which  the model having a minimum M2 was  chosen  to  the  best  model.  We  apply  this  new  method and procedure to the pass/ fail determination of  exam  scores.  In  this  case,  we  fix  the constant =1 for seven linear discriminant  functions  (LDFs  and  several  good  results  were obtained as follows: 1 M2 of Fisher's LDF are over 4.6\\% worse than Revised IP-OLDF. 2 A soft-margin  SVM  for  penalty c=1  (SVM1  is  worse  than  another  mathematical  programming (MP based LDFs and logistic regression . 3 The 95\\% CI of the best discriminant coefficients was obtained. Seven LDFs except for Fisher's LDF are almost the same as a trivial LDF for the linear separable model. Furthermore, if we choose the median of the coefficient of seven LDFs except for Fisher's LDF,  those are almost the same as the trivial LDF for the linear separable model.

  5. Synthesis and characterization of functional acrylic copolymers via RAFT mini-emulsion polymerization

    Yılmaz, Onur; Özkan, ćiǧdem Kılıçarislan; Yılmaz, Catalina N.; Yorgancıoǧlu, Ali; Özgünay, Hasan; Karavana, Hüseyin Ata

    2017-12-01

    Copolymers bearing reactive functional groups with controlled molecular weights are of importance since they can be used in many fields such as composites, coatings, membranes, catalysis, biology, optoelectronics, pharmaceuticals, etc. In the present study low molecular weight copolymers based on butyl acrylate (BA) and methyl methacrylate (MMA) in combination with reactive functional monomers of vinyl trietoxysilane (VTES), 3-trimetoxysilylpropyl methacrylate (TMSPMA) and glycidyl methacrylate (GMA) were synthesized via RAFT mini-emulsion technique using 2-cyano 2-propyldodecyldithiocarbonate as CTA agent. The results showed that the average molecular weights of copolymers were close to the theoretical values. On the other hand, PDI values were found to be higher than conventional RAFT polymers. The particle sizes of the latexes were small with very homogenous distributions and good stability. FTIR, H-NMR and TGA results verified the success of copolymer syntheses.

  6. Synthesis and Characterization of Block Copolymers with Unique Chemical Functionalities and Entropically-Hindering Moieties

    2017-08-14

    methanol as a function of chemistry , morphology and hydration levels. Accomplishments: This section is included in the "upload" section. Training...Copolymer Blend Membranes.” In Press, Polymer Engineering and Science, DOI: 10.1002 /pen.24508, 2017. 5. M. Pérez-Pérez and D. Suleiman. “Synthesis and...Synthesis and Characterization of Sulfonated Amine Block Copolymers for Energy Efficient Applications". Chemical Engineering Symposium, University of

  7. Introducing Linear Functions: An Alternative Statistical Approach

    Nolan, Caroline; Herbert, Sandra

    2015-01-01

    The introduction of linear functions is the turning point where many students decide if mathematics is useful or not. This means the role of parameters and variables in linear functions could be considered to be "threshold concepts". There is recognition that linear functions can be taught in context through the exploration of linear…

  8. Thermoresponsive Poly(2-Oxazoline) Molecular Brushes by Living Ionic Polymerization: Modulation of the Cloud Point by Random and Block Copolymer Pendant Chains

    Zhang, Ning; Luxenhofer, Robert; Jordan, Rainer

    2012-01-01

    random and block copolymers. Their aqueous solutions displayed a distinct thermoresponsive behavior as a function of the side-chain composition and sequence. The cloud point (CP) of MBs with random copolymer side chains is a linear function

  9. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong [Sichuan University, Chengdu (China)

    2013-08-15

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu{sup 2+}, Fe{sup 3+} and Zn{sup 2+}) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe.

  10. Synthesis and characterization of acrylate copolymer containing fluorescein functional group

    Hui, Guodong; Huang, Weiyun; Song, Yunzhao; Chen, Deben; Zhong, Anyong

    2013-01-01

    We report a novel method to fabricate fluorescent polymer (F-CPA) based on the esterification between acrylate copolymer (CPA) and fluorescein using N, N-dicyclohexylcarbodiimide (DCC)/4-dimethylaminopyridine (DMAP) as catalyst. The resulting copolymer was characterized by Fourier transform-infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ultraviolet-visible spectroscopy (UV-Vis) and fluorescence spectroscopy. In addition, the influences of concentration, solvents, pH and metal cations (Cu"2"+, Fe"3"+ and Zn"2"+) on the fluorescent behaviors of F-CPA are discussed in detail. All those observations suggest that the synthesized F-CPA is an excellent luminescent macromolecular material with simple synthesis method and excellent solubility. Moreover, its sensitive fluorescence response behaviors to solvents, pH and metal cations make it to become a polymer-based probe

  11. Functional Block Copolymers as Compatibilizers for Nanoclays in Polypropylene Nanocomposites

    Jankova Atanasova, Katja; Daugaard, Anders Egede; Stribeck, Norbert

    2011-01-01

    With the aim of creating tough nanocomposits (NC) [1] based on polypropylene (PP) and nanoclay (NCl) in the framework of the 7th EU program NANOTOUGH we have designed amphiphilic block copolymers utilizing Atom Transfer Radical Polymerization (ATRP) [2]. They consist of a hydrophobic block...... crystallites) is replaced by alien-reinforcement (of the MMT). Furthermore, the results from the impact strength and cyclic test of the prepared PP nanocomposites [3] are promicing....

  12. Functionalized and graft copolymers of chitosan and its pharmaceutical applications.

    Bhavsar, Chintan; Momin, Munira; Gharat, Sankalp; Omri, Abdelwahab

    2017-10-01

    Chitosan is the second most abundant natural polysaccharide. It belongs a family of polycationic polymers comprised of repetitive units of glucosamine and N-acetylglucosamine. Its biodegradability, nontoxicity, non-immunogenicity and biocompatibility along with properties like mucoadhesion, fungistatic and bacteriogenic have made chitosan an appreciated polymer with numerous applications in the pharmaceutical, comestics and food industry. However, the limited solubility of chitosan at alkaline and neutral pH limits its widespread commercial use. This can be circumvented by fabrication of chitosan by graft copolymerization with acyl, alkyl, monomeric and polymeric moieties. Areas covered: Modifications like quarterization, thiolation, acylation and grafting result in copolymers with higher mucoadhesion strength, increased hydrophobic interactions (advantageous in hydrophobic drug entrapment), and increased solubility in alkaline pH, the ability for adsorption of metal ions, protein and peptide delivery and nutrient delivery. Insights on methods of polymerization, including atomic transfer radical polymerization and click chemistry are discussed. Applications of such modified chitosan copolymers in medical and surgical, and drug delivery, including nasal, oral and buccal delivery have also been covered. Expert opinion: Despite a number of successful investigations, commercialization of chitosan copolymers still remains a challenge. Further advancements in polymerization techniques may address the unmet needs of the healthcare industry.

  13. New Linear and Star-Shaped Thermogelling Poly([R]-3-hydroxybutyrate) Copolymers.

    Barouti, Ghislaine; Liow, Sing Shy; Dou, Qingqing; Ye, Hongye; Orione, Clément; Guillaume, Sophie M; Loh, Xian Jun

    2016-07-18

    The synthesis of multi-arm poly([R]-3-hydroxybutyrate) (PHB)-based triblock copolymers (poly([R]-3-hydroxybutyrate)-b-poly(N-isopropylacrylamide)-b-[[poly(methyl ether methacrylate)-g-poly(ethylene glycol)]-co-[poly(methacrylate)-g-poly(propylene glycol)

  14. Functional materials derived from block copolymer self-assembly

    Li, Tao

    deposition methods, namely nanocasting and atomic layer deposition (ALD) will be applied to fabricate compact, inter-connected, and continuous metal oxide films. In this way, the structure integrity will be preserved after template removal during the annealing procedure. Another objective of this project......-casting, the block copolymer self-organizes into monolayer packed sphere pattern, without any surface treatment of the substrate and annealing process. Arrays of nano-pillars and nanowells of various materials are fabricated in dry etch processes over wafer scale without defects. We also show an in situ Al2O3 hard...

  15. Characterization and Some Properties of Functionalized Graft Copolymer

    Hegazy El-Sayed, A.; Kamal, H.; Mahmoud, Gh.A.; Khalifa, N.A.

    2000-01-01

    The study involved the investigation and characterization of membranes prepared by graft copolymerization of acrylonitrile (AN) and vinyl acetate (VAc) binary monomers onto low density polyethylene (LDPE) and isotactic polypropylene (IPP). The mutual gamma-irradiation method was used as a grafting technique. The effects of grafting and chemical treatments on the thermal properties and crystallinity of prepared graft copolymer have been investigated using DSC, TGA and XRD. IR spectra recorded before and after grafting and also for the chemically treated membranes to elucidate the structural changes occurred due to grafting and chemical treatments

  16. Understanding Linear Functions and Their Representations

    Wells, Pamela J.

    2015-01-01

    Linear functions are an important part of the middle school mathematics curriculum. Students in the middle grades gain fluency by working with linear functions in a variety of representations (NCTM 2001). Presented in this article is an activity that was used with five eighth-grade classes at three different schools. The activity contains 15 cards…

  17. Functionalization of carbon nanofibers with elastomeric block copolymer using carbodiimide chemistry

    Mapkar, Javed A.; Iyer, Ganesh [Chemical and Environmental Engineering Department, University of Toledo, Mail Stop 305, 2801 W Bancroft St., Toledo, OH 43606 (United States); Coleman, Maria R., E-mail: maria.coleman6@utoledo.edu [Chemical and Environmental Engineering Department, University of Toledo, Mail Stop 305, 2801 W Bancroft St., Toledo, OH 43606 (United States)

    2009-02-15

    Surface functionalization of carbon nanofibers (CNFs) with aminopropyl terminated polydimethylsiloxane [(PDMS-NH{sub 2})] and other organic diamines was achieved using carbodiimide chemistry. The carbodiimide chemistry provides faster reaction rate so that the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. CNF functionalized with PDMS-NH{sub 2} fibers were further functionalized with oligomer of polyimide (6FDA-BisP) using imidization reaction. The formation of block copolymer on the surface of CNF is proposed as an effective method to engineer the interphase between the fiber and the polymer, which is essential to modulate and enhance the properties of the nanocomposite. The efficiency of the carbodiimide chemistry to functionalize amine terminated groups on CNF and the functionalization of block copolymer was characterized using thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy.

  18. Functionalization of carbon nanofibers with elastomeric block copolymer using carbodiimide chemistry

    Mapkar, Javed A.; Iyer, Ganesh; Coleman, Maria R.

    2009-01-01

    Surface functionalization of carbon nanofibers (CNFs) with aminopropyl terminated polydimethylsiloxane [(PDMS-NH 2 )] and other organic diamines was achieved using carbodiimide chemistry. The carbodiimide chemistry provides faster reaction rate so that the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. CNF functionalized with PDMS-NH 2 fibers were further functionalized with oligomer of polyimide (6FDA-BisP) using imidization reaction. The formation of block copolymer on the surface of CNF is proposed as an effective method to engineer the interphase between the fiber and the polymer, which is essential to modulate and enhance the properties of the nanocomposite. The efficiency of the carbodiimide chemistry to functionalize amine terminated groups on CNF and the functionalization of block copolymer was characterized using thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy.

  19. Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

    Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon

    2018-02-07

    Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

  20. Introducing linear functions: an alternative statistical approach

    Nolan, Caroline; Herbert, Sandra

    2015-12-01

    The introduction of linear functions is the turning point where many students decide if mathematics is useful or not. This means the role of parameters and variables in linear functions could be considered to be `threshold concepts'. There is recognition that linear functions can be taught in context through the exploration of linear modelling examples, but this has its limitations. Currently, statistical data is easily attainable, and graphics or computer algebra system (CAS) calculators are common in many classrooms. The use of this technology provides ease of access to different representations of linear functions as well as the ability to fit a least-squares line for real-life data. This means these calculators could support a possible alternative approach to the introduction of linear functions. This study compares the results of an end-of-topic test for two classes of Australian middle secondary students at a regional school to determine if such an alternative approach is feasible. In this study, test questions were grouped by concept and subjected to concept by concept analysis of the means of test results of the two classes. This analysis revealed that the students following the alternative approach demonstrated greater competence with non-standard questions.

  1. Time-resolved SAXS studies of morphological changes in a blend of linear polyethylene with homogeneous ethylene-1-octene copolymer

    Ślusarczyk, Czesław, E-mail: cslusarczyk@ath.bielsko.pl

    2015-12-01

    Isothermal melt crystallization in the 15/85 (m/m) blend of a high density polyethylene (HDPE) and a homogeneous ethylene copolymer with 5.5 mol% 1-octene was studied by time-resolved SAXS method with synchrotron radiation over a wide-range of crystallization temperatures. The SAXS profile was analyzed by means of the correlation function which allows to elucidate the evolution of the morphological parameters of polyethylene lamellar structure (long period (LP), thicknesses of crystalline (L{sub C}) and amorphous (L{sub A}) layers) during a crystallization process. It was found that for the samples crystallized at 100 °C, 120 °C and 122 °C L{sub C} increases with time. The lamellar thickening rate strongly depends on crystallization temperature. At 40 °C thickening of the crystalline layers does not occur. The time evolution of the lamellar structure in the blend studied confirms the role of hexyl branches of homogeneous copolymer in the crystallization process of polyethylene. The branches introduce steric constraints which hinder the crystallization of HDPE, thus decreasing the size of the HDPE lamellar crystals.

  2. Radiation cross-linking of ethylene vinyl alcohol copolymer functionalized with m-isopropenyl-α,α-dimethyl benzyl isocyanate

    Ekman, K.B.; Naesman, J.H.

    1993-01-01

    An ethylene vinyl alcohol copolymer was functionalized with m-isopropenyl-α,α-dimethyl benzyl isocyanate using reactive processing in a mixer. The functionalization introduces pendant unsaturation to the polymer, which allows radiation cross-linked to gel contents >70% at radiation doses below 100 kGy. Unfunctionalized ethylene vinyl alcohol copolymer, on the other hand, forms no gel upon irradiation. The functionalization was completed within a few minutes of reactive mixing, which was confirmed with both FTIR and 13 C-NMR measurements. The oxygen permeability of ethylene vinyl alcohol copolymer increased with increasing degree of functionalization, and irradiation of the samples formed trapped radicals, which act as oxygen scavengers. Consequently no oxygen permeability was detected. However, radical activity was inhibited by annealing the samples at 110 C resulting in a 24% higher oxygen permeability value for the irradiated unfunctionalized copolymer. The oxygen permeability values of the irradiated functionalized samples were approximately 13% lower. Laminates of m-isopropenyl-α,α-dimethyl benzyl isocyanate functionalized ethylene vinyl alcohol copolymer and m-isopropenyl-α,α-dimethyl benzyl isocyanate functionalized ethylene hydroxyethyl methacrylate copolymer acquired improved adhesive strength both at dry and wet conditions as well as at elevated temperature upon exposure to radiation

  3. Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

    Dorenbos, G.

    2017-06-01

    Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

  4. Substituent effects on furan-phenylene copolymer for photovoltaic improvement: A density functional study

    Janprapa, Nuttaporn; Vchirawongkwin, Viwat; Kritayakornupong, Chinapong

    2018-06-01

    The structural, electronic and photovoltaic properties of furan-phenylene copolymer ((Fu-co-Ph)4) and its derivatives were evaluated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated band gaps of pristine furan and phenylene are in good agreement with the available experimental data. The lower band gap value of 2.72 eV was obtained from -NO2 and -NHCH3 substituents, leading to broader solar absorption range. With respected to the reorganization energy, -OCH3, -NHCH3, -OH, -SCH3, -CH3, -CF3, -NO2, and -F substituted (Fu-co-Ph)4 structures were classified as better electron donor materials. For combination with PC61BM, -NO2, -CN, -CF3 and -F functionalized copolymers demonstrated significantly higher open circuit voltage (Voc) values ranging from 1.07 to 2.10 eV. Our results revealed that electron withdrawing group substitution on furan-phenylene copolymers was an effective way for improving electronic and optical properties of donor materials used in photovoltaic applications.

  5. A non-linear kinematic hardening function

    Ottosen, N.S.

    1977-05-01

    Based on the classical theory of plasticity, and accepting the von Mises criterion as the initial yield criterion, a non-linear kinematic hardening function applicable both to Melan-Prager's and to Ziegler's hardening rule is proposed. This non-linear hardening function is determined by means of the uniaxial stress-strain curve, and any such curve is applicable. The proposed hardening function considers the problem of general reversed loading, and a smooth change in the behaviour from one plastic state to another nearlying plastic state is obtained. A review of both the kinematic hardening theory and the corresponding non-linear hardening assumptions is given, and it is shown that material behaviour is identical whether Melan-Prager's or Ziegler's hardening rule is applied, provided that the von Mises yield criterion is adopted. (author)

  6. Density Functional Study of Stacking Structures and Electronic Behaviors of AnE-PV Copolymer.

    Dong, Chuan-Ding; Beenken, Wichard J D

    2016-10-10

    In this work, we report an in-depth investigation on the π-stacking and interdigitating structures of poly(p-anthracene-ethynylene)-alt-poly(p-phenylene-vinylene) copolymer with octyl and ethyl-hexyl side chains and the resulting electronic band structures using density functional theory calculations. We found that in the π-stacking direction, the preferred stacking structure, determined by the steric effect of the branched ethyl-hexyl side chains, is featured by the anthracene-ethynylene units stacking on the phenylene-vinylene units of the neighboring chains and vice versa. This stacking structure, combined with the interdigitating structure where the branched side chains of the laterally neighboring chains are isolated, defines the energetically favorable structure of the ordered copolymer phase, which provides a good compromise between light absorption and charge-carrier transport.

  7. Linear scaling of density functional algorithms

    Stechel, E.B.; Feibelman, P.J.; Williams, A.R.

    1993-01-01

    An efficient density functional algorithm (DFA) that scales linearly with system size will revolutionize electronic structure calculations. Density functional calculations are reliable and accurate in determining many condensed matter and molecular ground-state properties. However, because current DFA's, including methods related to that of Car and Parrinello, scale with the cube of the system size, density functional studies are not routinely applied to large systems. Linear scaling is achieved by constructing functions that are both localized and fully occupied, thereby eliminating the need to calculate global eigenfunctions. It is, however, widely believed that exponential localization requires the existence of an energy gap between the occupied and unoccupied states. Despite this, the authors demonstrate that linear scaling can still be achieved for metals. Using a linear scaling algorithm, they have explicitly constructed localized, almost fully occupied orbitals for the quintessential metallic system, jellium. The algorithm is readily generalizable to any system geometry and Hamiltonian. They will discuss the conceptual issues involved, convergence properties and scaling for their new algorithm

  8. A linear combination of modified Bessel functions

    Shitzer, A.; Chato, J. C.

    1971-01-01

    A linear combination of modified Bessel functions is defined, discussed briefly, and tabulated. This combination was found to recur in the analysis of various heat transfer problems and in the analysis of the thermal behavior of living tissue when modeled by cylindrical shells.

  9. Thresholding projection estimators in functional linear models

    Cardot, Hervé; Johannes, Jan

    2010-01-01

    We consider the problem of estimating the regression function in functional linear regression models by proposing a new type of projection estimators which combine dimension reduction and thresholding. The introduction of a threshold rule allows to get consistency under broad assumptions as well as minimax rates of convergence under additional regularity hypotheses. We also consider the particular case of Sobolev spaces generated by the trigonometric basis which permits to get easily mean squ...

  10. Diagnostics for Linear Models With Functional Responses

    Xu, Hongquan; Shen, Qing

    2005-01-01

    Linear models where the response is a function and the predictors are vectors are useful in analyzing data from designed experiments and other situations with functional observations. Residual analysis and diagnostics are considered for such models. Studentized residuals are defined and their properties are studied. Chi-square quantile-quantile plots are proposed to check the assumption of Gaussian error process and outliers. Jackknife residuals and an associated test are proposed to det...

  11. Ion transport properties of mechanically stable symmetric ABCBA pentablock copolymers with quaternary ammonium functionalized midblock

    Ertem, S. Piril [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Caire, Benjamin R. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Tsai, Tsung-Han [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Zeng, Di [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Vandiver, Melissa A. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Kusoglu, Ahmet [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Seifert, Soenke [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Hayward, Ryan C. [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Weber, Adam Z. [Energy Conversion Group, Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley California 94720; Herring, Andrew M. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Coughlin, E. Bryan [Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive Amherst Massachusetts 01003; Liberatore, Matthew W. [Department of Chemical Engineering Department, University of Toledo, 2801 W Bancroft Street MS305 Toledo Ohio 43606

    2017-02-07

    Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ion exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br2 at 90 8C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. Xray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.

  12. Non-linear Shear and Uniaxial Extensional Rheology of Polyether-Ester-Sulfonate Copolymer Ionomer Melts

    Shabbir, Aamir; Huang, Qian; P. Baeza, Guilhem

    2017-01-01

    We present unique nonlinear shear and extensional rheology data of unentan-gled amorphous polyester ionomers based on polyethers and sulphonated phthalates with sodium/ lithium counterions. Previous linear viscoelastic (LVE) measurements1 showed significant elasticity in these ionomers due...

  13. Thermoplastic elastomers blends based on linear low density polyethylene, ethylene-1-octene copolymers and ground rubber tire

    Marisa Cristina Guimarães Rocha

    2014-01-01

    Full Text Available Blends of linear low density polyethylene (LLDPE ethylene-1-octene copolymers (EOC, with different 1-octene (OC content, and ground rubber tire (GRT were prepared by melt mixing in a twin screw extruder. Five different compositions of LLDPE/EOC/GRT blends were processed in the extruder to evaluate the effect of EOC addition to the LLDPE/GRT blends. The addition of EOC to LLDPE/GRT blends improves the mechanical properties. Besides, the replacement of 5% of GRT by EOC grades (OC = 20 or 30 wt % in the 50/50 LLDPE/GRT blend, leads to a significant increase of ultimate tensile properties. The EOC comonomer content affects the properties of LLDPE/EOC and LLDPE/EOC/GRT blends. Dynamical-mechanical analyses showed that, with the addition of EOC to LLDPE/GRT blends, the Tg of GRT and the Tg of EOC are closer. This effect is more pronounced when the EOC with the highest content of comonomer (30 wt % is added to LLDPE/GRT blend. In this case, only one peak related to the Tg of the rubber phase can be visualized in the amorphous region. These findings indicate that EOC may act as compatibilizer agent for LLDPE/GRT blends.

  14. Linear functional analysis for scientists and engineers

    Limaye, Balmohan V

    2016-01-01

    This book provides a concise and meticulous introduction to functional analysis. Since the topic draws heavily on the interplay between the algebraic structure of a linear space and the distance structure of a metric space, functional analysis is increasingly gaining the attention of not only mathematicians but also scientists and engineers. The purpose of the text is to present the basic aspects of functional analysis to this varied audience, keeping in mind the considerations of applicability. A novelty of this book is the inclusion of a result by Zabreiko, which states that every countably subadditive seminorm on a Banach space is continuous. Several major theorems in functional analysis are easy consequences of this result. The entire book can be used as a textbook for an introductory course in functional analysis without having to make any specific selection from the topics presented here. Basic notions in the setting of a metric space are defined in terms of sequences. These include total boundedness, c...

  15. Ultrahigh Molecular Weight Linear Block Copolymers: Rapid Access by Reversible-Deactivation Radical Polymerization and Self- Assembly into Large Domain Nanostructures

    Mapas, Jose Kenneth D.; Thomay, Tim; Cartwright, Alexander N.; Ilavsky, Jan; Rzayev, Javid

    2016-05-05

    Block copolymer (BCP) derived periodic nanostructures with domain sizes larger than 150 nm present a versatile platform for the fabrication of photonic materials. So far, the access to such materials has been limited to highly synthetically involved protocols. Herein, we report a simple, “user-friendly” method for the preparation of ultrahigh molecular weight linear poly(solketal methacrylate-b-styrene) block copolymers by a combination of Cu-wire-mediated ATRP and RAFT polymerizations. The synthesized copolymers with molecular weights up to 1.6 million g/mol and moderate dispersities readily assemble into highly ordered cylindrical or lamella microstructures with domain sizes as large as 292 nm, as determined by ultra-small-angle x-ray scattering and scanning electron microscopy analyses. Solvent cast films of the synthesized block copolymers exhibit stop bands in the visible spectrum correlated to their domain spacings. The described method opens new avenues for facilitated fabrication and the advancement of fundamental understanding of BCP-derived photonic nanomaterials for a variety of applications.

  16. Linear Prediction Using Refined Autocorrelation Function

    M. Shahidur Rahman

    2007-07-01

    Full Text Available This paper proposes a new technique for improving the performance of linear prediction analysis by utilizing a refined version of the autocorrelation function. Problems in analyzing voiced speech using linear prediction occur often due to the harmonic structure of the excitation source, which causes the autocorrelation function to be an aliased version of that of the vocal tract impulse response. To estimate the vocal tract characteristics accurately, however, the effect of aliasing must be eliminated. In this paper, we employ homomorphic deconvolution technique in the autocorrelation domain to eliminate the aliasing effect occurred due to periodicity. The resulted autocorrelation function of the vocal tract impulse response is found to produce significant improvement in estimating formant frequencies. The accuracy of formant estimation is verified on synthetic vowels for a wide range of pitch frequencies typical for male and female speakers. The validity of the proposed method is also illustrated by inspecting the spectral envelopes of natural speech spoken by high-pitched female speaker. The synthesis filter obtained by the current method is guaranteed to be stable, which makes the method superior to many of its alternatives.

  17. Rotational partition functions for linear molecules

    McDowell, R.S.

    1988-01-01

    An accurate closed-form expression for the rotational partition function of linear polyatomic molecules in 1 summation electronic states is derived, including the effect of nuclear spin (significant at very low temperatures) and of quartic and sextic centrifugal distortion terms (significant at moderate and high temperatures). The proper first-order quantum correction to the classical rigid-rotator partition function is shown to yield Q/sub r/ ≅β -1 exp(β/3), where βequivalenthcB/kT and B is the rotational constant in cm -1 ; for β≥0.2 additional power-series terms in β are necessary. Comparison between the results of this treatment and exact summations are made for HCN and C 2 H 2 at temperatures from 2 to 5000 K, including separate evaluation of the contributions of nuclear spin and centrifugal distortion

  18. Chemical modifications to vesicle forming diblock copolymers: Development of smart functional polymersome membranes

    Katz, Joshua S.

    2011-07-01

    A major limitation to current treatment regimens for diseases is the inability to adequately deliver therapeutics. Many routes to encapsulation of these materials have been explored to improve biodistribution and better protect encapsulants from harsh biological conditions. One vehicle particularly attractive for encapsulation of such materials is the polymersome. While promising for translation to clinical use, there are still limitations in polymer chemistry and resulting polymersome behavior that will slow their adaptation. This thesis addresses several of these limitations. The first major limitation to polymersomes is lack of control over their release rate. Release is generally by simple diffusion, leading to a burst. To address this burst, Aim 1 proposes a route to stabilizing polymersome membranes through their polymerization. PCL-PEG copolymers were terminally acrylated and the acrylates polymerized in the membrane following vesicle assembly. Polymerization enhanced mechanical robustness of the membranes and reduced diffusion of encapsulated contents. To ultimately trigger release, Aim 2 presents a novel route to synthesizing diblock copolymers, enabling insertion of a functional group at the blocks' junction. To facilitate triggering of release, we inserted UV-cleavable 2-nitrophenylalanine. Polymersomes assembled from this polymer collapse upon exposure to light and molecules release. Demonstrating further utility of this synthetic route, fluorescent vesicles were prepared using fluorescent lysine as the joining molecule. These vesicles labeled dendritic cells, providing a novel route to cell labeling and tracking. The second limitation to vesicles promising for biomedical applications (made of PCL-PEG) is their solid membranes. Aim 3 demonstrates partial (or full) replacement of the PCL block with a caprolactone analogue, TOSUO, which is non-crystalline and assembles into soft, deformable vesicles. Increasing TOSUO content in the copolymer leads to

  19. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    Brisset, Florian; Vieillard, Julien; Berton, Benjamin; Morin-Grognet, Sandrine; Duclairoir-Poc, Cécile; Le Derf, Franck

    2015-01-01

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique

  20. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    Brisset, Florian, E-mail: florian.brisset@etu.univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Vieillard, Julien, E-mail: julien.vieillard@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Berton, Benjamin, E-mail: benjamin.berton@univ-rouen.fr [EA 3233 SMS, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Morin-Grognet, Sandrine, E-mail: sandrine.morin@univ-rouen.fr [EA 3829 MERCI, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Duclairoir-Poc, Cécile, E-mail: cecile.duclairoir@univ-rouen.fr [EA 4312 LMSM, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Le Derf, Franck, E-mail: franck.lederf@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France)

    2015-02-28

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique.

  1. SiO{sub 2} nanodot arrays using functionalized block copolymer templates and selective silylation

    Kim, Su Min; Ku, Se Jin; Kim, Jin-Baek, E-mail: kjb@kaist.ac.kr [Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), 373-1, Guseong-Dong, Yuseong-Gu, Daejeon, 305-701 (Korea, Republic of)

    2010-06-11

    Silicon oxide nanodot arrays were fabricated using functionalized block copolymer templates and selective silylation. A polystyrene-b-poly(acrylic acid/acrylic anhydride) (PS-b-PAA/AN) thin film containing spherical nanodomains was used as a template to build nanoscopic silica structures. A PS-b-PAA/AN thin film was prepared by acid-catalyzed thermal deprotection of polystyrene-b-poly(tert-butyl acrylate) on an SU-8 resist film containing a photoacid generator. This resulting film has excellent solvent and thermal resistance due to crosslinked anhydride linkages in carboxyl-functionalized PAA/AN block domains. Silicon was introduced by spin-spraying of hexamethyldisilazane (HMDS) over the entire surface of a self-assembled PS-b-PAA/AN thin film. HMDS was selectively reacted with carboxylic acid groups in spherical domains of a PAA/AN block. SiO{sub 2} nanodot arrays were generated by oxygen reactive ion etching.

  2. Synthesis of Polystyrene-Based Random Copolymers with Balanced Number of Basic or Acidic Functional Groups

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    for the functionalization were applied. The first one involved direct functionalization of the template backbone through alkylation of the phenolic groups with suitable reagents. The second modification approach was based on "click" chemistry, where the introduction of alkyne groups onto the template backbone was followed......Pairs of polystyrene-based random copolymers with balanced number of pendant basic or acidic groups were synthesized utilizing the template strategy. The same poly[(4-hydroxystyrene)-ran-styrene] was used as a template backbone for modification. Two different synthetic approaches...... by copper-catalyzed 1,3 cycloaddition of aliphatic sulfonate- or amine-contaning azides. Both synthetic approaches proved to be highly efficient as evidenced by H-1-NMR analyses. The thermal properties were evaluated by differential scanning calorimetry and thermal gravimetric analyses and were influenced...

  3. On the characterization of dynamic supramolecular systems: a general mathematical association model for linear supramolecular copolymers and application on a complex two-component hydrogen-bonding system.

    Odille, Fabrice G J; Jónsson, Stefán; Stjernqvist, Susann; Rydén, Tobias; Wärnmark, Kenneth

    2007-01-01

    A general mathematical model for the characterization of the dynamic (kinetically labile) association of supramolecular assemblies in solution is presented. It is an extension of the equal K (EK) model by the stringent use of linear algebra to allow for the simultaneous presence of an unlimited number of different units in the resulting assemblies. It allows for the analysis of highly complex dynamic equilibrium systems in solution, including both supramolecular homo- and copolymers without the recourse to extensive approximations, in a field in which other analytical methods are difficult. The derived mathematical methodology makes it possible to analyze dynamic systems such as supramolecular copolymers regarding for instance the degree of polymerization, the distribution of a given monomer in different copolymers as well as its position in an aggregate. It is to date the only general means to characterize weak supramolecular systems. The model was fitted to NMR dilution titration data by using the program Matlab, and a detailed algorithm for the optimization of the different parameters has been developed. The methodology is applied to a case study, a hydrogen-bonded supramolecular system, salen 4+porphyrin 5. The system is formally a two-component system but in reality a three-component system. This results in a complex dynamic system in which all monomers are associated to each other by hydrogen bonding with different association constants, resulting in homo- and copolymers 4n5m as well as cyclic structures 6 and 7, in addition to free 4 and 5. The system was analyzed by extensive NMR dilution titrations at variable temperatures. All chemical shifts observed at different temperatures were used in the fitting to obtain the DeltaH degrees and DeltaS degrees values producing the best global fit. From the derived general mathematical expressions, system 4+5 could be characterized with respect to above-mentioned parameters.

  4. A logic circuit for solving linear function by digital method

    Ma Yonghe

    1986-01-01

    A mathematical method for determining the linear relation of physical quantity with rediation intensity is described. A logic circuit has been designed for solving linear function by digital method. Some applications and the circuit function are discussed

  5. Synthesis and characterization of functional copolymer/organo-silicate nanoarchitectures through interlamellar complex-radical (coterpolymerization

    2008-09-01

    Full Text Available The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical (coterpolymerization of intercalated monomer complexes of maleic anhydride (MA and itaconic acid (IA with dimethyl dodecylamine surface modified montmorillonite (organo-MMT (MA…DMDA-MMT and IA…DMDA-MMT n-butyl methacrylate (BMA and/or BMA/styrene monomer mixtures. The results of nanocomposite structure–composition– property relationship studies indicate that interlamellar complex-formation between anhydride/acid units and surface alkyl amine and rigid/flexible linkage balance in polymer chains are important factors providing the effective intercalation/ exfoliation of the polymer chains into the silicate galleries, the formation of nanostructural hybrids with higher thermal stability, dynamic mechanical behaviour and well dispersed morphology.

  6. Biomimetic triblock copolymer membrane arrays: a stable template for functional membrane proteins

    Gonzalez-Perez, A.; Jensen, Karin Bagger Stibius; Vissing, Thomas

    2009-01-01

    It is demonstrated that biomimetic stable triblock copolymer membrane arrays can be prepared using a scaffold containing 64 apertures of 300 μm diameter each. The membranes were made from a stock solution of block copolymers with decane as a solvent using a new deposition method. By using decane...

  7. Reduction of Linear Functional Systems using Fuhrmann's Equivalence

    Mohamed S. Boudellioua

    2016-11-01

    Full Text Available Functional systems arise in the treatment of systems of partial differential equations, delay-differential equations, multidimensional equations, etc. The problem of reducing a linear functional system to a system containing fewer equations and unknowns was first studied by Serre. Finding an equivalent presentation of a linear functional system containing fewer equations and fewer unknowns can generally simplify both the study of the structural properties of the linear functional system and of different numerical analysis issues, and it can sometimes help in solving the linear functional system. In this paper, Fuhrmann's equivalence is used to present a constructive result on the reduction of under-determined linear functional systems to a single equation involving a single unknown. This equivalence transformation has been studied by a number of authors and has been shown to play an important role in the theory of linear functional systems.

  8. Soft Functional Silicone Elastomers with High Dielectric Permittivty: Simple Additives vs. Cross-Linked Synthesized Copolymers

    Madsen, Frederikke Bahrt; Yu, Liyun; Skov, Anne Ladegaard

    Though dielectric elastomers (DEs) have many favorable properties, the issue of high driving voltages limits the commercial viability of the technology. Improved actuation at lower voltages can be obtained by decreasing the Young’s modulus and/or decreasing the dielectric permittivity of the elas......Though dielectric elastomers (DEs) have many favorable properties, the issue of high driving voltages limits the commercial viability of the technology. Improved actuation at lower voltages can be obtained by decreasing the Young’s modulus and/or decreasing the dielectric permittivity...... of the elastomer. A decrease in Young’s modulus, however, is often accompanied by the loss of mechanical stability and thereby the lifetime of the DE whereas addition of high permittivity fillers such as metal oxides often increases Young’s modulus such that improved actuation is not accomplished. New soft...... silicone elastomers with high dielectric permittivity were prepared through the use of chloropropyl-functional silicones. One method was through the synthesis of modular cross-linkable chloropropyl-functional copolymers that allow for a high degree of chemical freedom such that a tuneable silicone...

  9. Living cationic polymerization and polyhomologation: an ideal combination to synthesize functionalized polyethylene–polyisobutylene block copolymers

    Zhang, Hefeng

    2015-12-17

    A series of hydroxyl-terminated polyisobutylene-b-polyethylene (PIB-b-PE-OH) copolymers were synthesized by combining living cationic polymerization and polyhomologation. Allyl-terminated PIBs, synthesized by living cationic polymerization, were hydroborated with BH3·THF to produce 3-arm boron-linked stars, PIB3B, which served as macroinitiators for the in situ polyhomologation of dimethylsulfoxonium methylide. The resulting 3-arm star block copolymers, (PIB-b-PE)3B, were oxidized/hydrolysed to afford PIB-b-PE-OH. Characterization of all intermediates and final products by high temperature gel permeation chromatography (HT-GPC) and proton nuclear magnetic resonance spectroscopy (1H NMR) revealed the well-defined character of the copolymers. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC).

  10. Bacterial Reaction Centers Purified with Styrene Maleic Acid Copolymer Retain Native Membrane Functional Properties and Display Enhanced Stability**

    Swainsbury, David J K; Scheidelaar, Stefan; van Grondelle, Rienk; Killian, J Antoinette; Jones, Michael R

    2014-01-01

    Integral membrane proteins often present daunting challenges for biophysical characterization, a fundamental issue being how to select a surfactant that will optimally preserve the individual structure and functional properties of a given membrane protein. Bacterial reaction centers offer a rare opportunity to compare the properties of an integral membrane protein in different artificial lipid/surfactant environments with those in the native bilayer. Here, we demonstrate that reaction centers purified using a styrene maleic acid copolymer remain associated with a complement of native lipids and do not display the modified functional properties that typically result from detergent solubilization. Direct comparisons show that reaction centers are more stable in this copolymer/lipid environment than in a detergent micelle or even in the native membrane, suggesting a promising new route to exploitation of such photovoltaic integral membrane proteins in device applications. PMID:25212490

  11. Silicon containing copolymers

    Amiri, Sahar; Amiri, Sanam

    2014-01-01

    Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers?are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

  12. Determination of the linear coefficient of thermal expansion in polymer films at the nanoscale: influence of the composition of EVA copolymers and the molecular weight of PMMA.

    González-Benito, J; Castillo, E; Cruz-Caldito, J F

    2015-07-28

    Nanothermal-expansion of poly(ethylene-co-vinylacetate), EVA, and poly(methyl methacrylate), PMMA, in the form of films was measured to finally obtain linear coefficients of thermal expansion, CTEs. The simple deflection of a cantilever in an atomic force microscope, AFM, was used to monitor thermal expansions at the nanoscale. The influences of: (a) the structure of EVA in terms of its composition (vinylacetate content) and (b) the size of PMMA chains in terms of the molecular weight were studied. To carry out this, several polymer samples were used, EVA copolymers with different weight percents of the vinylacetate comonomer (12, 18, 25 and 40%) and PMMA polymers with different weight average molecular weights (33.9, 64.8, 75.600 and 360.0 kg mol(-1)). The dependencies of the vinyl acetate weight fraction of EVA and the molecular weight of PMMA on their corresponding CTEs were analyzed to finally explain them using new, intuitive and very simple models based on the rule of mixtures. In the case of EVA copolymers a simple equation considering the weighted contributions of each comonomer was enough to estimate the final CTE above the glass transition temperature. On the other hand, when the molecular weight dependence is considered the free volume concept was used as novelty. The expansion of PMMA, at least at the nanoscale, was well and easily described by the sum of the weighted contributions of the occupied and free volumes, respectively.

  13. Temperature-Responsive Biocompatible Copolymers Incorporating Hyperbranched Polyglycerols for Adjustable Functionality

    Alan J. House

    2011-08-01

    Full Text Available Temperature-triggered copolymers are proposed for a number of bio-applications but there is no ideal material platform, especially for injectable drug delivery. Options are needed for degradable biomaterials that not only respond to temperature but also easily accommodate linkage of active molecules. A first step toward realizing this goal is the design and synthesis of the novel materials reported herein. A multifunctional macromer, methacrylated hyperbranched polyglycerol (HPG-MA with an average of one acrylate unit per copolymer, was synthesized and copolymerized with N-isopropylacrylamide (NIPAAm, hydroxyethyl methacrylate-polylactide (HEMAPLA and acrylic acid (AAc. The potential to fully exploit the copolymers by modification of the multiple HPG hydroxyl groups will not be discussed here. Instead, this report focuses on the thermoresponsive, biocompatible, and degradation properties of the material. Poly(NIPAAm-co-HEMAPLA-co-AAc-co-HPG-MA displayed increasing lower critical solution temperatures (LCST as the HPG content increased over a range of macromer ratios. For the copolymer with the maximum HPG incorporation (17%, the LCST was ~30 °C. In addition, this sample showed no toxicity when human uterine fibroid cells were co-cultured with the copolymer for up to 72 h. This copolymer lost approximately 92% of its mass after 17 hours at 37 °C. Thus, the reported biomaterials offer attractive properties for the design of drug delivery systems where orthogonally triggered mechanisms of therapeutic release in relatively short time periods would be attractive.

  14. Fluids density functional theory and initializing molecular dynamics simulations of block copolymers

    Brown, Jonathan R.; Seo, Youngmi; Maula, Tiara Ann D.; Hall, Lisa M.

    2016-03-01

    Classical, fluids density functional theory (fDFT), which can predict the equilibrium density profiles of polymeric systems, and coarse-grained molecular dynamics (MD) simulations, which are often used to show both structure and dynamics of soft materials, can be implemented using very similar bead-based polymer models. We aim to use fDFT and MD in tandem to examine the same system from these two points of view and take advantage of the different features of each methodology. Additionally, the density profiles resulting from fDFT calculations can be used to initialize the MD simulations in a close to equilibrated structure, speeding up the simulations. Here, we show how this method can be applied to study microphase separated states of both typical diblock and tapered diblock copolymers in which there is a region with a gradient in composition placed between the pure blocks. Both methods, applied at constant pressure, predict a decrease in total density as segregation strength or the length of the tapered region is increased. The predictions for the density profiles from fDFT and MD are similar across materials with a wide range of interfacial widths.

  15. Critical Conditions for Liquid Chromatography of Statistical Copolymers: Functionality Type and Composition Distribution Characterization by UP-LCCC/ESI-MS.

    Epping, Ruben; Panne, Ulrich; Falkenhagen, Jana

    2017-02-07

    Statistical ethylene oxide (EO) and propylene oxide (PO) copolymers of different monomer compositions and different average molar masses additionally containing two kinds of end groups (FTD) were investigated by ultra high pressure liquid chromatography under critical conditions (UP-LCCC) combined with electrospray ionization time-of flight mass spectrometry (ESI-TOF-MS). Theoretical predictions of the existence of a critical adsorption point (CPA) for statistical copolymers with a given chemical and sequence distribution1 could be studied and confirmed. A fundamentally new approach to determine these critical conditions in a copolymer, alongside the inevitable chemical composition distribution (CCD), with mass spectrometric detection, is described. The shift of the critical eluent composition with the monomer composition of the polymers was determined. Due to the broad molar mass distribution (MMD) and the presumed existence of different end group functionalities as well as monomer sequence distribution (MSD), gradient separation only by CCD was not possible. Therefore, isocratic separation conditions at the CPA of definite CCD fractions were developed. Although the various present distributions partly superimposed the separation process, the goal of separation by end group functionality was still achieved on the basis of the additional dimension of ESI-TOF-MS. The existence of HO-H besides the desired allylO-H end group functionalities was confirmed and their amount estimated. Furthermore, indications for a MSD were found by UPLC/MS/MS measurements. This approach offers for the first time the possibility to obtain a fingerprint of a broad distributed statistical copolymer including MMD, FTD, CCD, and MSD.

  16. Retardation of the dewetting process due to the addition of functional copolymers at polymer-polymer interfaces

    Wunnicke, O; Lorenz-Haas, C; Leiner, V

    2002-01-01

    We studied the retardation of the dewetting process due to the addition of a functional copolymer in a polymer bilayer film. The model system consists of fully deuterated polystyrene (PS-d) on top of an amorphous polyamide (PA) sublayer on silicon substrates. Bilayer films were prepared with different content (0, 5, 10 and 30 vol. %) of a statistical copolymer (protonated styrene maleic anhydride acid (SMA2) containing 2% MA groups along the chain) being capable of forming hydrogen bonds with PA. The as-prepared as well as the annealed samples were investigated by neutron-reflectivity (NR) experiments, scanning force microscopy and optical microscopy. A significant retardation of dewetting is observed with the addition of SMA2. From model fits of NR curves the scattering length density profiles perpendicular to the sample surface were determined and an enrichment layer of SMA2 is detected. Retardation is explained by the intermixing of SMA2 and PS-d at the interface. (orig.)

  17. Slope Estimation in Noisy Piecewise Linear Functions.

    Ingle, Atul; Bucklew, James; Sethares, William; Varghese, Tomy

    2015-03-01

    This paper discusses the development of a slope estimation algorithm called MAPSlope for piecewise linear data that is corrupted by Gaussian noise. The number and locations of slope change points (also known as breakpoints) are assumed to be unknown a priori though it is assumed that the possible range of slope values lies within known bounds. A stochastic hidden Markov model that is general enough to encompass real world sources of piecewise linear data is used to model the transitions between slope values and the problem of slope estimation is addressed using a Bayesian maximum a posteriori approach. The set of possible slope values is discretized, enabling the design of a dynamic programming algorithm for posterior density maximization. Numerical simulations are used to justify choice of a reasonable number of quantization levels and also to analyze mean squared error performance of the proposed algorithm. An alternating maximization algorithm is proposed for estimation of unknown model parameters and a convergence result for the method is provided. Finally, results using data from political science, finance and medical imaging applications are presented to demonstrate the practical utility of this procedure.

  18. Basic methods of linear functional analysis

    Pryce, John D

    2011-01-01

    Introduction to the themes of mathematical analysis, geared toward advanced undergraduate and graduate students. Topics include operators, function spaces, Hilbert spaces, and elementary Fourier analysis. Numerous exercises and worked examples.1973 edition.

  19. Linear measure functional differential equations with infinite delay

    Monteiro, G. (Giselle Antunes); Slavík, A.

    2014-01-01

    We use the theory of generalized linear ordinary differential equations in Banach spaces to study linear measure functional differential equations with infinite delay. We obtain new results concerning the existence, uniqueness, and continuous dependence of solutions. Even for equations with a finite delay, our results are stronger than the existing ones. Finally, we present an application to functional differential equations with impulses.

  20. Impact of triblock copolymers on the biophysical function of naturally-derived lung surfactant

    Beck-Broichsitter, Moritz; Ruge, Christian A.; Bohr, Adam

    2017-01-01

    The current study aimed at investigating the general applicability of triblock copolymers consisting of poly(ethylene glycol) and poly(propylene glycol) (Pluronic®) as excipients for lung delivery. After thorough physicochemical characterization of the diverse polymers, their cytotoxicity...... was evaluated using alveolar epithelial cells. Next, a naturally-derived lung surfactant was challenged with the distinct triblock copolymers with respect to changes in microstructure, adsorption to the air/liquid interface and dynamic surface tension behavior under bubble pulsation. Biocompatibility assessment...

  1. Linear regression methods a ccording to objective functions

    Yasemin Sisman; Sebahattin Bektas

    2012-01-01

    The aim of the study is to explain the parameter estimation methods and the regression analysis. The simple linear regressionmethods grouped according to the objective function are introduced. The numerical solution is achieved for the simple linear regressionmethods according to objective function of Least Squares and theLeast Absolute Value adjustment methods. The success of the appliedmethods is analyzed using their objective function values.

  2. Variance Function Partially Linear Single-Index Models1.

    Lian, Heng; Liang, Hua; Carroll, Raymond J

    2015-01-01

    We consider heteroscedastic regression models where the mean function is a partially linear single index model and the variance function depends upon a generalized partially linear single index model. We do not insist that the variance function depend only upon the mean function, as happens in the classical generalized partially linear single index model. We develop efficient and practical estimation methods for the variance function and for the mean function. Asymptotic theory for the parametric and nonparametric parts of the model is developed. Simulations illustrate the results. An empirical example involving ozone levels is used to further illustrate the results, and is shown to be a case where the variance function does not depend upon the mean function.

  3. Block copolymer self-assembly and co-assembly : shape function and application

    Li, F.

    2009-01-01

    Amphiphilic block copolymers can, in selective solvents such as water, assemble into various shapes and architectures. Among those, polymer vesicles, polymer micelles and polymer fibers are very popular structures in current nanotechnology. These objects each have their own particular properties and

  4. Functional porous structures based on the pyrolysis of cured templates of block copolymer and phenolic resin

    Kosonen, H; Valkama, S; Nykanen, A; Toivanen, M; ten Brinke, G; Ruokolainen, J; Ikkala, O; Nykänen, Antti

    2006-01-01

    Porous materials with controlled pore size and large surface area (see Figure) have been prepared by crosslinking phenolic resin in the presence of a self-assembled block-copolymer template, followed by pyrolysis. Many phenolic hydroxyl groups remain at the matrix and pore walls, which can be used

  5. Polyethylene-Based Tadpole Copolymers

    Alkayal, Nazeeha; Zhang, Zhen; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

    2017-01-01

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser

  6. Use of linear discriminant function analysis in seed morphotype ...

    Use of linear discriminant function analysis in seed morphotype relationship study in 31 ... Data were collected on 100-seed weight, seed length and seed width. ... to the Mesoamerican gene pool, comprising the cultigroups Sieva-Big Lima, ...

  7. TRANSFER-FUNCTIONS OF A LINEARIZED MULTI-REGION REACTOR

    Higgins, Thomas J.

    1963-09-15

    The development of the transfer functions for a linearized multi-region reactor is studied, and an illustration is made of application of the corresponding theory by a numerical illustrative example. (auth)

  8. Argument estimates of certain multivalent functions involving a linear operator

    Nak Eun Cho

    2002-01-01

    Full Text Available The purpose of this paper is to derive some argument properties of certain multivalent functions in the open unit disk involving a linear operator. We also investigate their integral preserving property in a sector.

  9. LINTAB, Linear Interpolable Tables from any Continuous Variable Function

    1988-01-01

    1 - Description of program or function: LINTAB is designed to construct linearly interpolable tables from any function. The program will start from any function of a single continuous variable... FUNKY(X). By user input the function can be defined, (1) Over 1 to 100 X ranges. (2) Within each X range the function is defined by 0 to 50 constants. (3) At boundaries between X ranges the function may be continuous or discontinuous (depending on the constants used to define the function within each X range). 2 - Method of solution: LINTAB will construct a table of X and Y values where the tabulated (X,Y) pairs will be exactly equal to the function (Y=FUNKY(X)) and linear interpolation between the tabulated pairs will be within any user specified fractional uncertainty of the function for all values of X within the requested X range

  10. Linear density response function in the projector augmented wave method

    Yan, Jun; Mortensen, Jens Jørgen; Jacobsen, Karsten Wedel

    2011-01-01

    We present an implementation of the linear density response function within the projector-augmented wave method with applications to the linear optical and dielectric properties of both solids, surfaces, and interfaces. The response function is represented in plane waves while the single...... functions of Si, C, SiC, AlP, and GaAs compare well with previous calculations. While optical properties of semiconductors, in particular excitonic effects, are generally not well described by ALDA, we obtain excellent agreement with experiments for the surface loss function of graphene and the Mg(0001...

  11. Interior Point Method for Solving Fuzzy Number Linear Programming Problems Using Linear Ranking Function

    Yi-hua Zhong

    2013-01-01

    Full Text Available Recently, various methods have been developed for solving linear programming problems with fuzzy number, such as simplex method and dual simplex method. But their computational complexities are exponential, which is not satisfactory for solving large-scale fuzzy linear programming problems, especially in the engineering field. A new method which can solve large-scale fuzzy number linear programming problems is presented in this paper, which is named a revised interior point method. Its idea is similar to that of interior point method used for solving linear programming problems in crisp environment before, but its feasible direction and step size are chosen by using trapezoidal fuzzy numbers, linear ranking function, fuzzy vector, and their operations, and its end condition is involved in linear ranking function. Their correctness and rationality are proved. Moreover, choice of the initial interior point and some factors influencing the results of this method are also discussed and analyzed. The result of algorithm analysis and example study that shows proper safety factor parameter, accuracy parameter, and initial interior point of this method may reduce iterations and they can be selected easily according to the actual needs. Finally, the method proposed in this paper is an alternative method for solving fuzzy number linear programming problems.

  12. Microelectrode Arrays and the Use of PEG-Functionalized Diblock Copolymer Coatings

    Sakshi Uppal

    2014-09-01

    Full Text Available PEG-modified diblock copolymer surfaces have been examined for their compatibility with microelectrode array based analytical methods. The use of PEG-modified polymer surfaces on the arrays was initially problematic because the redox couples used in the experiments were adsorbed by the polymer. This led the current measured by cyclic voltammetry for the redox couple to be unstable and increase with time. However, two key findings allow the experiments to be successful. First, after multiple cyclic voltammograms the current associated with the redox couple does stabilize so that a good baseline current can be established. Second, the rate at which the current stabilizes is consistent every time a particular coated array is used. Hence, multiple analytical experiments can be conducted on an array coated with a PEG-modified diblock copolymer and the data obtained is comparable as long as the data for each experiment is collected at a consistent time point.

  13. Surface functionalization of cyclic olefin copolymer (COC) with evaporated TiO{sub 2} thin film

    El Fissi, Lamia, E-mail: lamia.elfissi@uclouvain.be [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium); Vandormael, Denis [SIRRIS Liege Science Park, 4102 Seraing (Belgium); Houssiau, Laurent [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Francis, Laurent A. [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium)

    2016-02-15

    Highlights: • TiO{sub 2}/COC (cyclic olefin copolymer) hybrid material for BioMEMS applications. • Thin layer of TiO{sub 2} was deposed on cyclic olefin copolymer using physical vapor deposition (PVD) technique. • The coating possess the highest level of adhesion with an excellent morphology of the hybrid material (TiO{sub 2}/COC). - Abstract: Cyclic olefin copolymer (COC) is a new class of thermoplastic polymers used for a variety of applications ranging from bio-sensing to optics. However, the hydrophobicity of native COC hampers the further development and application of this material [1]. In this work, we report the structural, morphological, and optical properties of the TiO{sub 2}/COC hybrid material, which provides a desirable substrate for optical devices and subsequent surface modifications. The TiO{sub 2} film on COC substrate was deposited by the evaporation method, and it was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), profilometry and atomic force microscope (AFM). Using an UV-vis spectrophotometer, we found that the transmittance of the TiO{sub 2}/COC hybrid material in the visible domain reached 80%. The TiO{sub 2}/COC hybrid appeared to be stable in most of the assessed polar solvents and acid/basic solutions. The new TiO{sub 2}/COC hybrid material and the robust fabrication method are expected to enable a variety of BioMEMS applications.

  14. Modulation of Quorum Sensing in a Gram Positive Pathogen by Linear Imprinted Copolymers with anti-Infective Properties

    Motib, Anfal; Guerreiro, Antonio; Al-Bayati, Firas; Piletska, Elena; Manzoor, Irfan; Shafeeq, Sulman; Kadam, Anagha; Kuipers, Oscar; Hiller, Luisa; Cowen, Todd; Piletsky, Sergey; Andrew, Peter; Yesilkaya, Hasan

    2017-01-01

    Here we describe the development, characterization and biological testing of a new type of linear molecularly imprinted polymer (LMIP) designed to act as anti-infective by blocking the quorum sensing (QS) mechanism and so preventing virulence of the pathogen Streptococcus pneumoniae. The LMIP is

  15. Transiently chaotic neural networks with piecewise linear output functions

    Chen, S.-S. [Department of Mathematics, National Taiwan Normal University, Taipei, Taiwan (China); Shih, C.-W. [Department of Applied Mathematics, National Chiao Tung University, 1001 Ta-Hsueh Road, Hsinchu, Taiwan (China)], E-mail: cwshih@math.nctu.edu.tw

    2009-01-30

    Admitting both transient chaotic phase and convergent phase, the transiently chaotic neural network (TCNN) provides superior performance than the classical networks in solving combinatorial optimization problems. We derive concrete parameter conditions for these two essential dynamic phases of the TCNN with piecewise linear output function. The confirmation for chaotic dynamics of the system results from a successful application of the Marotto theorem which was recently clarified. Numerical simulation on applying the TCNN with piecewise linear output function is carried out to find the optimal solution of a travelling salesman problem. It is demonstrated that the performance is even better than the previous TCNN model with logistic output function.

  16. Unstable volatility functions: the break preserving local linear estimator

    Casas, Isabel; Gijbels, Irene

    The objective of this paper is to introduce the break preserving local linear (BPLL) estimator for the estimation of unstable volatility functions. Breaks in the structure of the conditional mean and/or the volatility functions are common in Finance. Markov switching models (Hamilton, 1989......) and threshold models (Lin and Terasvirta, 1994) are amongst the most popular models to describe the behaviour of data with structural breaks. The local linear (LL) estimator is not consistent at points where the volatility function has a break and it may even report negative values for finite samples...

  17. Non-linear variation of the beta function with momentum

    Parzen, G.

    1983-07-01

    A theory is presented for computing the non-linear dependence of the β-functions on momentum. Results are found for the quadratic term. The results of the theory are compared with computed results. A procedure is proposed for computing the strengths of the sextupole correctors to correct the dependence of the β-function on momentum

  18. Linearization of non-commuting operators in the partition function

    Ahmed, M.

    1983-06-01

    A generalization of the Stratonovich-Hubbard scheme for evaluating the grand canonical partition function is given. The scheme involves linearization of products of non-commuting operators using the functional integral method. The non-commutivity of the operators leads to an additional term which can be absorbed in the single-particle Hamiltonian. (author)

  19. Some subclasses of multivalent functions involving a certain linear operator

    Srivastava, H. M.; Patel, J.

    2005-10-01

    The authors investigate various inclusion and other properties of several subclasses of the class of normalized p-valent analytic functions in the open unit disk, which are defined here by means of a certain linear operator. Problems involving generalized neighborhoods of analytic functions in the class are investigated. Finally, some applications of fractional calculus operators are considered.

  20. Cationic nanoparticles with quaternary ammonium-functionalized PLGA–PEG-based copolymers for potent gene transfection

    Wang, Yan-Hsung [Kaohsiung Medical University, School of Dentistry, College of Dental Medicine (China); Fu, Yin-Chih [Kaohsiung Medical University, Graduate Institute of Medicine, College of Medicine (China); Chiu, Hui-Chi [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China); Wang, Chau-Zen [Kaohsiung Medical University, Department of Physiology, College of Medicine (China); Lo, Shao-Ping [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China); Ho, Mei-Ling [Kaohsiung Medical University, Department of Physiology, College of Medicine (China); Liu, Po-Len [Kaohsiung Medical University, Department of Respiratory Therapy, College of Medicine (China); Wang, Chih-Kuang, E-mail: ckwang@kmu.edu.tw [Kaohsiung Medical University, Department of Medicinal and Applied Chemistry, College of Life Science (China)

    2013-11-15

    The objective of the present work was to develop new cationic nanoparticles (cNPs) with amphiphilic cationic copolymers for the delivery of plasmid DNA (pDNA). Cationic copolymers were built on the synthesis of quaternary ammonium salt compounds from diethylenetriamine (DETA) to include the positively charged head group and amphiphilic multi-grafts. PLGA-phe-PEG-qDETA (PPD), phe-PEG-qDETA-PLGA (PDP), and PLGA-phe-PEG-qDETA-PLGA (PPDP) cationic copolymers were created by this moiety of DETA quaternary ammonium, heterobifunctional polyethylene glycol (COOH-PEG-NH{sub 2}), phenylalanine (phe), and poly(lactic-co-glycolic acid) (PLGA). These new cNPs were prepared by the water miscible solvent displacement method. They exhibit good pDNA binding ability, as shown in a retardation assay that occurred at a particle size of ∼217 nm. The zeta potential was approximately +21 mV when the cNP concentration was 25 mg/ml. The new cNPs also have a better buffering capacity than PLGA NPs. However, the pDNA binding ability was demonstrated starting at a weight ratio of approximately 6.25 cNPs/pDNA. Gene transfection results showed that these cNPs had transfection effects similar to those of Lipofectamine 2000 in 293T cells. Furthermore, cNPs can also transfect human adipose-derived stem cells. The results indicate that the newly developed cNP is a promising candidate for a novel gene delivery vehicle.

  1. The Relationships between Weight Functions, Geometric Functions,and Compliance Functions in Linear Elastic Fracture Mechanics

    Yuan, Rong [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Linear elastic fracture mechanics is widely used in industry because it established simple and explicit relationships between the permissible loading conditions and the critical crack size that is allowed in a structure. Stress intensity factors are the above-mentioned functional expressions that relate load with crack size through geometric functions or weight functions. Compliance functions are to determine the crack/flaw size in a structure when optical inspection is inconvenient. As a result, geometric functions, weight functions and compliance functions have been intensively studied to determine the stress intensity factor expressions for different geometries. However, the relations between these functions have received less attention. This work is therefore to investigate the intrinsic relationships between these functions. Theoretical derivation was carried out and the results were verified on single-edge cracked plate under tension and bending. It is found out that the geometric function is essentially the non-dimensional weight function at the loading point. The compliance function is composed of two parts: a varying part due to crack extension and a constant part from the intact structure if no crack exists. The derivative of the compliance function at any location is the product of the geometric function and the weight function at the evaluation point. Inversely, the compliance function can be acquired by the integration of the product of the geometric function and the weight function with respect to the crack size. The integral constant is just the unchanging compliance from the intact structure. Consequently, a special application of the relations is to obtain the compliance functions along a crack once the geometric function and weight functions are known. Any of the three special functions can be derived once the other two functions are known. These relations may greatly simplify the numerical process in obtaining either geometric functions, weight

  2. Phosphate functionalized and lactic acid containing graft copolymer: synthesis and evaluation as biomaterial for bone tissue engineering applications.

    Datta, Pallab; Chatterjee, Jyotirmoy; Dhara, Santanu

    2013-01-01

    Polyvinyl alcohol (PVA) and polylactic acids (PLA) are biocompatible materials possessing some inherent contrasting limitations which have reduced the scope of their individual applicability. Specifically, overcoming strong hydrophobicity and introducing chemical groups for biofunctionalization are unmet challenges for PLA whilst chemical endeavors to render adequate aqueous stability and cell adhesion properties to PVA have not produced completely intended results. Objective of the present work is to explore synthesis of a graft polymer as an approach towards coupling biofunctional groups with PLA materials. In a two-step reaction, PPVA (phosphorylated polyvinyl alcohol or PVA pre-functionalized with phosphate) is esterified with lactic acid followed by polymerization into PLA in presence of stannous chloride as catalyst to obtain phosphorylated polyvinyl alcohol-graft-polylactic acid (PPVA-g-LA) copolymer. Product is characterized by nuclear magnetic resonance, X-ray diffraction, and thermogravimetric analysis. PPVA-g-LA shows an increase in uniaxial elongation compared to parent PPVA under condition of tensile loading. The graft copolymer also exhibits higher water contact angles compared to PPVA, but a more hydrophilic surface compared to PLA. Culture of MG-63 cells on solvent cast films of polymers demonstrates that PPVA-g-LA as a cell substrate can significantly (p acid-based biomaterials with subsequent improvement in cell response on the polymers. In this attempt, it also affords materials with tunable surface or bulk properties of relevance for tissue engineering applications.

  3. Non-covalent functionalization of carbon nanotubes: Controlling Chirality Selectivity via Alkyl Groups of Conjugated Co-Polymers

    Weight, Braden; Gifford, Brendan; Kilina, Svetlana

    Carbon nanotubes (CNTs) play an important role in nanotechnology, including electronics, chemical sensors, and solar cells. Their electronic and optical properties depend on the size and geometry (chirality) of the nanotube. However, one main concern regarding nanotube application in optoelectronic devices is the difficulty of separating them based upon chirality after synthesis, as all known synthesis methods produce more than one chirality simultaneously. To get around this, one method is the functionalization of the CNTs via non-covalent bonding of co-polymers by wrapping them around the tube. We use force field simulations to explore the effects of various structural manipulations to the co-polymer 9,9-dialkylfluorenyl-2,7-diyl bipyridine (PFO-BPY) to find the preferential mechanisms of selective interactions between the PFO-BPY and CNTs of various chiralities. In particular, we focus on the effect of the branching in alkyl side-groups of PFO-BPY on their binding to the CNT surface. We have observed correlations between the side-group structures and their wrapping morphology on the CNT-Polymer interactions. Our calculations demonstrate that the branching in the position closest to the conjugated backboned results in the strongest interaction with all CNT. This research was supported by the National Science Foundation (CHE 1413614) and the Center for Computationally-Assisted Science and Technology at NDSU.

  4. Functional linear models for association analysis of quantitative traits.

    Fan, Ruzong; Wang, Yifan; Mills, James L; Wilson, Alexander F; Bailey-Wilson, Joan E; Xiong, Momiao

    2013-11-01

    Functional linear models are developed in this paper for testing associations between quantitative traits and genetic variants, which can be rare variants or common variants or the combination of the two. By treating multiple genetic variants of an individual in a human population as a realization of a stochastic process, the genome of an individual in a chromosome region is a continuum of sequence data rather than discrete observations. The genome of an individual is viewed as a stochastic function that contains both linkage and linkage disequilibrium (LD) information of the genetic markers. By using techniques of functional data analysis, both fixed and mixed effect functional linear models are built to test the association between quantitative traits and genetic variants adjusting for covariates. After extensive simulation analysis, it is shown that the F-distributed tests of the proposed fixed effect functional linear models have higher power than that of sequence kernel association test (SKAT) and its optimal unified test (SKAT-O) for three scenarios in most cases: (1) the causal variants are all rare, (2) the causal variants are both rare and common, and (3) the causal variants are common. The superior performance of the fixed effect functional linear models is most likely due to its optimal utilization of both genetic linkage and LD information of multiple genetic variants in a genome and similarity among different individuals, while SKAT and SKAT-O only model the similarities and pairwise LD but do not model linkage and higher order LD information sufficiently. In addition, the proposed fixed effect models generate accurate type I error rates in simulation studies. We also show that the functional kernel score tests of the proposed mixed effect functional linear models are preferable in candidate gene analysis and small sample problems. The methods are applied to analyze three biochemical traits in data from the Trinity Students Study. © 2013 WILEY

  5. Synthesis of Functional Block Copolymers Carrying One Poly( p -phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure

    Menk, Florian

    2016-02-29

    Block copolymers composed of a MEH-PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60-95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optical properties depending on the polymer composition and the micellization procedure. Furthermore, the reactive ester carrying block copolymers enabled the introduction of anchor groups which facilitated the preparation of nanocomposites with CdSe/CdZnS core-shell QDs. The obtained composites were studied using time-resolved photoluminescence measurements. The results revealed an increased interaction based on an accelerated decay of the QD emission for composites as compared to the mixture of the QDs with unfunctionalized polymers. © 2016 American Chemical Society.

  6. Synthesis of Functional Block Copolymers Carrying One Poly( p -phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure

    Menk, Florian; Shin, Suyong; Kim, Kyung-Oh; Scherer, Martin; Gehrig, Dominik; Laquai, Fré dé ric; Choi, Tae-Lim; Zentel, Rudolf

    2016-01-01

    Block copolymers composed of a MEH-PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60-95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optical properties depending on the polymer composition and the micellization procedure. Furthermore, the reactive ester carrying block copolymers enabled the introduction of anchor groups which facilitated the preparation of nanocomposites with CdSe/CdZnS core-shell QDs. The obtained composites were studied using time-resolved photoluminescence measurements. The results revealed an increased interaction based on an accelerated decay of the QD emission for composites as compared to the mixture of the QDs with unfunctionalized polymers. © 2016 American Chemical Society.

  7. Linear circuit transfer functions an introduction to fast analytical techniques

    Basso, Christophe P

    2016-01-01

    Linear Circuit Transfer Functions: An introduction to Fast Analytical Techniques teaches readers how to determine transfer functions of linear passive and active circuits by applying Fast Analytical Circuits Techniques. Building on their existing knowledge of classical loop/nodal analysis, the book improves and expands their skills to unveil transfer functions in a swift and efficient manner. Starting with simple examples, the author explains step-by-step how expressing circuits time constants in different configurations leads to writing transfer functions in a compact and insightful way. By learning how to organize numerators and denominators in the fastest possible way, readers will speed-up analysis and predict the frequency resp nse of simple to complex circuits. In some cases, they will be able to derive the final expression by inspection, without writing a line of algebra. Key features: * Emphasizes analysis through employing time constant-based methods discussed in other text books but not widely us...

  8. Optimal choice of basis functions in the linear regression analysis

    Khotinskij, A.M.

    1988-01-01

    Problem of optimal choice of basis functions in the linear regression analysis is investigated. Step algorithm with estimation of its efficiency, which holds true at finite number of measurements, is suggested. Conditions, providing the probability of correct choice close to 1 are formulated. Application of the step algorithm to analysis of decay curves is substantiated. 8 refs

  9. A new chaotic Hopfield network with piecewise linear activation function

    Peng-Sheng, Zheng; Wan-Sheng, Tang; Jian-Xiong, Zhang

    2010-01-01

    This paper presents a new chaotic Hopfield network with a piecewise linear activation function. The dynamic of the network is studied by virtue of the bifurcation diagram, Lyapunov exponents spectrum and power spectrum. Numerical simulations show that the network displays chaotic behaviours for some well selected parameters

  10. On nonnegative solutions of second order linear functional differential equations

    Lomtatidze, Alexander; Vodstrčil, Petr

    2004-01-01

    Roč. 32, č. 1 (2004), s. 59-88 ISSN 1512-0015 Institutional research plan: CEZ:AV0Z1019905 Keywords : second order linear functional differential equations * nonnegative solution * two-point boundary value problem Subject RIV: BA - General Mathematics

  11. Geometrically non linear analysis of functionally graded material ...

    user

    when compared to the other engineering materials (Akhavan and Hamed, 2010). However, FGM plates under mechanical loading may undergo elastic instability. Hence, the non-linear behavior of functionally graded plates has to be understood for their optimum design. Reddy (2000) proposed the theoretical formulation ...

  12. The linear potential propagator via wave function expansion

    Nassar, Antonio B.; Cattani, Mauro S.D.

    2002-01-01

    We evaluate the quantum propagator for the motion of a particle in a linear potential via a recently developed formalism [A.B. Nassar et al., Phys. Rev. E56, 1230, (1997)]. In this formalism, the propagator comes about as a type of expansion of the wave function over the space of the initial velocities. (author)

  13. A Hamiltonian functional for the linearized Einstein vacuum field equations

    Rosas-RodrIguez, R

    2005-01-01

    By considering the Einstein vacuum field equations linearized about the Minkowski metric, the evolution equations for the gauge-invariant quantities characterizing the gravitational field are written in a Hamiltonian form by using a conserved functional as Hamiltonian; this Hamiltonian is not the analog of the energy of the field. A Poisson bracket between functionals of the field, compatible with the constraints satisfied by the field variables, is obtained. The generator of spatial translations associated with such bracket is also obtained

  14. Block coordination copolymers

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  15. Generalized Functional Linear Models With Semiparametric Single-Index Interactions

    Li, Yehua

    2010-06-01

    We introduce a new class of functional generalized linear models, where the response is a scalar and some of the covariates are functional. We assume that the response depends on multiple covariates, a finite number of latent features in the functional predictor, and interaction between the two. To achieve parsimony, the interaction between the multiple covariates and the functional predictor is modeled semiparametrically with a single-index structure. We propose a two step estimation procedure based on local estimating equations, and investigate two situations: (a) when the basis functions are pre-determined, e.g., Fourier or wavelet basis functions and the functional features of interest are known; and (b) when the basis functions are data driven, such as with functional principal components. Asymptotic properties are developed. Notably, we show that when the functional features are data driven, the parameter estimates have an increased asymptotic variance, due to the estimation error of the basis functions. Our methods are illustrated with a simulation study and applied to an empirical data set, where a previously unknown interaction is detected. Technical proofs of our theoretical results are provided in the online supplemental materials.

  16. Generalized Functional Linear Models With Semiparametric Single-Index Interactions

    Li, Yehua; Wang, Naisyin; Carroll, Raymond J.

    2010-01-01

    We introduce a new class of functional generalized linear models, where the response is a scalar and some of the covariates are functional. We assume that the response depends on multiple covariates, a finite number of latent features in the functional predictor, and interaction between the two. To achieve parsimony, the interaction between the multiple covariates and the functional predictor is modeled semiparametrically with a single-index structure. We propose a two step estimation procedure based on local estimating equations, and investigate two situations: (a) when the basis functions are pre-determined, e.g., Fourier or wavelet basis functions and the functional features of interest are known; and (b) when the basis functions are data driven, such as with functional principal components. Asymptotic properties are developed. Notably, we show that when the functional features are data driven, the parameter estimates have an increased asymptotic variance, due to the estimation error of the basis functions. Our methods are illustrated with a simulation study and applied to an empirical data set, where a previously unknown interaction is detected. Technical proofs of our theoretical results are provided in the online supplemental materials.

  17. Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

    Yunqi Li; Bishnu Prasad Bastakoti; Yusuke Yamauchi

    2016-01-01

    This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially p...

  18. Discrete linear canonical transforms based on dilated Hermite functions.

    Pei, Soo-Chang; Lai, Yun-Chiu

    2011-08-01

    Linear canonical transform (LCT) is very useful and powerful in signal processing and optics. In this paper, discrete LCT (DLCT) is proposed to approximate LCT by utilizing the discrete dilated Hermite functions. The Wigner distribution function is also used to investigate DLCT performances in the time-frequency domain. Compared with the existing digital computation of LCT, our proposed DLCT possess additivity and reversibility properties with no oversampling involved. In addition, the length of input/output signals will not be changed before and after the DLCT transformations, which is consistent with the time-frequency area-preserving nature of LCT; meanwhile, the proposed DLCT has very good approximation of continuous LCT.

  19. MANUFACTURING BIODEGRADABLE COMPOSITE MATERIALS BASED ON POLYETHYLENE AND FUNCTIONALIZED BY ALCOHOLYSIS OF ETHYLENE-VINYL ACETATE COPOLYMER

    Aleksandr A. Shabarin

    2016-06-01

    Full Text Available Introduction. The continuous growth of production and consumption of plastic packaging creates a serious problem of disposal of package. This problem has ecological character, because the contents of the landfills decompose for decades, emit toxic com¬pounds and pollute the environment. The work is devoted to obtaining and investigation mechanical and rheological properties of biodegradable composite materials based on polyethylene and starch. Materials and Methods. In this work the author used polyethylene grade HDPE 273- 83 (GOST 16338-85, Sevilen brand 12206-007 (TU 6-05-1636-97 and potato starch (GOST 53876-2010 as a filler. Functionalization of sevilen was carried in the 30 % ethanol solution KOH at a temperature 80 °C during 3 hours. Compounding components was carried out at the laboratory of the two rotary mixer HAAKE PolyLab Rheomix 600 OS with rotors Banbury. Formation of plates for elastic strength and rheological studies were carried out on a hydraulic press Gibitre. Elastic and strength tests were carried out on the tensile machine the UAI-7000 M. Rheology tests were carried out on the rheometer Haake MARS III. The humidity filler (starch authors determined by the thermogravimetric method on the analyzer of moisture “Evlas-2M”. Results. It is shown, that the filler should not contain more than 7% moisture. Functionalization of ethylene with vinyl acetate copolymer (sevilen has performed by the method of alkaline alcoholysis. By the method of IC – spectroscopy the authors confirmed the presence of hydroxyl groups in the polymer. Using as a compatibilizer functionalized by the method of alcoholises has greatly ( significantly improved physical, mechanical and rheological properties of composite materials. Optimal content of sevilen (F in the compound according to the results of experiments amount 10 %. Discussion and Conclusions. Using of functionalized by the method of alcoholysis ethy-lene-vinyl acetate copolymer as a

  20. Polyethylene-Based Tadpole Copolymers

    Alkayal, Nazeeha

    2017-02-15

    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The -OH groups of the 3-miktoarm star copolymers (PE-OH)-b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield\\'s resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

  1. Hydrogen bonding strength of diblock copolymers affects the self-assembled structures with octa-functionalized phenol POSS nanoparticles.

    Lu, Yi-Syuan; Yu, Chia-Yu; Lin, Yung-Chih; Kuo, Shiao-Wei

    2016-02-28

    In this study, the influence of the functional groups by the diblock copolymers of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), poly(styrene-b-2-vinylpyridine) (PS-b-P2VP), and poly(styrene-b-methyl methacrylate) (PS-b-PMMA) on their blends with octa-functionalized phenol polyhedral oligomeric silsesquioxane (OP-POSS) nanoparticles (NPs) was investigated. The relative hydrogen bonding strengths in these blends follow the order PS-b-P4VP/OP-POSS > PS-b-P2VP/OP-POSS > PS-b-PMMA/OP-POSS based on the Kwei equation from differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopic analyses. Small-angle X-ray scattering and transmission electron microscopic analyses show that the morphologies of the self-assembly structures are strongly dependent on the hydrogen bonding strength at relatively higher OP-POSS content. The PS-b-P4VP/OP-POSS hybrid complex system with the strongest hydrogen bonds shows the order-order transition from lamellae to cylinders and finally to body-centered cubic spheres upon increasing OP-POSS content. However, PS-b-P2VP/OP-POSS and PS-b-PMMA/OP-POSS hybrid complex systems, having relatively weaker hydrogen bonds, transformed from lamellae to cylinder structures at lower OP-POSS content (50 wt%).

  2. Optimal Piecewise Linear Basis Functions in Two Dimensions

    Brooks III, E D; Szoke, A

    2009-01-26

    We use a variational approach to optimize the center point coefficients associated with the piecewise linear basis functions introduced by Stone and Adams [1], for polygonal zones in two Cartesian dimensions. Our strategy provides optimal center point coefficients, as a function of the location of the center point, by minimizing the error induced when the basis function interpolation is used for the solution of the time independent diffusion equation within the polygonal zone. By using optimal center point coefficients, one expects to minimize the errors that occur when these basis functions are used to discretize diffusion equations, or transport equations in optically thick zones (where they approach the solution of the diffusion equation). Our optimal center point coefficients satisfy the requirements placed upon the basis functions for any location of the center point. We also find that the location of the center point can be optimized, but this requires numerical calculations. Curiously, the optimum center point location is independent of the values of the dependent variable on the corners only for quadrilaterals.

  3. Preparation of exenatide-loaded linear poly(ethylene glycol-brush poly(L-lysine block copolymer: potential implications on diabetic nephropathy

    Tong F

    2017-06-01

    Full Text Available Fei Tong Department of Pathology and Pathophysiology, Provincial Key Discipline of Pharmacology, Jiaxing University Medical College, Jiaxing, Zhejiang, People’s Republic of China Abstract: The poly(ethylene glycol-b-brush poly(l-lysine polymer (PEG-b-(PELG50-g-PLL3 was synthesized and evaluated as a nanocarrier for prolonging delivery of exenatide through the abdominal subcutaneous injection route. The isoelectric point of exenatide was 4.86, and exenatide could combine with PEG-b-(PELG50-g-PLL3 polymers via electrostatic interactions at pH 7.4. This polymer was a good candidate for achieving prolonged drug delivery for exenatide, considering its high molecular weight. Besides the physicochemical characterization of the polymer, in vitro and in vivo applications were researched as a sustained exenatide delivery system. In the in vitro release research, 20.16%–76.88% of total exenatide was released from the PEG-b-(PELG50-g-PLL3 polymer within 7 days. The synthesized block-brush polymers and exenatide–block-brush polymers were analyzed by nuclear magnetic resonance spectroscopy, gel permeation chromatography, transmission electron microscopy, nanoparticle size instrument, and scanning electron microscopy. The best formulation was selected for in vivo experimentation to achieve blood glucose control in diabetic rat models using free exenatide as the control. The hypoglycemic action of the formulation following subcutaneous injection in diabetic rats lasted 7 days, and the results indicated that exenatide–block-brush polymers demonstrate enhanced long-acting hypoglycemic action. Besides the hypoglycemic action, exenatide–block-brush polymers significantly alleviated diabetic nephropathy via improving renal function, decreasing oxidative stress injury, decreasing urinary albumin excretion rate, mitigating albumin/creatinine ratio, reducing blood lipids, abating kidney index, weakening apoptosis, and downregulating expression of connective

  4. Morphologies of precise polyethylene-based acid copolymers and ionomers

    Buitrago, C. Francisco

    Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been

  5. Filtering Non-Linear Transfer Functions on Surfaces.

    Heitz, Eric; Nowrouzezahrai, Derek; Poulin, Pierre; Neyret, Fabrice

    2014-07-01

    Applying non-linear transfer functions and look-up tables to procedural functions (such as noise), surface attributes, or even surface geometry are common strategies used to enhance visual detail. Their simplicity and ability to mimic a wide range of realistic appearances have led to their adoption in many rendering problems. As with any textured or geometric detail, proper filtering is needed to reduce aliasing when viewed across a range of distances, but accurate and efficient transfer function filtering remains an open problem for several reasons: transfer functions are complex and non-linear, especially when mapped through procedural noise and/or geometry-dependent functions, and the effects of perspective and masking further complicate the filtering over a pixel's footprint. We accurately solve this problem by computing and sampling from specialized filtering distributions on the fly, yielding very fast performance. We investigate the case where the transfer function to filter is a color map applied to (macroscale) surface textures (like noise), as well as color maps applied according to (microscale) geometric details. We introduce a novel representation of a (potentially modulated) color map's distribution over pixel footprints using Gaussian statistics and, in the more complex case of high-resolution color mapped microsurface details, our filtering is view- and light-dependent, and capable of correctly handling masking and occlusion effects. Our approach can be generalized to filter other physical-based rendering quantities. We propose an application to shading with irradiance environment maps over large terrains. Our framework is also compatible with the case of transfer functions used to warp surface geometry, as long as the transformations can be represented with Gaussian statistics, leading to proper view- and light-dependent filtering results. Our results match ground truth and our solution is well suited to real-time applications, requires only a few

  6. Polyketones as alternating copolymers of carbon monoxide

    Belov, Gennady P; Novikova, Elena V

    2004-01-01

    Characteristic features of the catalytic synthesis of alternating copolymers of carbon monoxide with various olefins, dienes, styrene and its derivatives are considered. The diversity of catalyst systems used for the copolymerisation of carbon monoxide is demonstrated and their influence on the structure and the molecular mass of the resulting copolymers is analysed. The data on the structure and physicochemical and mechanical properties of this new generation of functional copolymers are generalised and described systematically for the first time.

  7. Hydrophilization of poly(caprolactone copolymers through introduction of oligo(ethylene glycol moieties.

    Jonathan J Wurth

    Full Text Available In this study, a new family of poly(ε-caprolactone (PCL copolymers that bear oligo(ethylene glycol (OEG moieties is described. The synthesis of three different oligo(ethylene glycol functionalized epoxide monomers derived from 2-methyl-4-pentenoic acid, and their copolymerization with ε-caprolactone (CL to poly(CL-co-OEG-MPO copolymers is presented. The statistical copolymerization initiated with SnOct2/BnOH yielded the copolymers with varying OEG content and composition. The linear relationship between feed ratio and incorporation of the OEG co-monomer enables control over backbone functional group density. The introduction of OEG moieties influenced both the thermal and the hydrophilic characteristics of the copolymers. Both increasing OEG length and backbone content resulted in a decrease in static water contact angle. The introduction of OEG side chains in the PCL copolymers had no adverse influence on MC-3TE3-E1 cell interaction. However, changes to cell form factor (Φ were observed. While unmodified PCL promoted elongated (anisotropic morphologies (Φ = 0.094, PCL copolymer with tri-ethylene glycol side chains at or above seven percent backbone incorporation induced more isotropic cell morphologies (Φ = 0.184 similar to those observed on glass controls (Φ = 0.151.

  8. Silicone elastomers with high dielectric permittivity and high dielectric breakdown strength based on tunable functionalized copolymers

    Madsen, Frederikke Bahrt; Yu, Liyun; Daugaard, Anders Egede

    2015-01-01

    system, with respect to functionalization, is achieved. It is investigated how the different functionalization variables affect essential DE properties, including dielectric permittivity, dielectric loss, elastic modulus and dielectric breakdown strength, and the optimal degree of chemical......%) was obtained without compromising other vital DE properties such as elastic modulus, gel fraction, dielectric and viscous loss and electrical breakdown strength....

  9. How linear features alter predator movement and the functional response.

    McKenzie, Hannah W

    2012-01-18

    In areas of oil and gas exploration, seismic lines have been reported to alter the movement patterns of wolves (Canis lupus). We developed a mechanistic first passage time model, based on an anisotropic elliptic partial differential equation, and used this to explore how wolf movement responses to seismic lines influence the encounter rate of the wolves with their prey. The model was parametrized using 5 min GPS location data. These data showed that wolves travelled faster on seismic lines and had a higher probability of staying on a seismic line once they were on it. We simulated wolf movement on a range of seismic line densities and drew implications for the rate of predator-prey interactions as described by the functional response. The functional response exhibited a more than linear increase with respect to prey density (type III) as well as interactions with seismic line density. Encounter rates were significantly higher in landscapes with high seismic line density and were most pronounced at low prey densities. This suggests that prey at low population densities are at higher risk in environments with a high seismic line density unless they learn to avoid them.

  10. How linear features alter predator movement and the functional response.

    McKenzie, Hannah W; Merrill, Evelyn H; Spiteri, Raymond J; Lewis, Mark A

    2012-01-01

    In areas of oil and gas exploration, seismic lines have been reported to alter the movement patterns of wolves (Canis lupus). We developed a mechanistic first passage time model, based on an anisotropic elliptic partial differential equation, and used this to explore how wolf movement responses to seismic lines influence the encounter rate of the wolves with their prey. The model was parametrized using 5 min GPS location data. These data showed that wolves travelled faster on seismic lines and had a higher probability of staying on a seismic line once they were on it. We simulated wolf movement on a range of seismic line densities and drew implications for the rate of predator-prey interactions as described by the functional response. The functional response exhibited a more than linear increase with respect to prey density (type III) as well as interactions with seismic line density. Encounter rates were significantly higher in landscapes with high seismic line density and were most pronounced at low prey densities. This suggests that prey at low population densities are at higher risk in environments with a high seismic line density unless they learn to avoid them.

  11. A comprehensive structure-function analysis shed a new light on molecular mechanism by which a novel smart copolymer, NY-3-1, assists protein refolding.

    Ye, Chaohui; Ilghari, Dariush; Niu, Jianlou; Xie, Yaoyao; Wang, Yan; Wang, Chao; Li, Xiaokun; Liu, Bailin; Huang, Zhifeng

    2012-08-31

    An in-depth understanding of molecular basis by which smart polymers assist protein refolding can lead us to develop a more effective polymer for protein refolding. In this report, to investigate structure-function relationship of pH-sensitive smart polymers, a series of poly(methylacrylic acid (MAc)-acrylic acid (AA))s with different MAc/AA ratios and molecular weights were synthesized and then their abilities in refolding of denatured lysozyme were compared by measuring the lytic activity of the refolded lysozyme. Based on our analysis, there were optimal MAc/AA ratio (44% MAc), M(w) (1700 Da), and copolymer concentration (0.1%, w/v) at which the highest yield of protein refolding was achieved. Fluorescence, circular dichroism, and RP-HPLC analysis reported in this study demonstrated that the presence of P(MAc-AA)s in the refolding buffer significantly improved the refolding yield of denatured lysozyme without affecting the overall structure of the enzyme. Importantly, our bioseparation analysis, together with the analysis of zeta potential and particle size of the copolymer in refolding buffers with different copolymer concentrations, suggested that the polymer provided a negatively charged surface for an electrostatic interaction with the denatured lysozyme molecules and thereby minimized the hydrophobic-prone aggregation of unfolded proteins during the process of refolding. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Linear and Non-Linear Dose-Response Functions Reveal a Hormetic Relationship Between Stress and Learning

    Zoladz, Phillip R.; Diamond, David M.

    2008-01-01

    Over a century of behavioral research has shown that stress can enhance or impair learning and memory. In the present review, we have explored the complex effects of stress on cognition and propose that they are characterized by linear and non-linear dose-response functions, which together reveal a hormetic relationship between stress and learning. We suggest that stress initially enhances hippocampal function, resulting from amygdala-induced excitation of hippocampal synaptic plasticity, as ...

  13. NP-Hardness of optimizing the sum of Rational Linear Functions over an Asymptotic-Linear-Program

    Chermakani, Deepak Ponvel

    2012-01-01

    We convert, within polynomial-time and sequential processing, an NP-Complete Problem into a real-variable problem of minimizing a sum of Rational Linear Functions constrained by an Asymptotic-Linear-Program. The coefficients and constants in the real-variable problem are 0, 1, -1, K, or -K, where K is the time parameter that tends to positive infinity. The number of variables, constraints, and rational linear functions in the objective, of the real-variable problem is bounded by a polynomial ...

  14. Synthesis and Thermosensitive Behavior of Polyacrylamide Copolymers and Their Applications in Smart Textiles

    Tao Chen

    2015-05-01

    Full Text Available We tuned the lower critical solution temperature (LCST of amphiphilic poly(N-isopropylacrylamide (PNIPAAm via copolymerization with a hydrophilic comonomer of N-hydroxymethyl acrylamide (NHMAAm. A series of copolymers P(NIPAAm-co-NHMAAm were synthesized by atom transfer radical polymerization (ATRP using CuBr/(N,N,N',N',N''-Pentamethyldiethylenetriamine (PMDETA as a catalyst system and 2-bromo ethyl isobutyrate (EBiB as an initiator. The copolymers were well characterized by Fourier transform infrared spectroscopy (FT-IR, 1H Nuclear magnetic resonance (NMR, and Thermogravimetric analysis (TGA. The copolymers followed a simple rule in their thermosensitive behaviors and have a linear increase in the LCST as a function of NHMAAm mol%. The thermosensitive properties of the copolymer films were investigated and demonstrated hydrophilic-hydrophobic transitions. Finally, the copolymer was grafted onto cotton fabrics using citric acid (CA as a crosslinking agent and sodium hypophosphite (SHP as a catalyst following a two dipping, two padding process. The large number of hydroxyl groups in the copolymer makes grafting convenient and firm. The grafted cotton fabrics show obvious thermosensitive behaviors. The results demonstrate that the cotton fabrics become more hydrophobic when the temperature is higher than the LCST. This study presents a valuable route towards temperature-responsive smart textiles and their potential applications.

  15. A Copolymer Scaffold Functionalized with Nanodiamond Particles Enhances Osteogenic Metabolic Activity and Bone Regeneration.

    Yassin, Mohammed A; Mustafa, Kamal; Xing, Zhe; Sun, Yang; Fasmer, Kristine Eldevik; Waag, Thilo; Krueger, Anke; Steinmüller-Nethl, Doris; Finne-Wistrand, Anna; Leknes, Knut N

    2017-06-01

    Functionalizing polymer scaffolds with nanodiamond particles (nDPs) has pronounced effect on the surface properties, such as improved wettability, an increased active area and binding sites for cellular attachment and adhesion, and increased ability to immobilize biomolecules by physical adsorption. This study aims to evaluate the effect of poly(l-lactide-co-ε-caprolactone) (poly(LLA-co-CL)) scaffolds, functionalized with nDPs, on bone regeneration in a rat calvarial critical size defect. Poly(LLA-co-CL) scaffolds functionalized with nDPs are also compared with pristine scaffolds with reference to albumin adsorption and seeding efficiency of bone marrow stromal cells (BMSCs). Compared with pristine scaffolds, the experimental scaffolds exhibit a reduction in albumin adsorption and a significant increase in the seeding efficiency of BMSCs (p = 0.027). In the calvarial defects implanted with BMSC-seeded poly(LLA-co-CL)/nDPs scaffolds, live imaging at 12 weeks discloses a significant increase in osteogenic metabolic activity (p = 0.016). Microcomputed tomography, confirmed by histological data, reveals a substantial increase in bone volume (p = 0.021). The results show that compared with conventional poly(LLA-co-CL) scaffolds those functionalized with nDPs promote osteogenic metabolic activity and mineralization capacity. It is concluded that poly(LLA-co-CL) composite matrices functionalized with nDPs enhance osteoconductivity and therefore warrant further study as potential scaffolding material for bone tissue engineering. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis and conformational characterization of functional di-block copolymer brushes for microarray technology

    Di Carlo, Gabriele; Damin, Francesco [Institute of Chemistry of Molecular Recognition, National Research Council of Italy, Via M. Bianco 9, 20131 Milano (Italy); Armelao, Lidia [ISTM-CNR and INSTM, Department of Chemistry, University of Padova, Via F. Marzolo 1, 35131 Padova (Italy); Maccato, Chiara [Department of Chemistry and INSTM, University of Padova, Via F. Marzolo 1, 35131 Padova (Italy); Unlu, Selim [Department of Electrical and Computer Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Department of Biomedical Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Spuhler, Philipp S. [Department of Biomedical Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Chiari, Marcella, E-mail: marcella.chiari@icrm.cnr.it [Institute of Chemistry of Molecular Recognition, National Research Council of Italy, Via M. Bianco 9, 20131 Milano (Italy)

    2012-02-01

    Surface initiated polymerization (SIP) coupled with reversible addition-fragmentation chain transfer polymerization (RAFT) was used to functionalize microarray glass slides with block polymer brushes. N,N-dimethylacrylamide (DMA) and N-acryloyloxysuccinimide (NAS) (graft-poly[DMA-b-(DMA-co-NAS)]) brushes, with di-block architecture, were prepared from a novel RAFT chain transfer agent bearing a silanating moiety (RAFT silane) directly anchored onto the glass surfaces. Conformational characterization of the coatings was performed by Self Spectral Interference Fluorescence Microscopy (SSFM), an innovative technique that describes the location of a fluorescent DNA molecule relative to a surface with sub-nanometer accuracy. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) were used to characterize the coatings composition and morphology.

  17. Synthesis and conformational characterization of functional di-block copolymer brushes for microarray technology

    Di Carlo, Gabriele; Damin, Francesco; Armelao, Lidia; Maccato, Chiara; Unlu, Selim; Spuhler, Philipp S.; Chiari, Marcella

    2012-01-01

    Surface initiated polymerization (SIP) coupled with reversible addition-fragmentation chain transfer polymerization (RAFT) was used to functionalize microarray glass slides with block polymer brushes. N,N-dimethylacrylamide (DMA) and N-acryloyloxysuccinimide (NAS) (graft-poly[DMA-b-(DMA-co-NAS)]) brushes, with di-block architecture, were prepared from a novel RAFT chain transfer agent bearing a silanating moiety (RAFT silane) directly anchored onto the glass surfaces. Conformational characterization of the coatings was performed by Self Spectral Interference Fluorescence Microscopy (SSFM), an innovative technique that describes the location of a fluorescent DNA molecule relative to a surface with sub-nanometer accuracy. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) were used to characterize the coatings composition and morphology.

  18. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    Dong, Ban Xuan; Honmou, Yoshihiro; Komiyama, Hideaki; Furumaki, Shu; Iyoda, Tomokazu; Vacha, Martin

    2013-01-01

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    Dong, Ban Xuan

    2013-01-15

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Calculation of the exponential function of linear idempotent operators

    Chavoya-Aceves, O.; Luna, H.M.

    1989-01-01

    We give a method to calculate the exponential EXP[A r ] where A is a linear operator which satisfies the reaction A n =I, n is an integer and I is the identity operator. The method is generalised to operators such that A n +1=A and is applied to obtain some Lorentz transformations which generalise the notion of 'boost'. (Author)

  1. Simultaneous Optimization of Decisions Using a Linear Utility Function.

    Vos, Hans J.

    1990-01-01

    An approach is presented to simultaneously optimize decision rules for combinations of elementary decisions through a framework derived from Bayesian decision theory. The developed linear utility model for selection-mastery decisions was applied to a sample of 43 first year medical students to illustrate the procedure. (SLD)

  2. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L.; Vela, Alberto

    2015-01-01

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

  3. Diet models with linear goal programming: impact of achievement functions.

    Gerdessen, J C; de Vries, J H M

    2015-11-01

    Diet models based on goal programming (GP) are valuable tools in designing diets that comply with nutritional, palatability and cost constraints. Results derived from GP models are usually very sensitive to the type of achievement function that is chosen.This paper aims to provide a methodological insight into several achievement functions. It describes the extended GP (EGP) achievement function, which enables the decision maker to use either a MinSum achievement function (which minimizes the sum of the unwanted deviations) or a MinMax achievement function (which minimizes the largest unwanted deviation), or a compromise between both. An additional advantage of EGP models is that from one set of data and weights multiple solutions can be obtained. We use small numerical examples to illustrate the 'mechanics' of achievement functions. Then, the EGP achievement function is demonstrated on a diet problem with 144 foods, 19 nutrients and several types of palatability constraints, in which the nutritional constraints are modeled with fuzzy sets. Choice of achievement function affects the results of diet models. MinSum achievement functions can give rise to solutions that are sensitive to weight changes, and that pile all unwanted deviations on a limited number of nutritional constraints. MinMax achievement functions spread the unwanted deviations as evenly as possible, but may create many (small) deviations. EGP comprises both types of achievement functions, as well as compromises between them. It can thus, from one data set, find a range of solutions with various properties.

  4. Assessment of Polyacrylamide Based Co-Polymers Enhanced by Functional Group Modifications with Regards to Salinity and Hardness

    Saeed Akbari

    2017-11-01

    Full Text Available This research aims to test four new polymers for their stability under high salinity/high hardness conditions for their possible use in polymer flooding to improve oil recovery from hydrocarbon reservoirs. The four sulfonated based polyacrylamide co-polymers were FLOCOMB C7035; SUPERPUSHER SAV55; THERMOASSOCIATIF; and AN132 VHM which are basically sulfonated polyacrylamide copolymers of AM (acrylamide with AMPS (2-Acrylamido-2-Methylpropane Sulfonate. AN132 VHM has a molecular weight of 9–11 million Daltons with 32 mol % degree of sulfonation. SUPERPUSHER SAV55 mainly has about 35 mol % sulfonation degree and a molecular weight of 9–11 million Daltons. FLOCOMB C7035, in addition, has undergone post-hydrolysis step to increase polydispersity and molecular weight above 18 million Daltons but it has a sulfonation degree much lower than 32 mol %. THERMOASSOCIATIF has a molecular weight lower than 12 million Daltons and a medium sulfonation degree of around 32 mol %, and also contains LCST (lower critical solution temperature type block, which is responsible for its thermoassociative characteristics. This paper discusses the rheological behavior of these polymers in aqueous solutions (100–4500 ppm with NaCl (0.1–10 wt % measured at 25 °C. The effect of hardness was investigated by preparing a CaCl2-NaCl solution of same ionic strength as the 5 wt % of NaCl. In summary, it can be concluded that the rheological behavior of the newly modified co-polymers was in general agreement to the existing polymers, except that THERMOASSOCIATIF polymers showed unique behavior, which could possibly make them a better candidate for enhanced oil recovery (EOR application in high salinity conditions. The other three polymers, on the other hand, are better candidates for EOR applications in reservoirs containing high divalent ions. These results are expected to be helpful in selecting and screening the polymers for an EOR application.

  5. Linear and non-linear dose-response functions reveal a hormetic relationship between stress and learning.

    Zoladz, Phillip R; Diamond, David M

    2008-10-16

    Over a century of behavioral research has shown that stress can enhance or impair learning and memory. In the present review, we have explored the complex effects of stress on cognition and propose that they are characterized by linear and non-linear dose-response functions, which together reveal a hormetic relationship between stress and learning. We suggest that stress initially enhances hippocampal function, resulting from amygdala-induced excitation of hippocampal synaptic plasticity, as well as the excitatory effects of several neuromodulators, including corticosteroids, norepinephrine, corticotropin-releasing hormone, acetylcholine and dopamine. We propose that this rapid activation of the amygdala-hippocampus brain memory system results in a linear dose-response relation between emotional strength and memory formation. More prolonged stress, however, leads to an inhibition of hippocampal function, which can be attributed to compensatory cellular responses that protect hippocampal neurons from excitotoxicity. This inhibition of hippocampal functioning in response to prolonged stress is potentially relevant to the well-described curvilinear dose-response relationship between arousal and memory. Our emphasis on the temporal features of stress-brain interactions addresses how stress can activate, as well as impair, hippocampal functioning to produce a hormetic relationship between stress and learning.

  6. Fuzzy optimization of primal-dual pair using piecewise linear membership functions

    Pandey D.

    2012-01-01

    Full Text Available Present paper improves the model of Bector and Chandra [Fuzzy Sets and Systems, 125 (2002 317-325] on duality in fuzzy linear programming by using non-linear membership functions. Numerical problem discussed by these authors has also been worked out through our non-linear model to demonstrate improved optimality of the results.

  7. Adaptive Linear and Normalized Combination of Radial Basis Function Networks for Function Approximation and Regression

    Yunfeng Wu

    2014-01-01

    Full Text Available This paper presents a novel adaptive linear and normalized combination (ALNC method that can be used to combine the component radial basis function networks (RBFNs to implement better function approximation and regression tasks. The optimization of the fusion weights is obtained by solving a constrained quadratic programming problem. According to the instantaneous errors generated by the component RBFNs, the ALNC is able to perform the selective ensemble of multiple leaners by adaptively adjusting the fusion weights from one instance to another. The results of the experiments on eight synthetic function approximation and six benchmark regression data sets show that the ALNC method can effectively help the ensemble system achieve a higher accuracy (measured in terms of mean-squared error and the better fidelity (characterized by normalized correlation coefficient of approximation, in relation to the popular simple average, weighted average, and the Bagging methods.

  8. Effect of sequence dispersity on morphology of tapered diblock copolymers from molecular dynamics simulations.

    Levine, William G; Seo, Youngmi; Brown, Jonathan R; Hall, Lisa M

    2016-12-21

    Tapered diblock copolymers are similar to typical AB diblock copolymers but have an added transition region between the two blocks which changes gradually in composition from pure A to pure B. This tapered region can be varied from 0% (true diblock) to 100% (gradient copolymer) of the polymer length, and this allows some control over the microphase separated domain spacing and other material properties. We perform molecular dynamics simulations of linearly tapered block copolymers with tapers of various lengths, initialized from fluids density functional theory predictions. To investigate the effect of sequence dispersity, we compare systems composed of identical polymers, whose taper has a fixed sequence that most closely approximates a linear gradient, with sequentially disperse polymers, whose sequences are created statistically to yield the appropriate ensemble average linear gradient. Especially at high segregation strength, we find clear differences in polymer conformations and microstructures between these systems. Importantly, the statistical polymers are able to find more favorable conformations given their sequence, for instance, a statistical polymer with a larger fraction of A than the median will tend towards the A lamellae. The conformations of the statistically different polymers can thus be less stretched, and these systems have higher overall density. Consequently, the lamellae formed by statistical polymers have smaller domain spacing with sharper interfaces.

  9. Linear supermultiplets and non-holomorphic gauge coupling functions

    Binetruy, P.; Grimm, R.; Girardi, G.

    1991-04-01

    The general couplings of linear multiplets, including Chern-Simons forms, to chiral matter as well as to the standard supergravity-matter system are constructed. Insisting on a canonically normalised Einstein term in particular the appearance of non-holomorphic gauge couplings are discussed and duality transformations in full generality are performed. The implications of these structures for the effective description of sigma model anomalies are presented with and without coupling to supergravity, following recent proposals of Derendinger, Ferrara, Kounnas and Zwirner and of Cardoso and Ovrut. (author) 14 refs

  10. Quantum tests for the linearity and permutation invariance of Boolean functions

    Hillery, Mark [Department of Physics, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10021 (United States); Andersson, Erika [SUPA, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom)

    2011-12-15

    The goal in function property testing is to determine whether a black-box Boolean function has a certain property or is {epsilon}-far from having that property. The performance of the algorithm is judged by how many calls need to be made to the black box in order to determine, with high probability, which of the two alternatives is the case. Here we present two quantum algorithms, the first to determine whether the function is linear and the second to determine whether it is symmetric (invariant under permutations of the arguments). Both require order {epsilon}{sup -2/3} calls to the oracle, which is better than known classical algorithms. In addition, in the case of linearity testing, if the function is linear, the quantum algorithm identifies which linear function it is. The linearity test combines the Bernstein-Vazirani algorithm and amplitude amplification, while the test to determine whether a function is symmetric uses projective measurements and amplitude amplification.

  11. Partially linear varying coefficient models stratified by a functional covariate

    Maity, Arnab; Huang, Jianhua Z.

    2012-01-01

    We consider the problem of estimation in semiparametric varying coefficient models where the covariate modifying the varying coefficients is functional and is modeled nonparametrically. We develop a kernel-based estimator of the nonparametric

  12. Functionalized linear poly(amidoamine)s are efficient vectors for intracellular protein delivery

    Coué, G.M.J.P.C.; Engbersen, Johannes F.J.

    2011-01-01

    An effective intracellular protein delivery system was developed based on functionalized linear poly(amidoamine)s (PAAs) that form self-assembled cationic nanocomplexes with oppositely charged proteins. Three differently functionalized PAAs were synthesized, two of these having repetitive disulfide

  13. Partially linear varying coefficient models stratified by a functional covariate

    Maity, Arnab

    2012-10-01

    We consider the problem of estimation in semiparametric varying coefficient models where the covariate modifying the varying coefficients is functional and is modeled nonparametrically. We develop a kernel-based estimator of the nonparametric component and a profiling estimator of the parametric component of the model and derive their asymptotic properties. Specifically, we show the consistency of the nonparametric functional estimates and derive the asymptotic expansion of the estimates of the parametric component. We illustrate the performance of our methodology using a simulation study and a real data application.

  14. Linear measure functional differential equations with infinite delay

    Monteiro, Giselle Antunes; Slavík, A.

    2014-01-01

    Roč. 287, 11-12 (2014), s. 1363-1382 ISSN 0025-584X Institutional support: RVO:67985840 Keywords : measure functional differential equations * generalized ordinary differential equations * Kurzweil-Stieltjes integral Subject RIV: BA - General Mathematics Impact factor: 0.683, year: 2014 http://onlinelibrary.wiley.com/doi/10.1002/mana.201300048/abstract

  15. Processes and Reasoning in Representations of Linear Functions

    Adu-Gyamfi, Kwaku; Bossé, Michael J.

    2014-01-01

    This study examined student actions, interpretations, and language in respect to questions raised regarding tabular, graphical, and algebraic representations in the context of functions. The purpose was to investigate students' interpretations and specific ways of working within table, graph, and the algebraic on notions fundamental to a…

  16. Block copolymer membranes for aqueous solution applications

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  17. Block copolymer membranes for aqueous solution applications

    Nunes, Suzana Pereira

    2016-01-01

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  18. On MV-algebras of non-linear functions

    Antonio Di Nola

    2017-01-01

    Full Text Available In this paper, the main results are:a study of the finitely generated MV-algebras of continuous functions from the n-th power of the unit real interval I to I;a study of Hopfian MV-algebras; anda category-theoretic study of the map sending an MV-algebra as above to the range of its generators (up to a suitable form of homeomorphism.

  19. On MV-algebras of non-linear functions

    Antonio Di Nola

    2017-01-01

    Full Text Available In this paper, the main results are: a study of the finitely generated MV-algebras of continuous functions from the n-th power of the unit real interval I to I; a study of Hopfian MV-algebras; and a category-theoretic study of the map sending an MV-algebra as above to the range of its generators (up to a suitable form of homeomorphism.

  20. Approximate Stream Function wavemaker theory for highly non-linear waves in wave flumes

    Zhang, H.W.; Schäffer, Hemming Andreas

    2007-01-01

    An approximate Stream Function wavemaker theory for highly non-linear regular waves in flumes is presented. This theory is based on an ad hoe unified wave-generation method that combines linear fully dispersive wavemaker theory and wave generation for non-linear shallow water waves. This is done...... by applying a dispersion correction to the paddle position obtained for non-linear long waves. The method is validated by a number of wave flume experiments while comparing with results of linear wavemaker theory, second-order wavemaker theory and Cnoidal wavemaker theory within its range of application....

  1. A linear functional differential equation with distributions in the input

    Vadim Z. Tsalyuk

    2003-10-01

    Full Text Available This paper studies the functional differential equation $$ dot x(t = int_a^t {d_s R(t,s, x(s} + F'(t, quad t in [a,b], $$ where $F'$ is a generalized derivative, and $R(t,cdot$ and $F$ are functions of bounded variation. A solution is defined by the difference $x - F$ being absolutely continuous and satisfying the inclusion $$ frac{d}{dt} (x(t - F(t in int_a^t {d_s R(t,s,x(s}. $$ Here, the integral in the right is the multivalued Stieltjes integral presented in cite{VTs1} (in this article we review and extend the results in cite{VTs1}. We show that the solution set for the initial-value problem is nonempty, compact, and convex. A solution $x$ is said to have memory if there exists the function $x$ such that $x(a = x(a$, $x(b = x(b$, $ x(t in [x(t-0,x(t+0]$ for $t in (a,b$, and $frac{d}{dt} (x(t - F(t = int_a^t {d_s R(t,s,{x}(s}$, where Lebesgue-Stieltjes integral is used. We show that such solutions form a nonempty, compact, and convex set. It is shown that solutions with memory obey the Cauchy-type formula $$ x(t in C(t,ax(a + int_a^t C(t,s, dF(s. $$

  2. Application of Bottlebrush Block Copolymers as Photonic Crystals.

    Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

    2017-07-01

    Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Olefin–Styrene Copolymers

    Nunzia Galdi; Antonio Buonerba; Leone Oliva

    2016-01-01

    In this review are reported some of the most relevant achievements in the chemistry of the ethylene–styrene copolymerization and in the characterization of the copolymer materials. Focus is put on the relationship between the structure of the catalyst and that of the obtained copolymer. On the other hand, the wide variety of copolymer architecture is related to the properties of the material and to the potential utility.

  4. Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances

    Leonard Ionut Atanase

    2018-01-01

    Full Text Available This review is an attempt to update the recent advances in the self-assembly of amphiphilic block and graft copolymers. Their micellization behavior is highlighted for linear AB, ABC triblock terpolymers, and graft structures in non-aqueous selective polar and non-polar solvents, including solvent mixtures and ionic liquids. The micellar characteristics, such as particle size, aggregation number, and morphology, are examined as a function of the copolymers’ architecture and molecular characteristics.

  5. Least-squares fit of a linear combination of functions

    Niraj Upadhyay

    2013-12-01

    Full Text Available We propose that given a data-set $S=\\{(x_i,y_i/i=1,2,{\\dots}n\\}$ and real-valued functions $\\{f_\\alpha(x/\\alpha=1,2,{\\dots}m\\},$ the least-squares fit vector $A=\\{a_\\alpha\\}$ for $y=\\sum_\\alpha a_{\\alpha}f_\\alpha(x$ is $A = (F^TF^{-1}F^TY$ where $[F_{i\\alpha}]=[f_\\alpha(x_i].$ We test this formalism by deriving the algebraic expressions of the regression coefficients in $y = ax + b$ and in $y = ax^2 + bx + c.$ As a practical application, we successfully arrive at the coefficients in the semi-empirical mass formula of nuclear physics. The formalism is {\\it generic} - it has the potential of being applicable to any {\\it type} of $\\{x_i\\}$ as long as there exist appropriate $\\{f_\\alpha\\}.$ The method can be exploited with a CAS or an object-oriented language and is excellently suitable for parallel-processing.

  6. Differentiability of Palmer's linearization Theorem and converse result for density functions

    Castañeda, Alvaro; Robledo, Gonzalo

    2014-01-01

    We study differentiability properties in a particular case of the Palmer's linearization Theorem, which states the existence of an homeomorphism $H$ between the solutions of a linear ODE system having exponential dichotomy and a quasilinear system. Indeed, if the linear system is uniformly asymptotically stable, sufficient conditions ensuring that $H$ is a $C^{2}$ preserving orientation diffeomorphism are given. As an application, we generalize a converse result of density functions for a non...

  7. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

    Cho, Junhan

    2014-03-01

    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  8. Supporting Generative Thinking about Number Lines, the Cartesian Plane, and Graphs of Linear Functions

    Earnest, Darrell Steven

    2012-01-01

    This dissertation explores fifth and eighth grade students' interpretations of three kinds of mathematical representations: number lines, the Cartesian plane, and graphs of linear functions. Two studies were conducted. In Study 1, I administered the paper-and-pencil Linear Representations Assessment (LRA) to examine students'…

  9. Estimation of Multiple Point Sources for Linear Fractional Order Systems Using Modulating Functions

    Belkhatir, Zehor; Laleg-Kirati, Taous-Meriem

    2017-01-01

    This paper proposes an estimation algorithm for the characterization of multiple point inputs for linear fractional order systems. First, using polynomial modulating functions method and a suitable change of variables the problem of estimating

  10. A method for computing the stationary points of a function subject to linear equality constraints

    Uko, U.L.

    1989-09-01

    We give a new method for the numerical calculation of stationary points of a function when it is subject to equality constraints. An application to the solution of linear equations is given, together with a numerical example. (author). 5 refs

  11. Studies with Parabolic Parabolic Linear Parabolic (PPLP) momentum function in the LHC

    Solfaroli Camillocci, Matteo; Timko, Helga; Wenninger, Jorg; CERN. Geneva. ATS Department

    2018-01-01

    Measurements performed with a Parabolic Parabolic Linear Parabolic (PPLP) momentum function in the LHC. Three attempts have been performed with a pilot bunch and one with nominal bunch (1.1x1011 p/bunch).

  12. Wigner weight functions and Weyl symbols of non-negative definite linear operators

    Janssen, A.J.E.M.

    1989-01-01

    In this paper we present several necessary and, for radially symmetric functions, necessary and sufficient conditions for a function of two variables to be a Wigner weight function (Weyl symbol of a non-negative definite linear operator of L2(R)). These necessary conditions are in terms of spread

  13. Approximation of functions in two variables by some linear positive operators

    Mariola Skorupka

    1995-12-01

    Full Text Available We introduce some linear positive operators of the Szasz-Mirakjan type in the weighted spaces of continuous functions in two variables. We study the degree of the approximation of functions by these operators. The similar results for functions in one variable are given in [5]. Some operators of the Szasz-Mirakjan type are examined also in [3], [4].

  14. Índices de capacidade de relações funcionais lineares e não-lineares Capability index for linear and non-linear functions

    Edivaldo Antonio Bulba

    2004-01-01

    Full Text Available São apresentados métodos para determinação dos índices de capacidade tais como Cp e Cpk aplicados no "design for six sigma" (DFSS quando a característica de qualidade é não-observável e dada por Y = f(X1, X2, X3,....Xk, onde Xi são variáveis aleatórias com média e variância respectivamente iguais a miXi e sigma2Xi; f é uma função conhecida. A determinação é baseada na série de Taylor e o procedimento será ilustrado com exemplos práticos.Here we present methods to determine capabilit indices such as Cp and Cpk to be applied in "design for six sigma" (DFSS when the quality characteristic of interest Y is unobservable but given by Y = f(X1, X2, X3,....Xk, where Xi's are random variables with means and variance respectively equal to muXi and sigma2Xi; f is a known function. The determination is based on Taylor series and we illustrate the procedure with practical examples.

  15. Solving polynomial differential equations by transforming them to linear functional-differential equations

    Nahay, John Michael

    2008-01-01

    We present a new approach to solving polynomial ordinary differential equations by transforming them to linear functional equations and then solving the linear functional equations. We will focus most of our attention upon the first-order Abel differential equation with two nonlinear terms in order to demonstrate in as much detail as possible the computations necessary for a complete solution. We mention in our section on further developments that the basic transformation idea can be generali...

  16. Non-linear shape functions over time in the space-time finite element method

    Kacprzyk Zbigniew

    2017-01-01

    Full Text Available This work presents a generalisation of the space-time finite element method proposed by Kączkowski in his seminal of 1970’s and early 1980’s works. Kączkowski used linear shape functions in time. The recurrence formula obtained by Kączkowski was conditionally stable. In this paper, non-linear shape functions in time are proposed.

  17. Effect of nano particle sizes on the third-order optical non-linearities and nanostructure of copolymer P3HT:PCBM thin film for organic photovoltaics

    Badran, Hussain Ali; Ajeel, Khalid I.; Lazim, Haidar Gazy

    2016-01-01

    Highlights: • Active layer (P3HT:PCBM) has been deposited on substrate type by spin coating at 1000 rpm. • The device was completed by evaporating a 60 nm thick, circular gold electrodes onto the P3HT:PCBM. • Nonlinear refractive indices of the three particle sizes are found to be of the order of 10"−"7 cm"2/W - Abstract: Organic solar cells are based on (3-hexylthiophene):[6,6]-phenyl C61-butyric acid with methyl ester Bulk Heterojunction. An inverted structure has been fabricated using nano-anatase crystalline titanium dioxide, as the electron transport layer, which was prepared on either the Indium Tin Oxide coated glass (ITO—glass), or Silicon wafer, as well as on glass substrates by the sol–gel method, at different spin speed, using the spin-coating system. The effect of thickness on the surface morphology and on the optical properties of TiO_2 layer, was investigated using the Atomic Force Microscopy (AFM), X-ray diffraction, and UV–visible spectrophotometer. The samples were examined to feature currents and voltages, in the darkness and light extraction efficiency of the solar cell. The highest open-circuit voltage, V_o_c, and power conversion efficiency were 0.66% and 0.39%, fabricated with 90 nm, respectively. The non-linear optical properties of nano-anatase TiO_2 sol–gel, were investigated at different particle sizes, using the z-scan technique.

  18. Effect of nano particle sizes on the third-order optical non-linearities and nanostructure of copolymer P3HT:PCBM thin film for organic photovoltaics

    Badran, Hussain Ali, E-mail: badran_hussein@yahoo.com [Basrah University, Education College for Pure Sciences, Physics Department, Basrah (Iraq); Ajeel, Khalid I. [Basrah University, Education College for Pure Sciences, Physics Department, Basrah (Iraq); Lazim, Haidar Gazy [Misan University, Basic Education College, Science Department, Misan (Iraq)

    2016-04-15

    Highlights: • Active layer (P3HT:PCBM) has been deposited on substrate type by spin coating at 1000 rpm. • The device was completed by evaporating a 60 nm thick, circular gold electrodes onto the P3HT:PCBM. • Nonlinear refractive indices of the three particle sizes are found to be of the order of 10{sup −7} cm{sup 2}/W - Abstract: Organic solar cells are based on (3-hexylthiophene):[6,6]-phenyl C61-butyric acid with methyl ester Bulk Heterojunction. An inverted structure has been fabricated using nano-anatase crystalline titanium dioxide, as the electron transport layer, which was prepared on either the Indium Tin Oxide coated glass (ITO—glass), or Silicon wafer, as well as on glass substrates by the sol–gel method, at different spin speed, using the spin-coating system. The effect of thickness on the surface morphology and on the optical properties of TiO{sub 2} layer, was investigated using the Atomic Force Microscopy (AFM), X-ray diffraction, and UV–visible spectrophotometer. The samples were examined to feature currents and voltages, in the darkness and light extraction efficiency of the solar cell. The highest open-circuit voltage, V{sub oc}, and power conversion efficiency were 0.66% and 0.39%, fabricated with 90 nm, respectively. The non-linear optical properties of nano-anatase TiO{sub 2} sol–gel, were investigated at different particle sizes, using the z-scan technique.

  19. Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

    Rzayev, Zakir M O; Söylemez, A Ernur

    2011-04-01

    We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine

  20. Poly(methacrylic acid-ran-2-vinylpyridine Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

    Milan Marić

    2017-02-01

    Full Text Available Nitroxide-mediated polymerization using the succinimidyl ester functional unimolecular alkoxyamine initiator (NHS-BlocBuilder was used to first copolymerize tert-butyl methacrylate/2-vinylpyridine (tBMA/2VP with low dispersity (Đ = 1.30–1.41 and controlled growth (linear number average molecular Mn versus conversion, Mn = 3.8–10.4 kg·mol−1 across a wide composition of ranges (initial mol fraction 2VP, f2VP,0 = 0.10–0.90. The resulting statistical copolymers were first de-protected to give statistical polyampholytic copolymers comprised of methacrylic acid/2VP (MAA/2VP units. These copolymers exhibited tunable water-solubility due to the different pKas of the acidic MAA and basic 2VP units; being soluble at very low pH < 3 and high pH > 8. One of the tBMA/2VP copolymers was used as a macroinitiator for a 4-acryloylmorpholine/4-acryloylpiperidine (4AM/4AP mixture, to provide a second block with thermo-responsive behavior with tunable cloud point temperature (CPT, depending on the ratio of 4AM:4AP. Dynamic light scattering of the block copolymer at various pHs (3, 7 and 10 as a function of temperature indicated a rapid increase in particle size >2000 nm at 22–27 °C, corresponding to the 4AM/4AP segment’s thermos-responsiveness followed by a leveling in particle size to about 500 nm at higher temperatures.

  1. Crystallinity changes of electron-beam irradiated ethylene-vinyl alcohol copolymer (EVOH) as a function of radiation dose

    Nogueira, Beatriz R.; Martins, Joao F.T.; Oliveira, Rene R.; Moura, Esperidiana A.B.

    2011-01-01

    The treatment with electron-beam radiation is a promising approach to the controllable modification of the properties of the polymeric materials, in order to adjust their properties. In recent years, electron-beam irradiation have been efficiently applied in the flexible packaging industry to promote cross-linking and scission of the polymeric chains in order to improve material mechanical properties. On the other hand, ionizing irradiation can also affect the polymeric materials itself leading to a production of free radicals. These free radicals can in turn lead to degradation and or cross-linking phenomena. In the present work the changes in thermal properties of electron-beam irradiated ethylene-vinyl alcohol copolymer (EVOH) resin were investigated. The EVOH resin was irradiated up to 500 kGy using a 1.5 MeV electron beam accelerator, at room temperature in presence of air. The EVOH samples irradiated from 300 kGy presented increases in melting temperature, except for 350 kGy. The changes in properties of the EVOH resin after irradiation were evaluated by differential scanning calorimetry (DSC) and X-Rays Diffraction (XRD). The correlation between the properties of EVOH non-irradiated and irradiated EVOH samples were discussed. The XRD results showed a slight shift of diffraction peaks, as well as an increase of width, DSC results also showed differences on crystallinity degree, for irradiated EVOH samples, which suggests that a decrease or an increase in degree crystallinity of EVOH will depends on radiation dose applied. These results are very important because shows a slight decrease in crystallinity of irradiated EVOH, a decrease in the crystallinity degree usually is related with an increase of the amorphous phase due to, probably, the predominance of molecular chain cross-linking of EVOH over the molecular chain scission and degradation process, caused by ionizing radiation, and a consequent improvement of their properties, such as thermal, mechanical

  2. Functionalization of layered double hydroxides by intumescent flame retardant: Preparation, characterization, and application in ethylene vinyl acetate copolymer

    Huang Guobo; Fei Zhengdong; Chen Xiaoying; Qiu Fangli; Wang Xu; Gao Jianrong

    2012-01-01

    Highlights: ► LDHs were modified with compound PAHPA. ► EVA/PAHPA-LDHs nanocomposites were prepared by melt blending. ► PAHPA-LDHs improved the flame retardancy of the nanocomposites. - Abstract: A phosphorus-nitrogen containing compound, N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)-hexylacetamide-2-propyl acid (PAHPA), is synthesized and characterized. A novel flame retardant, namely layered double hydroxides (LDHs) modified with PAHPA (PAHPA-LDHs), is prepared by ion-exchange of LDHs with PAHPA. The results from Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and energy dispersive X-ray analysis with a high-angle annular dark-field scanning transmission electron microscope show that PAHPA intercalated LDHs. The X-ray diffraction and transmission electron microscopy (TEM) results show that PAHPA-LDHs achieve well dispersion in ethylene vinyl acetate copolymer (EVA) matrix and the EVA/PAHPA-LDHs nanocomposites (i.e. EVA filled with 5 wt% PAHPA-LDHs) are formed by polymer melt intercalation. Thermal stability and flammability properties are investigated by thermogravimetric analysis and cone calorimeter tests. The results show that the addition of PAHPA-LDHs improves thermal stability and reduces obviously the flammability of EVA resin. Compared with pure EVA resin, the peak heat release rate of the EVA/PAHPA-LDHs nanocomposites is reduced by about 43%. The results of scanning electron microscopy and TEM indicate that a compact and dense intumescent char is formed for the EVA/PAHPA-LDHs nanocomposites after combustion.

  3. The spin polarized linear response from density functional theory: Theory and application to atoms

    Fias, Stijn, E-mail: sfias@vub.ac.be; Boisdenghien, Zino; De Proft, Frank; Geerlings, Paul [General Chemistry (ALGC), Vrije Universiteit Brussel (Free University Brussels – VUB), Pleinlaan 2, 1050 Brussels (Belgium)

    2014-11-14

    Within the context of spin polarized conceptual density functional theory, the spin polarized linear response functions are introduced both in the [N, N{sub s}] and [N{sub α}, N{sub β}] representations. The mathematical relations between the spin polarized linear response functions in both representations are examined and an analytical expression for the spin polarized linear response functions in the [N{sub α}, N{sub β}] representation is derived. The spin polarized linear response functions were calculated for all atoms up to and including argon. To simplify the plotting of our results, we integrated χ(r, r′) to a quantity χ(r, r{sup ′}), circumventing the θ and ϕ dependence. This allows us to plot and to investigate the periodicity throughout the first three rows in the periodic table within the two different representations. For the first time, χ{sub αβ}(r, r{sup ′}), χ{sub βα}(r, r{sup ′}), and χ{sub SS}(r, r{sup ′}) plots have been calculated and discussed. By integration of the spin polarized linear response functions, different components to the polarisability, α{sub αα}, α{sub αβ}, α{sub βα}, and α{sub ββ} have been calculated.

  4. Oracle Inequalities for Convex Loss Functions with Non-Linear Targets

    Caner, Mehmet; Kock, Anders Bredahl

    This paper consider penalized empirical loss minimization of convex loss functions with unknown non-linear target functions. Using the elastic net penalty we establish a finite sample oracle inequality which bounds the loss of our estimator from above with high probability. If the unknown target...... of the same order as that of the oracle. If the target is linear we give sufficient conditions for consistency of the estimated parameter vector. Next, we briefly discuss how a thresholded version of our estimator can be used to perform consistent variable selection. We give two examples of loss functions...

  5. Applications of Kalman filters based on non-linear functions to numerical weather predictions

    G. Galanis

    2006-10-01

    Full Text Available This paper investigates the use of non-linear functions in classical Kalman filter algorithms on the improvement of regional weather forecasts. The main aim is the implementation of non linear polynomial mappings in a usual linear Kalman filter in order to simulate better non linear problems in numerical weather prediction. In addition, the optimal order of the polynomials applied for such a filter is identified. This work is based on observations and corresponding numerical weather predictions of two meteorological parameters characterized by essential differences in their evolution in time, namely, air temperature and wind speed. It is shown that in both cases, a polynomial of low order is adequate for eliminating any systematic error, while higher order functions lead to instabilities in the filtered results having, at the same time, trivial contribution to the sensitivity of the filter. It is further demonstrated that the filter is independent of the time period and the geographic location of application.

  6. Applications of Kalman filters based on non-linear functions to numerical weather predictions

    G. Galanis

    2006-10-01

    Full Text Available This paper investigates the use of non-linear functions in classical Kalman filter algorithms on the improvement of regional weather forecasts. The main aim is the implementation of non linear polynomial mappings in a usual linear Kalman filter in order to simulate better non linear problems in numerical weather prediction. In addition, the optimal order of the polynomials applied for such a filter is identified. This work is based on observations and corresponding numerical weather predictions of two meteorological parameters characterized by essential differences in their evolution in time, namely, air temperature and wind speed. It is shown that in both cases, a polynomial of low order is adequate for eliminating any systematic error, while higher order functions lead to instabilities in the filtered results having, at the same time, trivial contribution to the sensitivity of the filter. It is further demonstrated that the filter is independent of the time period and the geographic location of application.

  7. Completeness, special functions and uncertainty principles over q-linear grids

    Abreu, LuIs Daniel

    2006-01-01

    We derive completeness criteria for sequences of functions of the form f(xλ n ), where λ n is the nth zero of a suitably chosen entire function. Using these criteria, we construct complete nonorthogonal systems of Fourier-Bessel functions and their q-analogues, as well as other complete sets of q-special functions. We discuss connections with uncertainty principles over q-linear grids and the completeness of certain sets of q-Bessel functions is used to prove that, if a function f and its q-Hankel transform both vanish at the points {q -n } ∞ n=1 , 0 n } ∞ n=-∞

  8. Stress relaxation experiments on a lamellar polystyrene-polyisoprene diblock copolymer melt

    Holmqvist, P.; Castelletto, V.; Hamley, I.W.

    2001-01-01

    The non-linear rheology of the lamellar phase of a polystyrene-polyisoprene diblock copolymer is studied by oscillatory shear experiments. The relaxation of the shear modulus, G(t, gamma) is studied as a function of strain amplitude, gamma, up to large amplitude strains, gamma = 100%. The decay...... of G(t, gamma) is analysed using the model-independent CONTIN inverse Laplace transform algorithm to obtain a series of relaxation times, which reveals multiple relaxation processes. The timescale for the fastest relaxation processes is compared to those previously observed for diblock copolymer melts...... via dynamic light scattering experiments. The slowest relaxation process may be related to the shear-induced orientation of the lamellae. It is shown that time-strain separability G(t, gamma)= G(t)h(gamma) can be applied, and the damping function h(gamma) is consistent with a strongly strain...

  9. Isomorphism and the #betta#-function of the non-linear sigma model in symmetric spaces

    Hikami, S.

    1983-01-01

    The renormalization group #betta#-function of the non-linear sigma model in symmetric spaces is discussed via the isomorphic relation and the reciprocal relation about a parameter α. The four-loop term is investigated and the symmetric properties of the #betta#-function are studied. The four-loop term in the #betta#-function is shown to be vanishing for the orthogonal Anderson localization problem. (orig.)

  10. Impact of non-functionalized and ionic liquid modified carbon nanotubes on mechanical and thermal properties of ethylene- octene copolymer nanocomposites

    Ivanova, T; Meri, R Merijs; Zicans, J; Grigalovica, A; Roja, Zh; Reinholds, I

    2016-01-01

    In this article the development and characterization of composites made from metallocene based ethylene-octene copolymer (EOC) with 38% octene content, non-modified or modified multi walled carbon nanotubes (MWCNTs), covalently functionalised with long chain hexadecyl moiety imidazolium ionic liquid (IL-f-MWCNTs), is presented. The procedure of MWCNTs functionalization is discussed. In order to obtain a good dispersion of the filler, composites with MWCNTs and IL-f-MWCNTs in the concentration range of 0.5-12 wt.% were made by ultrasonication / thermoplastic mixing method. The results indicated improvement in mechanical properties with increase of the filler content. The methodology of the development of EOC matrix nanocomposites with IL-f-MWCNTs showed advantages of the conductive material creation with high mechanical stiffness compared to direct melt mixing of EOC with non-modified MWCNTs. A notable enhancement of thermal stability was observed in case of both pristine MWCNTs and IL-f-MWCNTs containing EOC nanocomposites, which was attributed to scavenging action of the nanofiller. Modification of EOC with IL-f-MWCNTs showed somewhat increased efficiency in enhancing overall thermal stability of the composites because of better dispersion of the nanofiller due to compatibilizing effect of IL modifier. (paper)

  11. A Study on Copolymer Systems of Styrene with Diethanolamine Side Group and Methyl Methacrylate

    Aslisah Acikses

    2018-01-01

    Full Text Available 4-Diethanolaminomethyl styrene (DEAMSt monomer was prepared by the modification of 4-chloromethyl styrene with diethanolamine. The copolymers in different combinations (0.11, 0.19, and 0.30 by mole of DEAMSt and methyl methacrylate (MMA were prepared by free radical polymerization method at 60°C in the presence of 1,4-dioxane and AIBN as initiator. The structures of DEAMSt and DEAMSt-MMA copolymer were characterized by FT-IR and 1H-NMR. The glass transition temperature (Tg of the copolymers was measured by DSC. Thermal decomposition behavior of the copolymers was investigated by TGA. The average molecular weights of the copolymers were determined by GPC. The dye uptaking properties of the copolymers were investigated using bromocresol green. Then, the dielectric constant, dielectric loss factor, and conductivity of copolymers were investigated as a function of temperature and frequency. The activation energies (Ea of the copolymers were determined by impedance analyzer.

  12. Thermoresponsive Poly(2-Oxazoline) Molecular Brushes by Living Ionic Polymerization: Modulation of the Cloud Point by Random and Block Copolymer Pendant Chains

    Zhang, Ning

    2012-08-10

    Molecular brushes (MBs) of poly(2-oxazoline)s were prepared by living anionic polymerization of 2-isopropenyl-2-oxazoline to form the backbone and living cationic ring-opening polymerization of 2-n-propyl-2-oxazoline and 2-methyl-2-oxazoline to form random and block copolymers. Their aqueous solutions displayed a distinct thermoresponsive behavior as a function of the side-chain composition and sequence. The cloud point (CP) of MBs with random copolymer side chains is a linear function of the hydrophilic monomer content and can be modulated in a wide range. For MBs with block copolymer side chains, it was found that the block sequence had a strong and surprising effect on the CP. While MBs with a distal hydrophobic block had a CP at 70 °C, MBs with hydrophilic outer blocks already precipitated at 32 °C. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Functional Thinking Ways in Relation to Linear Function Tables of Elementary School Students

    Tanisli, Dilek

    2011-01-01

    One of the basic components of algebraic thinking is functional thinking. Functional thinking involves focusing on the relationship between two (or more) varying quantities and such thinking facilitates the studies on both algebra and the notion of function. The development of functional thinking of students should start in the early grades and it…

  14. Taming waveform inversion non-linearity through phase unwrapping of the model and objective functions

    Alkhalifah, Tariq Ali

    2012-09-25

    Traveltime inversion focuses on the geometrical features of the waveform (traveltimes), which is generally smooth, and thus, tends to provide averaged (smoothed) information of the model. On other hand, general waveform inversion uses additional elements of the wavefield including amplitudes to extract higher resolution information, but this comes at the cost of introducing non-linearity to the inversion operator, complicating the convergence process. We use unwrapped phase-based objective functions in waveform inversion as a link between the two general types of inversions in a domain in which such contributions to the inversion process can be easily identified and controlled. The instantaneous traveltime is a measure of the average traveltime of the energy in a trace as a function of frequency. It unwraps the phase of wavefields yielding far less non-linearity in the objective function than that experienced with conventional wavefields, yet it still holds most of the critical wavefield information in its frequency dependency. However, it suffers from non-linearity introduced by the model (or reflectivity), as reflections from independent events in our model interact with each other. Unwrapping the phase of such a model can mitigate this non-linearity as well. Specifically, a simple modification to the inverted domain (or model), can reduce the effect of the model-induced non-linearity and, thus, make the inversion more convergent. Simple numerical examples demonstrate these assertions.

  15. Taming waveform inversion non-linearity through phase unwrapping of the model and objective functions

    Alkhalifah, Tariq Ali; Choi, Yun Seok

    2012-01-01

    Traveltime inversion focuses on the geometrical features of the waveform (traveltimes), which is generally smooth, and thus, tends to provide averaged (smoothed) information of the model. On other hand, general waveform inversion uses additional elements of the wavefield including amplitudes to extract higher resolution information, but this comes at the cost of introducing non-linearity to the inversion operator, complicating the convergence process. We use unwrapped phase-based objective functions in waveform inversion as a link between the two general types of inversions in a domain in which such contributions to the inversion process can be easily identified and controlled. The instantaneous traveltime is a measure of the average traveltime of the energy in a trace as a function of frequency. It unwraps the phase of wavefields yielding far less non-linearity in the objective function than that experienced with conventional wavefields, yet it still holds most of the critical wavefield information in its frequency dependency. However, it suffers from non-linearity introduced by the model (or reflectivity), as reflections from independent events in our model interact with each other. Unwrapping the phase of such a model can mitigate this non-linearity as well. Specifically, a simple modification to the inverted domain (or model), can reduce the effect of the model-induced non-linearity and, thus, make the inversion more convergent. Simple numerical examples demonstrate these assertions.

  16. Electrical characterization of fluorinated benzothiadiazole based conjugated copolymer – a promising material for high-performance solar cells

    Toušek, J.; Toušková, J.; Remeš, Z.

    2015-01-01

    Measurements of electrical conductivity, electron work function, carrier mobility ofholes and the diffusion length of excitons were performed on samples of conjugatedpolymers relevant to polymer solar cells. A state of the art fluorinated benzothiadiazolebased conjugated copolymer (PBDTTHD − DTBTff......) was studied and benchmarkedagainst the reference polymer poly-3-hexylthiophene (P3HT).We employed,respectively, four electrode conductivity measurements, Kelvin probe work functionmeasurements, carrier mobility using charge extraction by linearly increasing voltage(CELIV) measurements and diffusion length...

  17. BFLCRM: A BAYESIAN FUNCTIONAL LINEAR COX REGRESSION MODEL FOR PREDICTING TIME TO CONVERSION TO ALZHEIMER'S DISEASE.

    Lee, Eunjee; Zhu, Hongtu; Kong, Dehan; Wang, Yalin; Giovanello, Kelly Sullivan; Ibrahim, Joseph G

    2015-12-01

    The aim of this paper is to develop a Bayesian functional linear Cox regression model (BFLCRM) with both functional and scalar covariates. This new development is motivated by establishing the likelihood of conversion to Alzheimer's disease (AD) in 346 patients with mild cognitive impairment (MCI) enrolled in the Alzheimer's Disease Neuroimaging Initiative 1 (ADNI-1) and the early markers of conversion. These 346 MCI patients were followed over 48 months, with 161 MCI participants progressing to AD at 48 months. The functional linear Cox regression model was used to establish that functional covariates including hippocampus surface morphology and scalar covariates including brain MRI volumes, cognitive performance (ADAS-Cog), and APOE status can accurately predict time to onset of AD. Posterior computation proceeds via an efficient Markov chain Monte Carlo algorithm. A simulation study is performed to evaluate the finite sample performance of BFLCRM.

  18. Sliding mode control-based linear functional observers for discrete-time stochastic systems

    Singh, Satnesh; Janardhanan, Sivaramakrishnan

    2017-11-01

    Sliding mode control (SMC) is one of the most popular techniques to stabilise linear discrete-time stochastic systems. However, application of SMC becomes difficult when the system states are not available for feedback. This paper presents a new approach to design a SMC-based functional observer for discrete-time stochastic systems. The functional observer is based on the Kronecker product approach. Existence conditions and stability analysis of the proposed observer are given. The control input is estimated by a novel linear functional observer. This approach leads to a non-switching type of control, thereby eliminating the fundamental cause of chatter. Furthermore, the functional observer is designed in such a way that the effect of process and measurement noise is minimised. Simulation example is given to illustrate and validate the proposed design method.

  19. Novel method of interpolation and extrapolation of functions by a linear initial value problem

    Shatalov, M

    2008-09-01

    Full Text Available A novel method of function approximation using an initial value, linear, ordinary differential equation (ODE) is presented. The main advantage of this method is to obtain the approximation expressions in a closed form. This technique can be taught...

  20. Understanding Linear Function: A Comparison of Selected Textbooks from England and Shanghai

    Wang, Yuqian; Barmby, Patrick; Bolden, David

    2017-01-01

    This study describes a comparison of how worked examples in selected textbooks from England and Shanghai presented possible learning trajectories towards understanding linear function. Six selected English textbooks and one Shanghai compulsory textbook were analysed with regards to the understanding required for pure mathematics knowledge in…

  1. Sparse non-linear denoising: Generalization performance and pattern reproducibility in functional MRI

    Abrahamsen, Trine Julie; Hansen, Lars Kai

    2011-01-01

    We investigate sparse non-linear denoising of functional brain images by kernel Principal Component Analysis (kernel PCA). The main challenge is the mapping of denoised feature space points back into input space, also referred to as ”the pre-image problem”. Since the feature space mapping is typi...

  2. Case Studies Listening to Students Using Kinesthetic Movement While Learning to Graph Linear Functions

    Novak, Melissa A.

    2017-01-01

    The purpose of this qualitative practitioner research study was to describe middle school algebra students' experiences of learning linear functions through kinesthetic movement. Participants were comprised of 8th grade algebra students. Practitioner research was used because I wanted to improve my teaching so students will have more success in…

  3. Linear hyperbolic functional-differential equations with essentially bounded right-hand side

    Domoshnitsky, A.; Lomtatidze, Alexander; Maghakyan, A.; Šremr, Jiří

    2011-01-01

    Roč. 2011, - (2011), s. 242965 ISSN 1085-3375 Institutional research plan: CEZ:AV0Z10190503 Keywords : linear functional-differential equation of hyperbolic type * Darboux problem * unique solvability Subject RIV: BA - General Mathematics Impact factor: 1.318, year: 2011 http://www.hindawi.com/journals/ aaa /2011/242965/

  4. Non-commutative linear algebra and plurisubharmonic functions of quaternionic variables

    Alesker, Semyon

    2003-01-01

    We recall known and establish new properties of the Dieudonn\\'e and Moore determinants of quaternionic matrices.Using these linear algebraic results we develop a basic theory of plurisubharmonic functions of quaternionic variables. Then we introduce and briefly discuss quaternionic Monge-Amp\\'ere equations.

  5. A Linear Programming Model to Optimize Various Objective Functions of a Foundation Type State Support Program.

    Matzke, Orville R.

    The purpose of this study was to formulate a linear programming model to simulate a foundation type support program and to apply this model to a state support program for the public elementary and secondary school districts in the State of Iowa. The model was successful in producing optimal solutions to five objective functions proposed for…

  6. Interpolation of polytopic control Lyapunov functions for discrete–time linear systems

    Nguyen, T.T.; Lazar, M.; Spinu, V.; Boje, E.; Xia, X.

    2014-01-01

    This paper proposes a method for interpolating two (or more) polytopic control Lyapunov functions (CLFs) for discrete--time linear systems subject to polytopic constraints, thereby combining different control objectives. The corresponding interpolated CLF is used for synthesis of a stabilizing

  7. Linear estimates of structure functions from deep inelastic lepton-nucleon scattering data. Part 1

    Anikeev, V.B.; Zhigunov, V.P.

    1991-01-01

    This paper concerns the linear estimation of structure functions from muon(electron)-nucleon scattering. The expressions obtained for the structure functions estimate provide correct analysis of the random error and the bias The bias arises because of the finite number of experimental data and the finite resolution of experiment. The approach suggested may become useful for data handling from experiments at HERA. 9 refs

  8. SELECTION OF LINEAR DEMAND FUNCTION PARAMETERS FOR ENSURING THE CORRECT SUBSTITUTION EFFECT CALCULATION

    V. Popov

    2013-03-01

    Full Text Available In the course of microeconomics it is convenient to use additive functions of requirements in educational purposes, in which the volume of requirements is set by the linear function of the price, revenue and other factors. But in arriving at the substitution effect there is a number of problems in which impossible answers come out. The formula adjustment concluded by the author, which will allow to avoid contradictions, is described in the article.

  9. Multi-point boundary value problems for linear functional-differential equations

    Domoshnitsky, A.; Hakl, Robert; Půža, Bedřich

    2017-01-01

    Roč. 24, č. 2 (2017), s. 193-206 ISSN 1072-947X Institutional support: RVO:67985840 Keywords : boundary value problems * linear functional- differential equations * functional- differential inequalities Subject RIV: BA - General Mathematics OBOR OECD: Applied mathematics Impact factor: 0.290, year: 2016 https://www.degruyter.com/view/j/gmj.2017.24.issue-2/gmj-2016-0076/gmj-2016-0076.xml

  10. Multi-point boundary value problems for linear functional-differential equations

    Domoshnitsky, A.; Hakl, Robert; Půža, Bedřich

    2017-01-01

    Roč. 24, č. 2 (2017), s. 193-206 ISSN 1072-947X Institutional support: RVO:67985840 Keywords : boundary value problems * linear functional-differential equations * functional-differential inequalities Subject RIV: BA - General Mathematics OBOR OECD: Applied mathematics Impact factor: 0.290, year: 2016 https://www.degruyter.com/view/j/gmj.2017.24.issue-2/gmj-2016-0076/gmj-2016-0076. xml

  11. Nanoparticles based on novel amphiphilic polyaspartamide copolymers

    Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

    2010-01-01

    In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

  12. Predicting recovery of cognitive function soon after stroke: differential modeling of logarithmic and linear regression.

    Suzuki, Makoto; Sugimura, Yuko; Yamada, Sumio; Omori, Yoshitsugu; Miyamoto, Masaaki; Yamamoto, Jun-ichi

    2013-01-01

    Cognitive disorders in the acute stage of stroke are common and are important independent predictors of adverse outcome in the long term. Despite the impact of cognitive disorders on both patients and their families, it is still difficult to predict the extent or duration of cognitive impairments. The objective of the present study was, therefore, to provide data on predicting the recovery of cognitive function soon after stroke by differential modeling with logarithmic and linear regression. This study included two rounds of data collection comprising 57 stroke patients enrolled in the first round for the purpose of identifying the time course of cognitive recovery in the early-phase group data, and 43 stroke patients in the second round for the purpose of ensuring that the correlation of the early-phase group data applied to the prediction of each individual's degree of cognitive recovery. In the first round, Mini-Mental State Examination (MMSE) scores were assessed 3 times during hospitalization, and the scores were regressed on the logarithm and linear of time. In the second round, calculations of MMSE scores were made for the first two scoring times after admission to tailor the structures of logarithmic and linear regression formulae to fit an individual's degree of functional recovery. The time course of early-phase recovery for cognitive functions resembled both logarithmic and linear functions. However, MMSE scores sampled at two baseline points based on logarithmic regression modeling could estimate prediction of cognitive recovery more accurately than could linear regression modeling (logarithmic modeling, R(2) = 0.676, PLogarithmic modeling based on MMSE scores could accurately predict the recovery of cognitive function soon after the occurrence of stroke. This logarithmic modeling with mathematical procedures is simple enough to be adopted in daily clinical practice.

  13. Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

    Cottrell, I.W.; Empey, R.A.; Racciato, J.S.

    1978-08-08

    A water-soluble anionic graft copolymer of xanthan gum and polyacrylamide is described in which at least part of the amide function of the acrylamide portion of the copolymer is sulfomethylated and the xanthan gum portion of the copolymer is unreacted with formaldehyde. The copolymer is sulfomethylated by reaction with formaldehyde and sodium metabisulfite. The formaldehyde does not cause any appreciable cross-linking between hydroxyl groups of the xanthan moieties. The sulfomethylation of the acrylamido group takes place at temperatures from 35 to 70 C. The pH is 10 or higher, typically from 12 to 13. The degree of anionic character may be varied by adjusting the molar ratio of formaldehyde and sodium metabisulfite with respect to the copolymer. 10 claims.

  14. Unsteady Solution of Non-Linear Differential Equations Using Walsh Function Series

    Gnoffo, Peter A.

    2015-01-01

    Walsh functions form an orthonormal basis set consisting of square waves. The discontinuous nature of square waves make the system well suited for representing functions with discontinuities. The product of any two Walsh functions is another Walsh function - a feature that can radically change an algorithm for solving non-linear partial differential equations (PDEs). The solution algorithm of non-linear differential equations using Walsh function series is unique in that integrals and derivatives may be computed using simple matrix multiplication of series representations of functions. Solutions to PDEs are derived as functions of wave component amplitude. Three sample problems are presented to illustrate the Walsh function series approach to solving unsteady PDEs. These include an advection equation, a Burgers equation, and a Riemann problem. The sample problems demonstrate the use of the Walsh function solution algorithms, exploiting Fast Walsh Transforms in multi-dimensions (O(Nlog(N))). Details of a Fast Walsh Reciprocal, defined here for the first time, enable inversion of aWalsh Symmetric Matrix in O(Nlog(N)) operations. Walsh functions have been derived using a fractal recursion algorithm and these fractal patterns are observed in the progression of pairs of wave number amplitudes in the solutions. These patterns are most easily observed in a remapping defined as a fractal fingerprint (FFP). A prolongation of existing solutions to the next highest order exploits these patterns. The algorithms presented here are considered a work in progress that provide new alternatives and new insights into the solution of non-linear PDEs.

  15. Parameter-dependent PWQ Lyapunov function stability criteria for uncertain piecewise linear systems

    Morten Hovd

    2018-01-01

    Full Text Available The calculation of piecewise quadratic (PWQ Lyapunov functions is addressed in view of stability analysis of uncertain piecewise linear dynamics. As main contribution, the linear matrix inequality (LMI approach proposed in (Johansson and Rantzer, 1998 for the stability analysis of PWL and PWA dynamics is extended to account for parametric uncertainty based on a improved relaxation technique. The results are applied for the analysis of a Phase Locked Loop (PLL benchmark and the ability to guarantee a stability region in the parameter space well beyond the state of the art is demonstrated.

  16. STUDIES ON POLY (ETHYLENE TEREPHTHALATE)- POLY ( TETRAMETHYLENE ETHER ) MULTIBLOCK COPOLYMER.Ⅰ. COM POSITIONAL HOMOGENEITY

    ZHAN Yongjian; YING Qicong; WU Meiyan; QIAN Renyuan

    1991-01-01

    The compositional homogeneity of a poly (ethylene terephthalate )-poly (tetramethylene ether)multiblock copolymer sample with low content of hard segment was examined by GPC, TLC, and solubility method. The copolymer sample was found to have a uniform composition as a function of elution volume over the major portion of sample from GPC method. However within one elution fraction, the copolymer chains, although having the same hydrodynamic volume, may have some difference in composition. Two fractions with different composition were obtained by precipitation in ethanol. Some low molar mass copolymers were also separated by a TLC technique from the copolymer sample.

  17. Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

    Yunqi Li

    2016-04-01

    Full Text Available This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially polystyrene-block-poly(2-vinylpyridine-block-poly(ethylene oxide (abbreviated as PS-b-P2VP-b-PEO.

  18. Weighted functional linear regression models for gene-based association analysis.

    Belonogova, Nadezhda M; Svishcheva, Gulnara R; Wilson, James F; Campbell, Harry; Axenovich, Tatiana I

    2018-01-01

    Functional linear regression models are effectively used in gene-based association analysis of complex traits. These models combine information about individual genetic variants, taking into account their positions and reducing the influence of noise and/or observation errors. To increase the power of methods, where several differently informative components are combined, weights are introduced to give the advantage to more informative components. Allele-specific weights have been introduced to collapsing and kernel-based approaches to gene-based association analysis. Here we have for the first time introduced weights to functional linear regression models adapted for both independent and family samples. Using data simulated on the basis of GAW17 genotypes and weights defined by allele frequencies via the beta distribution, we demonstrated that type I errors correspond to declared values and that increasing the weights of causal variants allows the power of functional linear models to be increased. We applied the new method to real data on blood pressure from the ORCADES sample. Five of the six known genes with P models. Moreover, we found an association between diastolic blood pressure and the VMP1 gene (P = 8.18×10-6), when we used a weighted functional model. For this gene, the unweighted functional and weighted kernel-based models had P = 0.004 and 0.006, respectively. The new method has been implemented in the program package FREGAT, which is freely available at https://cran.r-project.org/web/packages/FREGAT/index.html.

  19. Orthogonality, Lommel integrals and cross product zeros of linear combinations of Bessel functions.

    Ziener, Christian H; Kurz, Felix T; Buschle, Lukas R; Kampf, Thomas

    2015-01-01

    The cylindrical Bessel differential equation and the spherical Bessel differential equation in the interval [Formula: see text] with Neumann boundary conditions are considered. The eigenfunctions are linear combinations of the Bessel function [Formula: see text] or linear combinations of the spherical Bessel functions [Formula: see text]. The orthogonality relations with analytical expressions for the normalization constant are given. Explicit expressions for the Lommel integrals in terms of Lommel functions are derived. The cross product zeros [Formula: see text] and [Formula: see text] are considered in the complex plane for real as well as complex values of the index [Formula: see text] and approximations for the exceptional zero [Formula: see text] are obtained. A numerical scheme based on the discretization of the two-dimensional and three-dimensional Laplace operator with Neumann boundary conditions is presented. Explicit representations of the radial part of the Laplace operator in form of a tridiagonal matrix allow the simple computation of the cross product zeros.

  20. Fluctuations of two-time quantities and non-linear response functions

    Corberi, F; Lippiello, E; Sarracino, A; Zannetti, M

    2010-01-01

    We study the fluctuations of the autocorrelation and autoresponse functions and, in particular, their variances and covariance. In a first general part of the paper, we show the equivalence of the variance of the response function to the second-order susceptibility of a composite operator, and we derive an equilibrium fluctuation-dissipation theorem beyond linear order, relating it to the other variances. In a second part of the paper we apply the formalism in the study of non-disordered ferromagnets, in equilibrium or in the coarsening kinetics following a critical or sub-critical quench. We show numerically that the variances and the non-linear susceptibility obey scaling with respect to the coherence length ξ in equilibrium, and with respect to the growing length L(t) after a quench, similar to what is known for the autocorrelation and the autoresponse functions

  1. KEELE, Minimization of Nonlinear Function with Linear Constraints, Variable Metric Method

    Westley, G.W.

    1975-01-01

    1 - Description of problem or function: KEELE is a linearly constrained nonlinear programming algorithm for locating a local minimum of a function of n variables with the variables subject to linear equality and/or inequality constraints. 2 - Method of solution: A variable metric procedure is used where the direction of search at each iteration is obtained by multiplying the negative of the gradient vector by a positive definite matrix which approximates the inverse of the matrix of second partial derivatives associated with the function. 3 - Restrictions on the complexity of the problem: Array dimensions limit the number of variables to 20 and the number of constraints to 50. These can be changed by the user

  2. Amphiphilic block copolymers for biomedical applications

    Zupancich, John Andrew

    Amphiphilic block copolymer self-assembly provides a versatile means to prepare nanoscale objects in solution. Control over aggregate shape is granted through manipulation of amphiphile composition and the synthesis of well-defined polymers offers the potential to produce micelles with geometries optimized for specific applications. Currently, polymer micelles are being investigated as vehicles for the delivery of therapeutics and attempts to increase efficacy has motivated efforts to incorporate bioactive ligands and stimuli-responsive character into these structures. This thesis reports the synthesis and self-assembly of biocompatible, degradable polymeric amphiphiles. Spherical, cylindrical, and bilayered vesicle structures were generated spontaneously by the direct dispersion of poly(ethylene oxide)-b-poly(gamma-methyl-ε-caprolactone) block copolymers in water and solutions were characterized with cryogenic transmission electron microscopy (cryo-TEM). The dependence of micelle structure on diblock copolymer composition was examined through the systematic variation of the hydrophobic block molecular weight. A continuous evolution of morphology was observed with coexistence of aggregate structures occurring in windows of composition intermediate to that of pure spheres, cylinders and vesicles. A number of heterobifunctional poly(ethylene oxide) polymers were synthesized for the preparation of ligand-functionalized amphiphilic diblock copolymers. The effect of ligand conjugation on block copolymer self-assembly and micelle morphology was also examined. An RGD-containing peptide sequence was efficiently conjugated to a set of well characterized poly(ethylene oxide)-b-poly(butadiene) copolymers. The reported aggregate morphologies of peptide-functionalized polymeric amphiphiles deviated from canonical structures and the micelle clustering, cylinder fragmentation, network formation, and multilayer vesicle generation documented with cryo-TEM was attributed to

  3. Viscoelastic effects in three-dimensional microphase separation of block copolymers : Dynamic mean-field density functional approach

    Maurits, NM; Zvelindovsky, AV; Fraaije, JGEM

    1998-01-01

    In the present paper, we extend the dynamic mean-field density functional method which describes microphase separation phenomena in polymer liquids, to account for viscoelastic effects. The effect of simple steady shear on polymer orientation and elongation is taken into account by adapting the

  4. Theoretical foundations of functional data analysis, with an introduction to linear operators

    Hsing, Tailen

    2015-01-01

    Theoretical Foundations of Functional Data Analysis, with an Introduction to Linear Operators provides a uniquely broad compendium of the key mathematical concepts and results that are relevant for the theoretical development of functional data analysis (FDA).The self-contained treatment of selected topics of functional analysis and operator theory includes reproducing kernel Hilbert spaces, singular value decomposition of compact operators on Hilbert spaces and perturbation theory for both self-adjoint and non self-adjoint operators. The probabilistic foundation for FDA is described from the

  5. Functional models for commutative systems of linear operators and de Branges spaces on a Riemann surface

    Zolotarev, Vladimir A

    2009-01-01

    Functional models are constructed for commutative systems {A 1 ,A 2 } of bounded linear non-self-adjoint operators which do not contain dissipative operators (which means that ξ 1 A 1 +ξ 2 A 2 is not a dissipative operator for any ξ 1 , ξ 2 element of R). A significant role is played here by the de Branges transform and the function classes occurring in this context. Classes of commutative systems of operators {A 1 ,A 2 } for which such a construction is possible are distinguished. Realizations of functional models in special spaces of meromorphic functions on Riemann surfaces are found, which lead to reasonable analogues of de Branges spaces on these Riemann surfaces. It turns out that the functions E(p) and E-tilde(p) determining the order of growth in de Branges spaces on Riemann surfaces coincide with the well-known Baker-Akhiezer functions. Bibliography: 11 titles.

  6. Non-linear multivariable predictive control of an alcoholic fermentation process using functional link networks

    Luiz Augusto da Cruz Meleiro

    2005-06-01

    Full Text Available In this work a MIMO non-linear predictive controller was developed for an extractive alcoholic fermentation process. The internal model of the controller was represented by two MISO Functional Link Networks (FLNs, identified using simulated data generated from a deterministic mathematical model whose kinetic parameters were determined experimentally. The FLN structure presents as advantages fast training and guaranteed convergence, since the estimation of the weights is a linear optimization problem. Besides, the elimination of non-significant weights generates parsimonious models, which allows for fast execution in an MPC-based algorithm. The proposed algorithm showed good potential in identification and control of non-linear processes.Neste trabalho um controlador preditivo não linear multivariável foi desenvolvido para um processo de fermentação alcoólica extrativa. O modelo interno do controlador foi representado por duas redes do tipo Functional Link (FLN, identificadas usando dados de simulação gerados a partir de um modelo validado experimentalmente. A estrutura FLN apresenta como vantagem o treinamento rápido e convergência garantida, já que a estimação dos seus pesos é um problema de otimização linear. Além disso, a eliminação de pesos não significativos gera modelos parsimoniosos, o que permite a rápida execução em algoritmos de controle preditivo baseado em modelo. Os resultados mostram que o algoritmo proposto tem grande potencial para identificação e controle de processos não lineares.

  7. Generating linear regression model to predict motor functions by use of laser range finder during TUG.

    Adachi, Daiki; Nishiguchi, Shu; Fukutani, Naoto; Hotta, Takayuki; Tashiro, Yuto; Morino, Saori; Shirooka, Hidehiko; Nozaki, Yuma; Hirata, Hinako; Yamaguchi, Moe; Yorozu, Ayanori; Takahashi, Masaki; Aoyama, Tomoki

    2017-05-01

    The purpose of this study was to investigate which spatial and temporal parameters of the Timed Up and Go (TUG) test are associated with motor function in elderly individuals. This study included 99 community-dwelling women aged 72.9 ± 6.3 years. Step length, step width, single support time, variability of the aforementioned parameters, gait velocity, cadence, reaction time from starting signal to first step, and minimum distance between the foot and a marker placed to 3 in front of the chair were measured using our analysis system. The 10-m walk test, five times sit-to-stand (FTSTS) test, and one-leg standing (OLS) test were used to assess motor function. Stepwise multivariate linear regression analysis was used to determine which TUG test parameters were associated with each motor function test. Finally, we calculated a predictive model for each motor function test using each regression coefficient. In stepwise linear regression analysis, step length and cadence were significantly associated with the 10-m walk test, FTSTS and OLS test. Reaction time was associated with the FTSTS test, and step width was associated with the OLS test. Each predictive model showed a strong correlation with the 10-m walk test and OLS test (P motor function test. Moreover, the TUG test time regarded as the lower extremity function and mobility has strong predictive ability in each motor function test. Copyright © 2017 The Japanese Orthopaedic Association. Published by Elsevier B.V. All rights reserved.

  8. СREATION OF CORRELATION FUNCTIONS OF LINEAR CONTINUOUS SYSTEMS BASED ON THEIR FUNDAMENTAL MATRICES

    N. A. Vunder

    2015-11-01

    Full Text Available The paper presents a method of creating correlation matrices and functions of the state vectors and outputs of the linear continuous systems functioning under the conditions of stochastic stationary, in a broad sense, effects. Fundamental matrices form the basis of the method. We have shown that for the linear continuous systems with single dimensional input and single dimensional output the correlation output function of such system can be found as the free movement of this system generated by its initial state. This state is constructed from the variance matrix of the state vector and the transposed output matrix. We have elucidated that when a continuous system belongs to a class of multi-dimensional input – multi-dimensional output systems, the following options are available for solving the problem of creation of the correlation function of a linear system. The first option is to partition the system into separate channels. Then the approach developed for systems with onedimensional input and one-dimensional output is applied to each of the separate channels. The second option is used to preserve the vector nature of the stochastic external influence. It consists in partition of output vector to scalar components by separating output matrix into separate rows with subsequent formation of the correlation function according to the scheme for single dimensional input and single dimensional output type systems. The third option is based on the scalarization of matrix correlation output function by applying the singular value decomposition to it. That gives the possibility to form scalar majorant and minorant of correlation output functions. We have established that a key component of a computational procedure of creating the correlation function of continuous linear system is a variance matrix of the system state vector. In the case of functioning under an exogenous stochastic effect like "white noise" the variance matrix is calculated by

  9. Generalized prolate spheroidal wave functions for optical finite fractional Fourier and linear canonical transforms.

    Pei, Soo-Chang; Ding, Jian-Jiun

    2005-03-01

    Prolate spheroidal wave functions (PSWFs) are known to be useful for analyzing the properties of the finite-extension Fourier transform (fi-FT). We extend the theory of PSWFs for the finite-extension fractional Fourier transform, the finite-extension linear canonical transform, and the finite-extension offset linear canonical transform. These finite transforms are more flexible than the fi-FT and can model much more generalized optical systems. We also illustrate how to use the generalized prolate spheroidal functions we derive to analyze the energy-preservation ratio, the self-imaging phenomenon, and the resonance phenomenon of the finite-sized one-stage or multiple-stage optical systems.

  10. Isotherms and thermodynamics by linear and non-linear regression analysis for the sorption of methylene blue onto activated carbon: Comparison of various error functions

    Kumar, K. Vasanth; Porkodi, K.; Rocha, F.

    2008-01-01

    A comparison of linear and non-linear regression method in selecting the optimum isotherm was made to the experimental equilibrium data of methylene blue sorption by activated carbon. The r 2 was used to select the best fit linear theoretical isotherm. In the case of non-linear regression method, six error functions, namely coefficient of determination (r 2 ), hybrid fractional error function (HYBRID), Marquardt's percent standard deviation (MPSD), average relative error (ARE), sum of the errors squared (ERRSQ) and sum of the absolute errors (EABS) were used to predict the parameters involved in the two and three parameter isotherms and also to predict the optimum isotherm. For two parameter isotherm, MPSD was found to be the best error function in minimizing the error distribution between the experimental equilibrium data and predicted isotherms. In the case of three parameter isotherm, r 2 was found to be the best error function to minimize the error distribution structure between experimental equilibrium data and theoretical isotherms. The present study showed that the size of the error function alone is not a deciding factor to choose the optimum isotherm. In addition to the size of error function, the theory behind the predicted isotherm should be verified with the help of experimental data while selecting the optimum isotherm. A coefficient of non-determination, K 2 was explained and was found to be very useful in identifying the best error function while selecting the optimum isotherm

  11. Synthesis and Characterization of Novel Magnetite Nanoparticle Block Copolymer Complexes

    Zhang, Qian

    2007-01-01

    Superparamagnetic Magnetite (Fe3O4) nanoparticles were synthesized and complexed with carboxylate-functionalized block copolymers, and aqueous dispersions of the complexes were investigated as functions of their chemical and morphological structures. The block copolymer dispersants possessed either poly(ethylene oxide), poly(ethylene oxide-co-propylene oxide), or poly(ethylene oxide-b-propylene oxide) outer blocks, and all contained a polyurethane center block with pendant carboxylate functi...

  12. Non-Linear Back-propagation: Doing Back-Propagation withoutDerivatives of the Activation Function

    Hertz, John; Krogh, Anders Stærmose; Lautrup, Benny

    1997-01-01

    The conventional linear back-propagation algorithm is replaced by a non-linear version, which avoids the necessity for calculating the derivative of the activation function. This may be exploited in hardware realizations of neural processors. In this paper we derive the non-linear back...

  13. Nonparametric adaptive estimation of linear functionals for low frequency observed Lévy processes

    Kappus, Johanna

    2012-01-01

    For a Lévy process X having finite variation on compact sets and finite first moments, µ( dx) = xv( dx) is a finite signed measure which completely describes the jump dynamics. We construct kernel estimators for linear functionals of µ and provide rates of convergence under regularity assumptions. Moreover, we consider adaptive estimation via model selection and propose a new strategy for the data driven choice of the smoothing parameter.

  14. Two-fluid static spherical configurations with linear mass function in the Einstein-Cartan theory

    Gallakhmetov, A.M.

    2002-01-01

    In the framework of the Einstein-Cartan theory, two-fluid static spherical configurations with linear mass function are considered. One of these modelling anisotropic matter distributions within star and the other fluid is a perfect fluid representing a source of torsion. It is shown that the solutions of the Einstein equations for anisotropic relativistic spheres in General Relativity may generate the solutions in the Einstein-Cartan theory. Some exact solutions are obtained

  15. Guaranteed and computable bounds of the limit load for variational problems with linear growth energy functionals

    Haslinger, Jaroslav; Repin, S.; Sysala, Stanislav

    2016-01-01

    Roč. 61, č. 5 (2016), s. 527-564 ISSN 0862-7940 R&D Projects: GA MŠk LQ1602 Institutional support: RVO:68145535 Keywords : functionals with linear growth * limit load * truncation method * perfect plasticity Subject RIV: BA - General Mathematics Impact factor: 0.618, year: 2016 http://link.springer.com/article/10.1007/s10492-016-0146-6

  16. Localization of periodic orbits of polynomial vector fields of even degree by linear functions

    Starkov, Konstantin E. [CITEDI-IPN, Av. del Parque 1310, Mesa de Otay, Tijuana, BC (Mexico)] e-mail: konst@citedi.mx

    2005-08-01

    This paper is concerned with the localization problem of periodic orbits of polynomial vector fields of even degree by using linear functions. Conditions of the localization of all periodic orbits in sets of a simple structure are obtained. Our results are based on the solution of the conditional extremum problem and the application of homogeneous polynomial forms of even degrees. As examples, the Lanford system, the jerky system with one quadratic monomial and a quartically perturbed harmonic oscillator are considered.

  17. Localization of periodic orbits of polynomial vector fields of even degree by linear functions

    Starkov, Konstantin E.

    2005-01-01

    This paper is concerned with the localization problem of periodic orbits of polynomial vector fields of even degree by using linear functions. Conditions of the localization of all periodic orbits in sets of a simple structure are obtained. Our results are based on the solution of the conditional extremum problem and the application of homogeneous polynomial forms of even degrees. As examples, the Lanford system, the jerky system with one quadratic monomial and a quartically perturbed harmonic oscillator are considered

  18. Fibonacci collocation method with a residual error Function to solve linear Volterra integro differential equations

    Salih Yalcinbas

    2016-01-01

    Full Text Available In this paper, a new collocation method based on the Fibonacci polynomials is introduced to solve the high-order linear Volterra integro-differential equations under the conditions. Numerical examples are included to demonstrate the applicability and validity of the proposed method and comparisons are made with the existing results. In addition, an error estimation based on the residual functions is presented for this method. The approximate solutions are improved by using this error estimation.

  19. Self-assembling block copolymer systems involving competing length scales : A route toward responsive materials

    Nap, R; Erukhimovich, [No Value; ten Brinke, G; Erukhimovich, Igor

    2004-01-01

    The phase behavior of block copolymers melts involving competing length scales, i.e., able to microphase separate on two different length scales, is theoretically investigated using a self-consistent field approach. The specific block copolymers studied consist of a linear A-block linked to an

  20. Towards developing an efficient sensitive element for trinitrotoluene detection: TiO{sub 2} thin films functionalized with molecularly imprinted copolymer films

    Lazau, Carmen [National Institute for Research and Development in Electrochemistry and Condensed Matter, Condensed Matter Department, 1 P. Andronescu Street, 300224 Timisoara (Romania); Iordache, Tanta-Verona [National Research and Development Institute for Chemistry and Petrochemistry INCDCP-ICECHIM, Advanced Polymer Materials and Polymer Recycling, 202 Splaiul Independentei, 060021 Bucharest (Romania); Florea, Ana-Mihaela [National Research and Development Institute for Chemistry and Petrochemistry INCDCP-ICECHIM, Advanced Polymer Materials and Polymer Recycling, 202 Splaiul Independentei, 060021 Bucharest (Romania); University Politehnica of Bucharest, The Faculty of Applied Chemistry and Materials Science, Bioresources and Polymer Science Department, 1-7 Polizu, 011061 Bucharest (Romania); Orha, Corina [National Institute for Research and Development in Electrochemistry and Condensed Matter, Condensed Matter Department, 1 P. Andronescu Street, 300224 Timisoara (Romania); Bandas, Cornelia, E-mail: cornelia.bandas@gmail.com [National Institute for Research and Development in Electrochemistry and Condensed Matter, Condensed Matter Department, 1 P. Andronescu Street, 300224 Timisoara (Romania); Radu, Anita-Laura; Sarbu, Andrei [National Research and Development Institute for Chemistry and Petrochemistry INCDCP-ICECHIM, Advanced Polymer Materials and Polymer Recycling, 202 Splaiul Independentei, 060021 Bucharest (Romania); Rotariu, Traian [Technical Military Academy, Chemistry Department, Bucharest (Romania)

    2016-10-30

    Highlights: • A new concept for creating reusable and more sensitive sensors for trinitrotoluene. • Titanium oxide thin films as transducers deposited by a new hydrothermal process. • Trinitrotoluene-molecularly imprinted receptors obtained by a two-step procedure. - Abstract: In this study, TiO{sub 2} films were successfully grown in-situ onto a FTO substrate by a hydrothermal method, using TiCl{sub 4} as Ti precursor, and further on functionalized with a 2,4,6-trinitrotoluene-molecularly imprinted polymer (TNT-MIP) film as a preliminary step in developing a trinitrotoluene (TNT) reusable sensor to overcome the international security issues. For investigating the TiO{sub 2} film thickness, crystalline structure and morphology, the films were autoclaved at 200 °C at different times. The X-ray diffraction showed that TiO{sub 2} films possessed a rutile structure, with no cracks visible by atomic force microscopy (AFM), and the films morphology observed by scanning electron microscopy (SEM) was highly dependent upon the hydrothermal treatment time. Yet, the TiO{sub 2} films with a more porous surface were more suitable for TNT-MIP film deposit. Rheology of precursor polymer film solutions, based on poly (acrylonitrile-co-acrylic acid), poly (acrylonitrile-co-methacrylic acid) or poly (acrylonitrile- co-itaconic acid), and the structure and adherence of TNT-MIP films were investigated in order to establish the correct recipe of the MIP. The removal yield of TNT from the imprinted films, the thickness, the porosity and the compatibility with the inorganic TiO{sub 2} film were adequate for the poly (acrylonitrile-co-acrylic acid) system with an acrylonitrile: acrylic acid practical ratio of 86.1:13.9 (wt./wt.). Farmore, AFM morphology corroborated with SEM results highlighted the effect of TNT imprinting in the copolymer matrix as the surface of the imprinted layer was quite different from that of the non-imprinted layer.

  1. Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

    Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

    2017-08-01

    Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Influence of Functionality on Direct Arylation of Model Systems as a Route Toward Fluorinated Copolymers via Direct Arylation Polymerization (DArP)

    Livi, Francesco; Gobalasingham, Nemal S.; Bundgaard, Eva

    2015-01-01

    A screening of direct arylation conditions on amodel small molecule system is carried out to develop suitableconditions for the direct arylation polymerization (DArP) of fluorinatedcopolymers, which are incompatible with conditionspreviously utilized successfully for nonfluorinated systems. Themo......,4-phenylene)dithiophene. Polymers arefree of β-defects and significant homocoupling. This work furtherunderscores the attractive simplicity, relevance, and easeof DArP while reconfirming its broad compatibility withincreasingly popular fluorinated copolymers....

  3. Estimation of Multiple Point Sources for Linear Fractional Order Systems Using Modulating Functions

    Belkhatir, Zehor

    2017-06-28

    This paper proposes an estimation algorithm for the characterization of multiple point inputs for linear fractional order systems. First, using polynomial modulating functions method and a suitable change of variables the problem of estimating the locations and the amplitudes of a multi-pointwise input is decoupled into two algebraic systems of equations. The first system is nonlinear and solves for the time locations iteratively, whereas the second system is linear and solves for the input’s amplitudes. Second, closed form formulas for both the time location and the amplitude are provided in the particular case of single point input. Finally, numerical examples are given to illustrate the performance of the proposed technique in both noise-free and noisy cases. The joint estimation of pointwise input and fractional differentiation orders is also presented. Furthermore, a discussion on the performance of the proposed algorithm is provided.

  4. Setting a generalized functional linear model (GFLM for the classification of different types of cancer

    Miguel Flores

    2016-11-01

    Full Text Available This work aims to classify the DNA sequences of healthy and malignant cancer respectively. For this, supervised and unsupervised classification methods from a functional context are used; i.e. each strand of DNA is an observation. The observations are discretized, for that reason different ways to represent these observations with functions are evaluated. In addition, an exploratory study is done: estimating the mean and variance of each functional type of cancer. For the unsupervised classification method, hierarchical clustering with different measures of functional distance is used. On the other hand, for the supervised classification method, a functional generalized linear model is used. For this model the first and second derivatives are used which are included as discriminating variables. It has been verified that one of the advantages of working in the functional context is to obtain a model to correctly classify cancers by 100%. For the implementation of the methods it has been used the fda.usc R package that includes all the techniques of functional data analysis used in this work. In addition, some that have been developed in recent decades. For more details of these techniques can be consulted Ramsay, J. O. and Silverman (2005 and Ferraty et al. (2006.

  5. Linearized semiclassical initial value time correlation functions with maximum entropy analytic continuation.

    Liu, Jian; Miller, William H

    2008-09-28

    The maximum entropy analytic continuation (MEAC) method is used to extend the range of accuracy of the linearized semiclassical initial value representation (LSC-IVR)/classical Wigner approximation for real time correlation functions. LSC-IVR provides a very effective "prior" for the MEAC procedure since it is very good for short times, exact for all time and temperature for harmonic potentials (even for correlation functions of nonlinear operators), and becomes exact in the classical high temperature limit. This combined MEAC+LSC/IVR approach is applied here to two highly nonlinear dynamical systems, a pure quartic potential in one dimensional and liquid para-hydrogen at two thermal state points (25 and 14 K under nearly zero external pressure). The former example shows the MEAC procedure to be a very significant enhancement of the LSC-IVR for correlation functions of both linear and nonlinear operators, and especially at low temperature where semiclassical approximations are least accurate. For liquid para-hydrogen, the LSC-IVR is seen already to be excellent at T=25 K, but the MEAC procedure produces a significant correction at the lower temperature (T=14 K). Comparisons are also made as to how the MEAC procedure is able to provide corrections for other trajectory-based dynamical approximations when used as priors.

  6. Estimation of Nonlinear Functions of State Vector for Linear Systems with Time-Delays and Uncertainties

    Il Young Song

    2015-01-01

    Full Text Available This paper focuses on estimation of a nonlinear function of state vector (NFS in discrete-time linear systems with time-delays and model uncertainties. The NFS represents a multivariate nonlinear function of state variables, which can indicate useful information of a target system for control. The optimal nonlinear estimator of an NFS (in mean square sense represents a function of the receding horizon estimate and its error covariance. The proposed receding horizon filter represents the standard Kalman filter with time-delays and special initial horizon conditions described by the Lyapunov-like equations. In general case to calculate an optimal estimator of an NFS we propose using the unscented transformation. Important class of polynomial NFS is considered in detail. In the case of polynomial NFS an optimal estimator has a closed-form computational procedure. The subsequent application of the proposed receding horizon filter and nonlinear estimator to a linear stochastic system with time-delays and uncertainties demonstrates their effectiveness.

  7. Linear algebra

    Shilov, Georgi E

    1977-01-01

    Covers determinants, linear spaces, systems of linear equations, linear functions of a vector argument, coordinate transformations, the canonical form of the matrix of a linear operator, bilinear and quadratic forms, Euclidean spaces, unitary spaces, quadratic forms in Euclidean and unitary spaces, finite-dimensional space. Problems with hints and answers.

  8. Sequential double excitations from linear-response time-dependent density functional theory

    Mosquera, Martín A.; Ratner, Mark A.; Schatz, George C., E-mail: g-schatz@northwestern.edu [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chen, Lin X. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

    2016-05-28

    Traditional UV/vis and X-ray spectroscopies focus mainly on the study of excitations starting exclusively from electronic ground states. However there are many experiments where transitions from excited states, both absorption and emission, are probed. In this work we develop a formalism based on linear-response time-dependent density functional theory to investigate spectroscopic properties of excited states. We apply our model to study the excited-state absorption of a diplatinum(II) complex under X-rays, and transient vis/UV absorption of pyrene and azobenzene.

  9. Fall with linear drag and Wien's displacement law: approximate solution and Lambert function

    Vial, Alexandre

    2012-01-01

    We present an approximate solution for the downward time of travel in the case of a mass falling with a linear drag force. We show how a quasi-analytical solution implying the Lambert function can be found. We also show that solving the previous problem is equivalent to the search for Wien's displacement law. These results can be of interest for undergraduate students, as they show that some transcendental equations found in physics may be solved without purely numerical methods. Moreover, as will be seen in the case of Wien's displacement law, solutions based on series expansion can be very accurate even with few terms. (paper)

  10. The solution of linear and nonlinear systems of Volterra functional equations using Adomian-Pade technique

    Dehghan, Mehdi; Shakourifar, Mohammad; Hamidi, Asgar

    2009-01-01

    The purpose of this study is to implement Adomian-Pade (Modified Adomian-Pade) technique, which is a combination of Adomian decomposition method (Modified Adomian decomposition method) and Pade approximation, for solving linear and nonlinear systems of Volterra functional equations. The results obtained by using Adomian-Pade (Modified Adomian-Pade) technique, are compared to those obtained by using Adomian decomposition method (Modified Adomian decomposition method) alone. The numerical results, demonstrate that ADM-PADE (MADM-PADE) technique, gives the approximate solution with faster convergence rate and higher accuracy than using the standard ADM (MADM).

  11. ONETEP: linear-scaling density-functional theory with plane-waves

    Haynes, P D; Mostof, A A; Skylaris, C-K; Payne, M C

    2006-01-01

    This paper provides a general overview of the methodology implemented in onetep (Order-N Electronic Total Energy Package), a parallel density-functional theory code for largescale first-principles quantum-mechanical calculations. The distinctive features of onetep are linear-scaling in both computational effort and resources, obtained by making well-controlled approximations which enable simulations to be performed with plane-wave accuracy. Titanium dioxide clusters of increasing size designed to mimic surfaces are studied to demonstrate the accuracy and scaling of onetep

  12. Minimization of Linear Functionals Defined on| Solutions of Large-Scale Discrete Ill-Posed Problems

    Elden, Lars; Hansen, Per Christian; Rojas, Marielba

    2003-01-01

    The minimization of linear functionals de ned on the solutions of discrete ill-posed problems arises, e.g., in the computation of con dence intervals for these solutions. In 1990, Elden proposed an algorithm for this minimization problem based on a parametric-programming reformulation involving...... the solution of a sequence of trust-region problems, and using matrix factorizations. In this paper, we describe MLFIP, a large-scale version of this algorithm where a limited-memory trust-region solver is used on the subproblems. We illustrate the use of our algorithm in connection with an inverse heat...

  13. The non-linear relationship between body size and function in parrotfishes

    Lokrantz, J.; Nyström, M.; Thyresson, M.; Johansson, C.

    2008-12-01

    Parrotfishes are a group of herbivores that play an important functional role in structuring benthic communities on coral reefs. Increasingly, these fish are being targeted by fishermen, and resultant declines in biomass and abundance may have severe consequences for the dynamics and regeneration of coral reefs. However, the impact of overfishing extends beyond declining fish stocks. It can also lead to demographic changes within species populations where mean body size is reduced. The effect of reduced mean body size on population dynamics is well described in literature but virtually no information exists on how this may influence important ecological functions. The study investigated how one important function, scraping (i.e., the capacity to remove algae and open up bare substratum for coral larval settlement), by three common species of parrotfishes ( Scarus niger, Chlorurus sordidus, and Chlorurus strongylocephalus) on coral reefs at Zanzibar (Tanzania) was influenced by the size of individual fishes. There was a non-linear relationship between body size and scraping function for all species examined, and impact through scraping was also found to increase markedly when fish reached a size of 15 20 cm. Thus, coral reefs which have a high abundance and biomass of parrotfish may nonetheless be functionally impaired if dominated by small-sized individuals. Reductions in mean body size within parrotfish populations could, therefore, have functional impacts on coral reefs that previously have been overlooked.

  14. Block copolymer battery separator

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  15. A time-dependent density functional theory investigation of plasmon resonances of linear Au atomic chains

    Liu Dan-Dan; Zhang Hong

    2011-01-01

    We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time-dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  16. Pleiotropy analysis of quantitative traits at gene level by multivariate functional linear models.

    Wang, Yifan; Liu, Aiyi; Mills, James L; Boehnke, Michael; Wilson, Alexander F; Bailey-Wilson, Joan E; Xiong, Momiao; Wu, Colin O; Fan, Ruzong

    2015-05-01

    In genetics, pleiotropy describes the genetic effect of a single gene on multiple phenotypic traits. A common approach is to analyze the phenotypic traits separately using univariate analyses and combine the test results through multiple comparisons. This approach may lead to low power. Multivariate functional linear models are developed to connect genetic variant data to multiple quantitative traits adjusting for covariates for a unified analysis. Three types of approximate F-distribution tests based on Pillai-Bartlett trace, Hotelling-Lawley trace, and Wilks's Lambda are introduced to test for association between multiple quantitative traits and multiple genetic variants in one genetic region. The approximate F-distribution tests provide much more significant results than those of F-tests of univariate analysis and optimal sequence kernel association test (SKAT-O). Extensive simulations were performed to evaluate the false positive rates and power performance of the proposed models and tests. We show that the approximate F-distribution tests control the type I error rates very well. Overall, simultaneous analysis of multiple traits can increase power performance compared to an individual test of each trait. The proposed methods were applied to analyze (1) four lipid traits in eight European cohorts, and (2) three biochemical traits in the Trinity Students Study. The approximate F-distribution tests provide much more significant results than those of F-tests of univariate analysis and SKAT-O for the three biochemical traits. The approximate F-distribution tests of the proposed functional linear models are more sensitive than those of the traditional multivariate linear models that in turn are more sensitive than SKAT-O in the univariate case. The analysis of the four lipid traits and the three biochemical traits detects more association than SKAT-O in the univariate case. © 2015 WILEY PERIODICALS, INC.

  17. Exact potential and scattering amplitudes from the tachyon non-linear β -function

    Coletti, E.; Forini, V.; Nardelli, G.; Orselli, M.; Grignani, G.

    2004-01-01

    We compute, on the disk, the non-linear tachyon β-function, β T , of the open bosonic string theory. β T is determined both in an expansion to the third power of the field and to all orders in derivatives and in an expansion to any power of the tachyon field in the leading order in derivatives. We construct the Witten-Shatashvili (WS) space-time effective action S and prove that it has a very simple universal form in terms of the renormalized tachyon field and β T . The expression for S is well suited to studying both processes that are far off-shell, such as tachyon condensation, and close to the mass-shell, such as perturbative on-shell amplitudes. We evaluate S in a small derivative expansion, providing the exact tachyon potential. The normalization of S is fixed by requiring that the field redefinition that maps S into the tachyon effective action derived from the cubic string field theory is regular on-shell. The normalization factor is in precise agreement with the one required for verifying all the conjectures on tachyon condensation. The coordinates in the space of couplings in which the tachyon β-function is non linear are the most appropriate to study RG fixed points that can be interpreted as solitons of S, i.e. D-branes. (author)

  18. Synthesizing Configurable Biochemical Implementation of Linear Systems from Their Transfer Function Specifications.

    Tai-Yin Chiu

    Full Text Available The ability to engineer synthetic systems in the biochemical context is constantly being improved and has a profound societal impact. Linear system design is one of the most pervasive methods applied in control tasks, and its biochemical realization has been proposed by Oishi and Klavins and advanced further in recent years. However, several technical issues remain unsolved. Specifically, the design process is not fully automated from specification at the transfer function level, systems once designed often lack dynamic adaptivity to environmental changes, matching rate constants of reactions is not always possible, and implementation may be approximative and greatly deviate from the specifications. Building upon the work of Oishi and Klavins, this paper overcomes these issues by introducing a design flow that transforms a transfer-function specification of a linear system into a set of chemical reactions, whose input-output response precisely conforms to the specification. This system is implementable using the DNA strand displacement technique. The underlying configurability is embedded into primitive components and template modules, and thus the entire system is adaptive. Simulation of DNA strand displacement implementation confirmed the feasibility and superiority of the proposed synthesis flow.

  19. Synthesis of graft copolymers onto starch and its semiconducting properties

    Nevin Çankaya

    Full Text Available Literature review has revealed that, although there are studies about grafting on natural polymers, especially on starch, few of them are about electrical properties of graft polymers. Starch methacrylate (St.met was obtained by esterification of OH groups on natural starch polymer for this purpose. Grafting of synthesized N-cyclohexyl acrylamide (NCA and commercial methyl methacrylate (MMA monomers with St.met was done by free radical polymerization method. The graft copolymers were characterized with FT-IR spectra, thermal and elemental analysis. Thermal stabilities of the graft copolymers were determined by TGA (thermo gravimetric analysis method and thermal stability of the copolymers is decreased via grafting. The electrical conductivity of the polymers was measured as a function of temperature and it has been observed that electrical conductivity increases with increasing temperature. The absorbance and transmittance versus wavelength of the polymers have been measured. Keywords: Starch, Graft copolymer, Semiconducting, Thermal stability, Starch methacrylate

  20. Simulation of electron energy loss spectra of nanomaterials with linear-scaling density functional theory

    Tait, E W; Payne, M C; Ratcliff, L E; Haynes, P D; Hine, N D M

    2016-01-01

    Experimental techniques for electron energy loss spectroscopy (EELS) combine high energy resolution with high spatial resolution. They are therefore powerful tools for investigating the local electronic structure of complex systems such as nanostructures, interfaces and even individual defects. Interpretation of experimental electron energy loss spectra is often challenging and can require theoretical modelling of candidate structures, which themselves may be large and complex, beyond the capabilities of traditional cubic-scaling density functional theory. In this work, we present functionality to compute electron energy loss spectra within the onetep linear-scaling density functional theory code. We first demonstrate that simulated spectra agree with those computed using conventional plane wave pseudopotential methods to a high degree of precision. The ability of onetep to tackle large problems is then exploited to investigate convergence of spectra with respect to supercell size. Finally, we apply the novel functionality to a study of the electron energy loss spectra of defects on the (1 0 1) surface of an anatase slab and determine concentrations of defects which might be experimentally detectable. (paper)

  1. EXPALS, Least Square Fit of Linear Combination of Exponential Decay Function

    Douglas Gardner, C.

    1980-01-01

    1 - Description of problem or function: This program fits by least squares a function which is a linear combination of real exponential decay functions. The function is y(k) = summation over j of a(j) * exp(-lambda(j) * k). Values of the independent variable (k) and the dependent variable y(k) are specified as input data. Weights may be specified as input information or set by the program (w(k) = 1/y(k)). 2 - Method of solution: The Prony-Householder iteration method is used. For unequally-spaced data, a number of interpolation options are provided. This revision includes an option to call a differential correction subroutine REFINE to improve the approximation to unequally-spaced data when equal-interval interpolation is faulty. If convergence is achieved, the probable errors in the computed parameters are calculated also. 3 - Restrictions on the complexity of the problem: Generally, it is desirable to have at least 10n observations where n equals the number of terms and to input k+n significant figures if k significant figures are expected

  2. Spectral Signatures of Polarons in Conjugated Co-polymers

    Wiebeler, Christian; Tautz, Raphael; Feldmann, Jochen; von Hauff, Elizabeth; Da Como, Enrico; Schumacher, Stefan

    2013-01-01

    We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and

  3. Improvement of CPU time of Linear Discriminant Function based on MNM criterion by IP

    Shuichi Shinmura

    2014-05-01

    Full Text Available Revised IP-OLDF (optimal linear discriminant function by integer programming is a linear discriminant function to minimize the number of misclassifications (NM of training samples by integer programming (IP. However, IP requires large computation (CPU time. In this paper, it is proposed how to reduce CPU time by using linear programming (LP. In the first phase, Revised LP-OLDF is applied to all cases, and all cases are categorized into two groups: those that are classified correctly or those that are not classified by support vectors (SVs. In the second phase, Revised IP-OLDF is applied to the misclassified cases by SVs. This method is called Revised IPLP-OLDF.In this research, it is evaluated whether NM of Revised IPLP-OLDF is good estimate of the minimum number of misclassifications (MNM by Revised IP-OLDF. Four kinds of the real data—Iris data, Swiss bank note data, student data, and CPD data—are used as training samples. Four kinds of 20,000 re-sampling cases generated from these data are used as the evaluation samples. There are a total of 149 models of all combinations of independent variables by these data. NMs and CPU times of the 149 models are compared with Revised IPLP-OLDF and Revised IP-OLDF. The following results are obtained: 1 Revised IPLP-OLDF significantly improves CPU time. 2 In the case of training samples, all 149 NMs of Revised IPLP-OLDF are equal to the MNM of Revised IP-OLDF. 3 In the case of evaluation samples, most NMs of Revised IPLP-OLDF are equal to NM of Revised IP-OLDF. 4 Generalization abilities of both discriminant functions are concluded to be high, because the difference between the error rates of training and evaluation samples are almost within 2%.   Therefore, Revised IPLP-OLDF is recommended for the analysis of big data instead of Revised IP-OLDF. Next, Revised IPLP-OLDF is compared with LDF and logistic regression by 100-fold cross validation using 100 re-sampling samples. Means of error rates of

  4. Synthesis and characterization of hydroxyl-functionalized caprolactone copolymers and their effect on adhesion, proliferation, and differentiation of human mesenchymal stem cells.

    Seyednejad, Hajar; Vermonden, Tina; Fedorovich, Natalja E; van Eijk, Roel; van Steenbergen, Mies J; Dhert, Wouter J A; van Nostrum, Cornelus F; Hennink, Wim E

    2009-11-09

    The aim of this study was to develop new hydrophilic polyesters for tissue engineering applications. In our approach, poly(benzyloxymethyl glycolide-co-epsilon-caprolactone)s (pBHMG-CLs) were synthesized through melt copolymerization of epsilon-caprolactone (CL) and benzyl-protected hydroxymethyl glycolide (BHMG). Deprotection of the polymers yielded copolymers with pendant hydroxyl groups, poly(hydroxymethylglycolide-co-epsilon-caprolactone) (pHMG-CL). The synthesized polymers were characterized by GPC, NMR, and DSC techniques. The resulting copolymers consisting of up to 10% of HMG monomer were semicrystalline with a melting temperature above body temperature. Water contact angle measurements of polymeric films showed that increasing HMG content resulted in higher surface hydrophilicity, as evidenced from a decrease in receding contact angle from 68 degrees for PCL to 40 degrees for 10% HMG-CL. Human mesenchymal stem cells showed good adherence onto pHMG-CL films as compared to the more hydrophobic PCL surfaces. The cells survived and were able to differentiate toward osteogenic lineage on pHMG-CL surfaces. This study shows that the aforementioned hydrophilic polymers are attractive candidates for the design of scaffolds for tissue engineering applications.

  5. Electrical characterization of fluorinated benzothiadiazole based conjugated copolymer – a promising material for high-performance solar cells

    J. Toušek

    2015-12-01

    Full Text Available Measurements of electrical conductivity, electron work function, carrier mobility of holes and the diffusion length of excitons were performed on samples of conjugated polymers relevant to polymer solar cells. A state of the art fluorinated benzothiadiazole based conjugated copolymer (PBDTTHD − DTBTff was studied and benchmarked against the reference polymer poly-3-hexylthiophene (P3HT. We employed, respectively, four electrode conductivity measurements, Kelvin probe work function measurements, carrier mobility using charge extraction by linearly increasing voltage (CELIV measurements and diffusion length determinaton using surface photovoltage measurements.

  6. Technical report. The application of probability-generating functions to linear-quadratic radiation survival curves.

    Kendal, W S

    2000-04-01

    To illustrate how probability-generating functions (PGFs) can be employed to derive a simple probabilistic model for clonogenic survival after exposure to ionizing irradiation. Both repairable and irreparable radiation damage to DNA were assumed to occur by independent (Poisson) processes, at intensities proportional to the irradiation dose. Also, repairable damage was assumed to be either repaired or further (lethally) injured according to a third (Bernoulli) process, with the probability of lethal conversion being directly proportional to dose. Using the algebra of PGFs, these three processes were combined to yield a composite PGF that described the distribution of lethal DNA lesions in irradiated cells. The composite PGF characterized a Poisson distribution with mean, chiD+betaD2, where D was dose and alpha and beta were radiobiological constants. This distribution yielded the conventional linear-quadratic survival equation. To test the composite model, the derived distribution was used to predict the frequencies of multiple chromosomal aberrations in irradiated human lymphocytes. The predictions agreed well with observation. This probabilistic model was consistent with single-hit mechanisms, but it was not consistent with binary misrepair mechanisms. A stochastic model for radiation survival has been constructed from elementary PGFs that exactly yields the linear-quadratic relationship. This approach can be used to investigate other simple probabilistic survival models.

  7. Polyether/Polyester Graft Copolymers

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  8. Solving the Fully Fuzzy Bilevel Linear Programming Problem through Deviation Degree Measures and a Ranking Function Method

    Aihong Ren

    2016-01-01

    This paper is concerned with a class of fully fuzzy bilevel linear programming problems where all the coefficients and decision variables of both objective functions and the constraints are fuzzy numbers. A new approach based on deviation degree measures and a ranking function method is proposed to solve these problems. We first introduce concepts of the feasible region and the fuzzy optimal solution of a fully fuzzy bilevel linear programming problem. In order to obtain a fuzzy optimal solut...

  9. Simulations of nanocrystals under pressure: Combining electronic enthalpy and linear-scaling density-functional theory

    Corsini, Niccolò R. C., E-mail: niccolo.corsini@imperial.ac.uk; Greco, Andrea; Haynes, Peter D. [Department of Physics and Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Hine, Nicholas D. M. [Department of Physics and Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Cavendish Laboratory, J. J. Thompson Avenue, Cambridge CB3 0HE (United Kingdom); Molteni, Carla [Department of Physics, King' s College London, Strand, London WC2R 2LS (United Kingdom)

    2013-08-28

    We present an implementation in a linear-scaling density-functional theory code of an electronic enthalpy method, which has been found to be natural and efficient for the ab initio calculation of finite systems under hydrostatic pressure. Based on a definition of the system volume as that enclosed within an electronic density isosurface [M. Cococcioni, F. Mauri, G. Ceder, and N. Marzari, Phys. Rev. Lett.94, 145501 (2005)], it supports both geometry optimizations and molecular dynamics simulations. We introduce an approach for calibrating the parameters defining the volume in the context of geometry optimizations and discuss their significance. Results in good agreement with simulations using explicit solvents are obtained, validating our approach. Size-dependent pressure-induced structural transformations and variations in the energy gap of hydrogenated silicon nanocrystals are investigated, including one comparable in size to recent experiments. A detailed analysis of the polyamorphic transformations reveals three types of amorphous structures and their persistence on depressurization is assessed.

  10. A Hybrid Density Functional Theory/Molecular Mechanics Approach for Linear Response Properties in Heterogeneous Environments.

    Rinkevicius, Zilvinas; Li, Xin; Sandberg, Jaime A R; Mikkelsen, Kurt V; Ågren, Hans

    2014-03-11

    We introduce a density functional theory/molecular mechanical approach for computation of linear response properties of molecules in heterogeneous environments, such as metal surfaces or nanoparticles embedded in solvents. The heterogeneous embedding environment, consisting from metallic and nonmetallic parts, is described by combined force fields, where conventional force fields are used for the nonmetallic part and capacitance-polarization-based force fields are used for the metallic part. The presented approach enables studies of properties and spectra of systems embedded in or placed at arbitrary shaped metallic surfaces, clusters, or nanoparticles. The capability and performance of the proposed approach is illustrated by sample calculations of optical absorption spectra of thymidine absorbed on gold surfaces in an aqueous environment, where we study how different organizations of the gold surface and how the combined, nonadditive effect of the two environments is reflected in the optical absorption spectrum.

  11. Distribution functions for the linear region of the S-N curve

    Mueller, Christian; Waechter, Michael; Masendorf, Rainer; Esderts, Alfons [TU Clausthal, Clausthal-Zellerfeld (Germany). Inst. for Plant Engineering and Fatigue Analysis

    2017-08-01

    This study establishes a database containing the results of fatigue tests from the linear region of the S-N curve using sources from the literature. Each set of test results originates from testing metallic components on a single load level. Eighty-nine test series with sample sizes of 14 ≤ n ≤ 500 are included in the database, resulting in a sum of 6,086 individual test results. The test series are tested in terms of the type of distribution function (log-normal or 2-parameter Weibull) using the Shapiro-Wilk test, the Anderson-Darling test and probability plots. The majority of the tested individual test results follows a log-normal distribution.

  12. Correlation function for density perturbations in an expanding universe. I. Linear theory

    McClelland, J.; Silk, J.

    1977-01-01

    We derive analytic solutions for the evolution of linearized adiabatic spherically symmetric density perturbations and the two-point correlation function in two regimes of the early universe: the radiation-dominated regime prior to decoupling, and the matter-dominated regime after decoupling. The solutions are for an Einstein--de Sitter universe, and include pressure effects. In the radiation era, we find that individual spherically symmetric adiabatic density perturbations smaller than the Jeans length flow outward like water waves instead of oscillating as infinite plane waves. It seems likely that the only primordial structures on scales smaller than the maximum Jeans length which could survive are very regular waves such as infinite plane waves. However, structure does build up in the correlation function over distances comparable with the maximum Jeans length in the radiation regime, and could lead to the eventual formation of galaxy superclusters. This scale (approx.10 17 Ω -2 M/sub sun)/therefore provides a natural dimension for large-scale structure arising out of the early universe. A general technique is described for constructing solutions for the evolution of the two-point correlation function, and applied to study white noise and power-law initial conditions for primordial inhomogeneities

  13. On the Validity of the Streaming Model for the Redshift-Space Correlation Function in the Linear Regime

    Fisher, Karl B.

    1995-08-01

    The relation between the galaxy correlation functions in real-space and redshift-space is derived in the linear regime by an appropriate averaging of the joint probability distribution of density and velocity. The derivation recovers the familiar linear theory result on large scales but has the advantage of clearly revealing the dependence of the redshift distortions on the underlying peculiar velocity field; streaming motions give rise to distortions of θ(Ω0.6/b) while variations in the anisotropic velocity dispersion yield terms of order θ(Ω1.2/b2). This probabilistic derivation of the redshift-space correlation function is similar in spirit to the derivation of the commonly used "streaming" model, in which the distortions are given by a convolution of the real-space correlation function with a velocity distribution function. The streaming model is often used to model the redshift-space correlation function on small, highly nonlinear, scales. There have been claims in the literature, however, that the streaming model is not valid in the linear regime. Our analysis confirms this claim, but we show that the streaming model can be made consistent with linear theory provided that the model for the streaming has the functional form predicted by linear theory and that the velocity distribution is chosen to be a Gaussian with the correct linear theory dispersion.

  14. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  15. Assessment of the setup dependence of detector response functions for mega-voltage linear accelerators

    Fox, Christopher; Simon, Tom; Simon, Bill; Dempsey, James F.; Kahler, Darren; Palta, Jatinder R.; Liu Chihray; Yan Guanghua [Sun Nuclear Inc., 425-A Pineda Court, Melbourne, Florida 32940 and Department of Radiation Oncology, University of Florida, P.O. Box 100385, Gainesville, Florida 32610-0385 (United States); NRE, 202 Nuclear Science Building, University of Florida, P.O. Box 118300, Gainesville, Florida 32611-8300 and Sun Nuclear Inc., 425-A Pineda Court, Melbourne, Florida 32940 (United States); Sun Nuclear Inc., 425-A Pineda Court, Melbourne, Florida 32940 (United States); ViewRay Inc., 2 Thermo Fisher Way, Oakwood Village, Ohio 44146 (United States); Department of Radiation Oncology, University of Florida, P.O. Box 100385, Gainesville, Florida 32610-0385 (United States)

    2010-02-15

    Purpose: Accurate modeling of beam profiles is important for precise treatment planning dosimetry. Calculated beam profiles need to precisely replicate profiles measured during machine commissioning. Finite detector size introduces perturbations into the measured profiles, which, in turn, impact the resulting modeled profiles. The authors investigate a method for extracting the unperturbed beam profiles from those measured during linear accelerator commissioning. Methods: In-plane and cross-plane data were collected for an Elekta Synergy linac at 6 MV using ionization chambers of volume 0.01, 0.04, 0.13, and 0.65 cm{sup 3} and a diode of surface area 0.64 mm{sup 2}. The detectors were orientated with the stem perpendicular to the beam and pointing away from the gantry. Profiles were measured for a 10x10 cm{sup 2} field at depths ranging from 0.8 to 25.0 cm and SSDs from 90 to 110 cm. Shaping parameters of a Gaussian response function were obtained relative to the Edge detector. The Gaussian function was deconvolved from the measured ionization chamber data. The Edge detector profile was taken as an approximation to the true profile, to which deconvolved data were compared. Data were also collected with CC13 and Edge detectors for additional fields and energies on an Elekta Synergy, Varian Trilogy, and Siemens Oncor linear accelerator and response functions obtained. Response functions were compared as a function of depth, SSD, and detector scan direction. Variations in the shaping parameter were introduced and the effect on the resulting deconvolution profiles assessed. Results: Up to 10% setup dependence in the Gaussian shaping parameter occurred, for each detector for a particular plane. This translated to less than a {+-}0.7 mm variation in the 80%-20% penumbral width. For large volume ionization chambers such as the FC65 Farmer type, where the cavity length to diameter ratio is far from 1, the scan direction produced up to a 40% difference in the shaping

  16. Assessment of the setup dependence of detector response functions for mega-voltage linear accelerators

    Fox, Christopher; Simon, Tom; Simon, Bill; Dempsey, James F.; Kahler, Darren; Palta, Jatinder R.; Liu Chihray; Yan Guanghua

    2010-01-01

    Purpose: Accurate modeling of beam profiles is important for precise treatment planning dosimetry. Calculated beam profiles need to precisely replicate profiles measured during machine commissioning. Finite detector size introduces perturbations into the measured profiles, which, in turn, impact the resulting modeled profiles. The authors investigate a method for extracting the unperturbed beam profiles from those measured during linear accelerator commissioning. Methods: In-plane and cross-plane data were collected for an Elekta Synergy linac at 6 MV using ionization chambers of volume 0.01, 0.04, 0.13, and 0.65 cm 3 and a diode of surface area 0.64 mm 2 . The detectors were orientated with the stem perpendicular to the beam and pointing away from the gantry. Profiles were measured for a 10x10 cm 2 field at depths ranging from 0.8 to 25.0 cm and SSDs from 90 to 110 cm. Shaping parameters of a Gaussian response function were obtained relative to the Edge detector. The Gaussian function was deconvolved from the measured ionization chamber data. The Edge detector profile was taken as an approximation to the true profile, to which deconvolved data were compared. Data were also collected with CC13 and Edge detectors for additional fields and energies on an Elekta Synergy, Varian Trilogy, and Siemens Oncor linear accelerator and response functions obtained. Response functions were compared as a function of depth, SSD, and detector scan direction. Variations in the shaping parameter were introduced and the effect on the resulting deconvolution profiles assessed. Results: Up to 10% setup dependence in the Gaussian shaping parameter occurred, for each detector for a particular plane. This translated to less than a ±0.7 mm variation in the 80%-20% penumbral width. For large volume ionization chambers such as the FC65 Farmer type, where the cavity length to diameter ratio is far from 1, the scan direction produced up to a 40% difference in the shaping parameter between in

  17. EEG sensorimotor rhythms' variation and functional connectivity measures during motor imagery: linear relations and classification approaches.

    Stefano Filho, Carlos A; Attux, Romis; Castellano, Gabriela

    2017-01-01

    Hands motor imagery (MI) has been reported to alter synchronization patterns amongst neurons, yielding variations in the mu and beta bands' power spectral density (PSD) of the electroencephalography (EEG) signal. These alterations have been used in the field of brain-computer interfaces (BCI), in an attempt to assign distinct MI tasks to commands of such a system. Recent studies have highlighted that information may be missing if knowledge about brain functional connectivity is not considered. In this work, we modeled the brain as a graph in which each EEG electrode represents a node. Our goal was to understand if there exists any linear correlation between variations in the synchronization patterns-that is, variations in the PSD of mu and beta bands-induced by MI and alterations in the corresponding functional networks. Moreover, we (1) explored the feasibility of using functional connectivity parameters as features for a classifier in the context of an MI-BCI; (2) investigated three different types of feature selection (FS) techniques; and (3) compared our approach to a more traditional method using the signal PSD as classifier inputs. Ten healthy subjects participated in this study. We observed significant correlations ( p  < 0.05) with values ranging from 0.4 to 0.9 between PSD variations and functional network alterations for some electrodes, prominently in the beta band. The PSD method performed better for data classification, with mean accuracies of (90 ± 8)% and (87 ± 7)% for the mu and beta band, respectively, versus (83 ± 8)% and (83 ± 7)% for the same bands for the graph method. Moreover, the number of features for the graph method was considerably larger. However, results for both methods were relatively close, and even overlapped when the uncertainties of the accuracy rates were considered. Further investigation regarding a careful exploration of other graph metrics may provide better alternatives.

  18. Synthesis, Characterization and Photoinduction of Optical Anisotropy in Liquid Crystalline Diblock Azo-Copolymers

    Forcén, P; Oriol, L; Sánchez, C

    2007-01-01

    Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline WC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobeazene content in these copolymers ranges from 52 to 7 wt %. For an azo conteat dowri to 20% they exhibit a LC...... anisotropy induced in these films by illumination with linearly polarized 488 nm light was studied and the resuits compared with those of the azo homopolymer and of a random copolymer with a similar composition. The formation of azo aggregates inside the azo blocks is strongly reduced in going from...... the homopolymer to the copolymers. Photoinduced azo orientation perpendicular to the 488 nm light polarization was found in aH the polymers. The orientational order parameter is very similar in the homopolymer and in the block copolymers with an azo content down to 20 wt %, while it is much lower in the random...

  19. Sheared Layers in the Continental Crust: Nonlinear and Linearized inversion for Ps receiver functions

    Park, J. J.

    2017-12-01

    Sheared Layers in the Continental Crust: Nonlinear and Linearized inversion for Ps receiver functions Jeffrey Park, Yale University The interpretation of seismic receiver functions (RFs) in terms of isotropic and anisotropic layered structure can be complex. The relationship between structure and body-wave scattering is nonlinear. The anisotropy can involve more parameters than the observations can readily constrain. Finally, reflectivity-predicted layer reverberations are often not prominent in data, so that nonlinear waveform inversion can search in vain to match ghost signals. Multiple-taper correlation (MTC) receiver functions have uncertainties in the frequency domain that follow Gaussian statistics [Park and Levin, 2016a], so grid-searches for the best-fitting collections of interfaces can be performed rapidly to minimize weighted misfit variance. Tests for layer-reverberations can be performed in the frequency domain without reflectivity calculations, allowing flexible modelling of weak, but nonzero, reverberations. Park and Levin [2016b] linearized the hybridization of P and S body waves in an anisotropic layer to predict first-order Ps conversion amplitudes at crust and mantle interfaces. In an anisotropic layer, the P wave acquires small SV and SH components. To ensure continuity of displacement and traction at the top and bottom boundaries of the layer, shear waves are generated. Assuming hexagonal symmetry with an arbitrary symmetry axis, theory confirms the empirical stacking trick of phase-shifting transverse RFs by 90 degrees in back-azimuth [Shiomi and Park, 2008; Schulte-Pelkum and Mahan, 2014] to enhance 2-lobed and 4-lobed harmonic variation. Ps scattering is generated by sharp interfaces, so that RFs resemble the first derivative of the model. MTC RFs in the frequency domain can be manipulated to obtain a first-order reconstruction of the layered anisotropy, under the above modeling constraints and neglecting reverberations. Examples from long

  20. Bivariate least squares linear regression: Towards a unified analytic formalism. I. Functional models

    Caimmi, R.

    2011-08-01

    Concerning bivariate least squares linear regression, the classical approach pursued for functional models in earlier attempts ( York, 1966, 1969) is reviewed using a new formalism in terms of deviation (matrix) traces which, for unweighted data, reduce to usual quantities leaving aside an unessential (but dimensional) multiplicative factor. Within the framework of classical error models, the dependent variable relates to the independent variable according to the usual additive model. The classes of linear models considered are regression lines in the general case of correlated errors in X and in Y for weighted data, and in the opposite limiting situations of (i) uncorrelated errors in X and in Y, and (ii) completely correlated errors in X and in Y. The special case of (C) generalized orthogonal regression is considered in detail together with well known subcases, namely: (Y) errors in X negligible (ideally null) with respect to errors in Y; (X) errors in Y negligible (ideally null) with respect to errors in X; (O) genuine orthogonal regression; (R) reduced major-axis regression. In the limit of unweighted data, the results determined for functional models are compared with their counterparts related to extreme structural models i.e. the instrumental scatter is negligible (ideally null) with respect to the intrinsic scatter ( Isobe et al., 1990; Feigelson and Babu, 1992). While regression line slope and intercept estimators for functional and structural models necessarily coincide, the contrary holds for related variance estimators even if the residuals obey a Gaussian distribution, with the exception of Y models. An example of astronomical application is considered, concerning the [O/H]-[Fe/H] empirical relations deduced from five samples related to different stars and/or different methods of oxygen abundance determination. For selected samples and assigned methods, different regression models yield consistent results within the errors (∓ σ) for both

  1. Acetate and phosphate anion adsorption linear sweep voltammograms simulated using density functional theory

    Savizi, Iman Shahidi Pour

    2011-04-01

    Specific adsorption of anions to electrode surfaces may alter the rates of electrocatalytic reactions. Density functional theory (DFT) methods are used to predict the adsorption free energy of acetate and phosphate anions as a function of Pt(1 1 1) electrode potential. Four models of the electrode potential are used including a simple vacuum slab model, an applied electric field model with and without the inclusion of a solvating water bi-layer, and the double reference model. The linear sweep voltammogram (LSV) due to anion adsorption is simulated using the DFT results. The inclusion of solvation at the electrochemical interface is necessary for accurately predicting the adsorption peak position. The Langmuir model is sufficient for predicting the adsorption peak shape, indicating coverage effects are minor in altering the LSV for acetate and phosphate adsorption. Anion adsorption peak positions are determined for solution phase anion concentrations present in microbial fuel cells and microbial electrolysis cells and discussion is provided as to the impact of anion adsorption on oxygen reduction and hydrogen evolution reaction rates in these devices. © 2011 Elsevier Ltd. All rights reserved.

  2. On a finite moment perturbation of linear functionals and the inverse Szegö transformation

    Edinson Fuentes

    2016-05-01

    Full Text Available Given a sequence of moments $\\{c_{n}\\}_{n\\in\\ze}$ associated with an Hermitian linear functional $\\mathcal{L}$ defined in the space of Laurent polynomials, we study a new functional $\\mathcal{L}_{\\Omega}$ which is a perturbation of $\\mathcal{L}$ in such a way that a finite number of moments are perturbed. Necessary and sufficient conditions are given for the regularity of $\\mathcal{L}_{\\Omega}$, and a connection formula between the corresponding families of orthogonal polynomials is obtained. On the other hand, assuming $\\mathcal{L}_{\\Omega}$ is positive definite, the perturbation is analyzed through the inverse Szegö transformation. Resumen. Dada una sucesión de momentos $\\{c_{n}\\}_{n\\in\\ze}$ asociada a un funcional lineal hermitiano $\\mathcal{L}$ definido en el espacio de los polinomios de Laurent, estudiamos un nuevo funcional $\\mathcal{L}_{\\Omega}$ que consiste en una perturbación de $\\mathcal{L}$ de tal forma que se perturba un número finito de momentos de la sucesión. Se encuentran condiciones necesarias y suficientes para la regularidad de $\\mathcal{L}_{\\Omega}$, y se obtiene una fórmula de conexión que relaciona las familias de polinomios ortogonales correspondientes. Por otro lado, suponiendo que $\\mathcal{L}_{\\Omega}$ es definido positivo, se analiza la perturbación mediante de la transformación inversa de Szegö.

  3. The correlation function for density perturbations in an expanding universe. I - Linear theory

    Mcclelland, J.; Silk, J.

    1977-01-01

    The evolution of the two-point correlation function for adiabatic density perturbations in the early universe is studied. Analytical solutions are obtained for the evolution of linearized spherically symmetric adiabatic density perturbations and the two-point correlation function for these perturbations in the radiation-dominated portion of the early universe. The results are then extended to the regime after decoupling. It is found that: (1) adiabatic spherically symmetric perturbations comparable in scale with the maximum Jeans length would survive the radiation-dominated regime; (2) irregular fluctuations are smoothed out up to the scale of the maximum Jeans length in the radiation era, but regular fluctuations might survive on smaller scales; (3) in general, the only surviving structures for irregularly shaped adiabatic density perturbations of arbitrary but finite scale in the radiation regime are the size of or larger than the maximum Jeans length in that regime; (4) infinite plane waves with a wavelength smaller than the maximum Jeans length but larger than the critical dissipative damping scale could survive the radiation regime; and (5) black holes would also survive the radiation regime and might accrete sufficient mass after decoupling to nucleate the formation of galaxies.

  4. Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

    2008-10-01

    Full Text Available The acrylate monomer, 7-acryloyloxy-4-methyl coumarin (AMC has been synthesized by reacting 7-hydroxy-4-methyl coumarin, with acryloyl chloride in the presence of NaOH at 0–5°C. Copolymers of 7-acryloyloxy-4-methyl coumarin (AMC with vinyl acetate (VAc were synthesized in DMF (dimethyl formamide solution at 70±1°C using 2,2′-azobisisobutyronitrile (AIBN as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by Fourier transform infra red (FTIR spectroscopy. The copolymer composition was evaluated by 1H-NMR (proton nuclear magnetic resonance and was further used to determine reactivity ratios. The monomer reactivity ratios for AMC (M1-VAc (M2 pair were determined by the application of conventional linearization methods such as Fineman-Ross (r1 = 0.6924; r2 = 0.6431, Kelen-Tüdõs (r1 = 0.6776; r2 = 0.6374 and extended Kelen-Tüdõs (r1 = 0.6657; r2 = 0.6256. Thermo gravimetric analysis showed that thermal decomposition of the copolymers occurred in single stage in the temperature range of 263–458°C. The molecular weights of the polymers were determined using gel permeation chromatography. The homo and copolymers were tested for their antimicrobial properties against selected microorganisms.

  5. Summary goodness-of-fit statistics for binary generalized linear models with noncanonical link functions.

    Canary, Jana D; Blizzard, Leigh; Barry, Ronald P; Hosmer, David W; Quinn, Stephen J

    2016-05-01

    Generalized linear models (GLM) with a canonical logit link function are the primary modeling technique used to relate a binary outcome to predictor variables. However, noncanonical links can offer more flexibility, producing convenient analytical quantities (e.g., probit GLMs in toxicology) and desired measures of effect (e.g., relative risk from log GLMs). Many summary goodness-of-fit (GOF) statistics exist for logistic GLM. Their properties make the development of GOF statistics relatively straightforward, but it can be more difficult under noncanonical links. Although GOF tests for logistic GLM with continuous covariates (GLMCC) have been applied to GLMCCs with log links, we know of no GOF tests in the literature specifically developed for GLMCCs that can be applied regardless of link function chosen. We generalize the Tsiatis GOF statistic originally developed for logistic GLMCCs, (TG), so that it can be applied under any link function. Further, we show that the algebraically related Hosmer-Lemeshow (HL) and Pigeon-Heyse (J(2) ) statistics can be applied directly. In a simulation study, TG, HL, and J(2) were used to evaluate the fit of probit, log-log, complementary log-log, and log models, all calculated with a common grouping method. The TG statistic consistently maintained Type I error rates, while those of HL and J(2) were often lower than expected if terms with little influence were included. Generally, the statistics had similar power to detect an incorrect model. An exception occurred when a log GLMCC was incorrectly fit to data generated from a logistic GLMCC. In this case, TG had more power than HL or J(2) . © 2015 John Wiley & Sons Ltd/London School of Economics.

  6. Unique solvability of a non-linear non-local boundary-value problem for systems of non-linear functional differential equations

    Dilna, N.; Rontó, András

    2010-01-01

    Roč. 60, č. 3 (2010), s. 327-338 ISSN 0139-9918 R&D Projects: GA ČR(CZ) GA201/06/0254 Institutional research plan: CEZ:AV0Z10190503 Keywords : non-linear boundary value-problem * functional differential equation * non-local condition * unique solvability * differential inequality Subject RIV: BA - General Mathematics Impact factor: 0.316, year: 2010 http://link.springer.com/article/10.2478%2Fs12175-010-0015-9

  7. Simulation of herbicide degradation in different soils by use of Pedo-transfer functions (PTF) and non-linear kinetics.

    von Götz, N; Richter, O

    1999-03-01

    The degradation behaviour of bentazone in 14 different soils was examined at constant temperature and moisture conditions. Two soils were examined at different temperatures. On the basis of these data the influence of soil properties and temperature on degradation was assessed and modelled. Pedo-transfer functions (PTF) in combination with a linear and a non-linear model were found suitable to describe the bentazone degradation in the laboratory as related to soil properties. The linear PTF can be combined with a rate related to the temperature to account for both soil property and temperature influence at the same time.

  8. Wavelet-based linear-response time-dependent density-functional theory

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.; Philouze, Christian; Balakirev, Maxim Y.

    2012-06-01

    Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

  9. Time-dependent density functional theory of open quantum systems in the linear-response regime.

    Tempel, David G; Watson, Mark A; Olivares-Amaya, Roberto; Aspuru-Guzik, Alán

    2011-02-21

    Time-dependent density functional theory (TDDFT) has recently been extended to describe many-body open quantum systems evolving under nonunitary dynamics according to a quantum master equation. In the master equation approach, electronic excitation spectra are broadened and shifted due to relaxation and dephasing of the electronic degrees of freedom by the surrounding environment. In this paper, we develop a formulation of TDDFT linear-response theory (LR-TDDFT) for many-body electronic systems evolving under a master equation, yielding broadened excitation spectra. This is done by mapping an interacting open quantum system onto a noninteracting open Kohn-Sham system yielding the correct nonequilibrium density evolution. A pseudoeigenvalue equation analogous to the Casida equations of the usual LR-TDDFT is derived for the Redfield master equation, yielding complex energies and Lamb shifts. As a simple demonstration, we calculate the spectrum of a C(2 +) atom including natural linewidths, by treating the electromagnetic field vacuum as a photon bath. The performance of an adiabatic exchange-correlation kernel is analyzed and a first-order frequency-dependent correction to the bare Kohn-Sham linewidth based on the Görling-Levy perturbation theory is calculated.

  10. Determination of a Differential Item Functioning Procedure Using the Hierarchical Generalized Linear Model

    Tülin Acar

    2012-01-01

    Full Text Available The aim of this research is to compare the result of the differential item functioning (DIF determining with hierarchical generalized linear model (HGLM technique and the results of the DIF determining with logistic regression (LR and item response theory–likelihood ratio (IRT-LR techniques on the test items. For this reason, first in this research, it is determined whether the students encounter DIF with HGLM, LR, and IRT-LR techniques according to socioeconomic status (SES, in the Turkish, Social Sciences, and Science subtest items of the Secondary School Institutions Examination. When inspecting the correlations among the techniques in terms of determining the items having DIF, it was discovered that there was significant correlation between the results of IRT-LR and LR techniques in all subtests; merely in Science subtest, the results of the correlation between HGLM and IRT-LR techniques were found significant. DIF applications can be made on test items with other DIF analysis techniques that were not taken to the scope of this research. The analysis results, which were determined by using the DIF techniques in different sample sizes, can be compared.

  11. Efficient block preconditioned eigensolvers for linear response time-dependent density functional theory

    Vecharynski, Eugene [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Brabec, Jiri [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Shao, Meiyue [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Govind, Niranjan [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.; Yang, Chao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division

    2017-12-01

    We present two efficient iterative algorithms for solving the linear response eigen- value problem arising from the time dependent density functional theory. Although the matrix to be diagonalized is nonsymmetric, it has a special structure that can be exploited to save both memory and floating point operations. In particular, the nonsymmetric eigenvalue problem can be transformed into a product eigenvalue problem that is self-adjoint with respect to a K-inner product. This product eigenvalue problem can be solved efficiently by a modified Davidson algorithm and a modified locally optimal block preconditioned conjugate gradient (LOBPCG) algorithm that make use of the K-inner product. The solution of the product eigenvalue problem yields one component of the eigenvector associated with the original eigenvalue problem. However, the other component of the eigenvector can be easily recovered in a postprocessing procedure. Therefore, the algorithms we present here are more efficient than existing algorithms that try to approximate both components of the eigenvectors simultaneously. The efficiency of the new algorithms is demonstrated by numerical examples.

  12. Improved application of independent component analysis to functional magnetic resonance imaging study via linear projection techniques.

    Long, Zhiying; Chen, Kewei; Wu, Xia; Reiman, Eric; Peng, Danling; Yao, Li

    2009-02-01

    Spatial Independent component analysis (sICA) has been widely used to analyze functional magnetic resonance imaging (fMRI) data. The well accepted implicit assumption is the spatially statistical independency of intrinsic sources identified by sICA, making the sICA applications difficult for data in which there exist interdependent sources and confounding factors. This interdependency can arise, for instance, from fMRI studies investigating two tasks in a single session. In this study, we introduced a linear projection approach and considered its utilization as a tool to separate task-related components from two-task fMRI data. The robustness and feasibility of the method are substantiated through simulation on computer data and fMRI real rest data. Both simulated and real two-task fMRI experiments demonstrated that sICA in combination with the projection method succeeded in separating spatially dependent components and had better detection power than pure model-based method when estimating activation induced by each task as well as both tasks.

  13. Generalized functional linear models for gene-based case-control association studies.

    Fan, Ruzong; Wang, Yifan; Mills, James L; Carter, Tonia C; Lobach, Iryna; Wilson, Alexander F; Bailey-Wilson, Joan E; Weeks, Daniel E; Xiong, Momiao

    2014-11-01

    By using functional data analysis techniques, we developed generalized functional linear models for testing association between a dichotomous trait and multiple genetic variants in a genetic region while adjusting for covariates. Both fixed and mixed effect models are developed and compared. Extensive simulations show that Rao's efficient score tests of the fixed effect models are very conservative since they generate lower type I errors than nominal levels, and global tests of the mixed effect models generate accurate type I errors. Furthermore, we found that the Rao's efficient score test statistics of the fixed effect models have higher power than the sequence kernel association test (SKAT) and its optimal unified version (SKAT-O) in most cases when the causal variants are both rare and common. When the causal variants are all rare (i.e., minor allele frequencies less than 0.03), the Rao's efficient score test statistics and the global tests have similar or slightly lower power than SKAT and SKAT-O. In practice, it is not known whether rare variants or common variants in a gene region are disease related. All we can assume is that a combination of rare and common variants influences disease susceptibility. Thus, the improved performance of our models when the causal variants are both rare and common shows that the proposed models can be very useful in dissecting complex traits. We compare the performance of our methods with SKAT and SKAT-O on real neural tube defects and Hirschsprung's disease datasets. The Rao's efficient score test statistics and the global tests are more sensitive than SKAT and SKAT-O in the real data analysis. Our methods can be used in either gene-disease genome-wide/exome-wide association studies or candidate gene analyses. © 2014 WILEY PERIODICALS, INC.

  14. Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers

    Misichronis, Konstantinos [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wang, Weiyu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Cheng, Shiwang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Wang, Yangyang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Shrestha, Umesh [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Dadmun, Mark D. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Mays, Jimmy W. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Saito, Tomonori [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

    2018-01-29

    Multigraft copolymer superelastomers consisting of a poly(n-butyl acrylate) backbone and polystyrene side chains were synthesized and the viscoelastic properties of the non-sulfonated and sulfonated final materials were investigated using extensional rheology (SER3). The non-linear viscoelastic experiments revealed significantly increased true stresses (up to 10 times higher) after sulfonating only 2–3% of the copolymer while the materials maintained high elongation (<700%). The linear viscoelastic experiments showed that the storage and loss modulus are increased by sulfonation and that the copolymers can be readily tuned and further improved by increasing the number of branching points and the molecular weight of the backbone. Here, in this way, we show that by tuning not only the molecular characteristics of the multigraft copolymers but also their architecture and chemical interaction, we can acquire thermoplastic superelastomer materials with desired viscoelastic properties.

  15. Controlling block copolymer phase behavior using ionic surfactant

    Ray, D.; Aswal, V. K. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India E-mail: debes.phys@gmail.com (India)

    2016-05-23

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  16. Functions Represented as Linear Sequential Data: Relationships between Presentation and Student Responses

    Ayalon, Michal; Watson, Anne; Lerman, Steve

    2015-01-01

    This study investigates students' ways of attending to linear sequential data in two tasks, and conjectures possible relationships between those ways and elements of the task design. Drawing on the substantial literature about such situations, we focus for this paper on linear rate of change, and on covariation and correspondence approaches to…

  17. Pressure and temperature effects in homopolymer blends and diblock copolymers

    Frielinghaus, H.; Schwahn, D.; Mortensen, K.

    1997-01-01

    Thermal composition fluctuations in a homogeneous binary polymer blend and in a diblock copolymer were measured by small-angle neutron scattering as a function of temperature and pressure. The experimental data were analyzed with theoretical expressions, including the important effect of thermal...... fluctuations. Phase boundaries, the Flory-Huggins interaction parameter and the Ginzburg number were obtained. The packing of the molecules changes with pressure. Therefore, the degree of thermal fluctuation as a function of packing and temperature was studied. While in polymer blends packing leads, in some...... respects, to a universal behaviour, such behaviour is not found in diblock copolymers. It is shown that the Ginzburg number decreases with pressure sensitively in blends, while it is constant in diblock copolymers. The Ginzburg number is an estimation of the transition between the universality classes...

  18. Linear representation of algebras with non-associative operations which are satisfy in the balanced functional equations

    Ehsani, Amir

    2015-01-01

    Algebras with a pair of non-associative binary operations (f, g) which are satisfy in the balanced quadratic functional equations with four object variables considered. First, we obtain a linear representation for the operations, of this kind of binary algebras (A,f,g), over an abelian group (A, +) and then we generalize the linear representation of operations, to an algebra (A,F) with non-associative binary operations which are satisfy in the balanced quadratic functional equations with four object variables. (paper)

  19. Micro pore arrays in free standing cyclic olefin copolymer membranes: fabrication and surface functionalization strategies for in-vitro barrier tissue models

    Gel, M.; Kandasamy, S.; Cartledge, K.; Be, C. L.; Haylock, D.

    2013-12-01

    In recent years there has been growing interest in micro engineered in-vitro models of tissues and organs. These models are designed to mimic the in-vivo like physiological conditions with a goal to study human physiology in an organ-specific context or to develop in-vitro disease models. One of the challenges in the development of these models is the formation of barrier tissues in which the permeability is controlled locally by the tissues cultured at the interface. In-vitro models of barrier tissues are typically created by generating a monolayer of cells grown on thin porous membranes. This paper reports a robust preparation method for free standing porous cyclic olefin copolymer (COC) membranes. We also demonstrate that gelatin coated membranes facilitate formation of highly confluent monolayer of HUVECs. Membranes with thickness in the range of 2-3 um incorporating micro pores with diameter approximately 20 um were fabricated and integrated with microfluidic channels. The performance of the device was demonstrated with a model system mimicking the endothelial barrier in bone marrow sinusoids.

  20. Wavelet-based linear-response time-dependent density-functional theory

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.

    2012-01-01

    Highlights: ► We has been implemented LR-TD-DFT in the pseudopotential wavelet-based program. ► We have compared the results against all-electron Gaussian-type program. ► Orbital energies converges significantly faster for BigDFT than for DEMON2K. ► We report the X-ray crystal structure of the small organic molecule flugi6. ► Measured and calculated absorption spectrum of flugi6 is also reported. - Abstract: Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N 2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

  1. Analysis of perturbations of moments associated with orthogonality linear functionals through the Szegö transformation

    Edinson Fuentes

    2015-06-01

    Full Text Available In this paper, we consider perturbations to a sequence of moments associated with an orthogonality linear functional that is represented by a positive measure supported in [−1, 1]. In particular, given a perturbation to such a measure on the real line, we analyze the perturbation obtained on the corresponding measure on the unit circle, when both measures are related through the Szeg´´o transformation. A similar perturbation is analyzed through the inverse Szeg´´o transformation. In both cases, we show that the applied perturbation can be expressed in terms of the singular part of the measures, and also in terms of the corresponding sequences of moments. Resumen. En el presente trabajo, analizamos las perturbaciones a una sucesión de momentos asociada a un funcional lineal de ortogonalidad que se representa por una medida positiva con soporte en [−1, 1]. En particular, dada una cierta perturbación a dicha medida en la recta real, analizamos la perturbación obtenida en la correspondiente medida en la circunferencia unidad, cuando dichas medidas están relacionadas por la transformación de Szeg´´o. También se analiza una perturbación similar a través de la transformación inversa de Szeg´´o. En ambos casos, se muestra que la perturbación aplicada puede ser expresada en términos de la parte singular de las medidas, y también a través de las correspondientes sucesiones de momentos.

  2. Development of demand functions and their inclusion in linear programming forecasting models

    Chamberlin, J.H.

    1976-05-01

    The purpose of the paper is to present a method for including demand directly within a linear programming model, and to use this method to analyze the effect of the Liquid Metal Fast Breeder Reactor upon the nuclear energy system

  3. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    Determan, Michael Duane [Iowa State Univ., Ames, IA (United States)

    2005-12-17

    -responsive properties of the pentablock copolymer. Demonstrate potential biomedical applications of these materials with in vitro drug release studies from pentablock copolymer hydrogels. The intent of this work is to contribute to the knowledge necessary for further tailoring of these, and other functional block copolymer materials for biomedical applications.

  4. Design of block copolymer membranes using segregation strength trend lines

    Sutisna, Burhannudin

    2016-05-18

    Block copolymer self-assembly and non-solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution and high porosity. The method has the potential to be used with a broad range of tailor-made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene-b-ethylene oxide) diblocks and extended it to newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS-b-P2VP-b-PEO membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS), which revealed a hexagonal micelle order with domain spacing clearly correlated to the membrane interpore distances.

  5. The effect of Moidal non-linear blending function for dual-energy CT on CT image quality

    Zhang Fan; Yang Li

    2011-01-01

    Objective: To compare the difference between linear blending and non-linear blending function for dual-energy CT, and to evaluate the effect on CT image quality. Methods: The model was made of a piece of fresh pork liver inserted with 5 syringes containing various concentrations of iodine solutions (16.3, 26.4, 48.7, 74.6 and 112.3 HU). Linear blending images were automatically reformatted after the model was scanned in the dual-energy mode. Non-linear blending images were reformatted using the software of optimal contrast in Syngo workstation. Images were divided into 3 groups, including linear blending group, non-linear blending group and 120 kV group. Contrast noise ratio (CNR) were measured and calculated respectively in the 3 groups and the different figure of merit (FOM) values between the groups were compared using one-way ANOVA. Twenty patients scanned in the dual-energy mode were randomly selected and the SNR of their liver, renal cortex, spleen, pancreas and abdominal aorta were measured. The independent sample t test was used to compare the difference of signal to noise ratio (SNR) between linear blending group and non linear blending group. Two readers' agreement score and single-blind method were used to investigate the conspicuity difference between linear blending group and non linear blending group. Results: With models of different CT values, the FOM values in non-linear blending group were 20.65± 8.18, 11.40±4.25, 1.60±0.82, 2.40±1.13, 45.49±17.86. In 74.6 HU and 112.3 HU models, the differences of the FOM values observed among the three groups were statistically significant (P<0.05), which were 0.30±0.06 and 14.43±4.59 for linear blending group, and 0.22±0.05 and 15.31±5.16 for 120 kV group. And non-linear blending group had a better FOM value. The SNR of renal cortex and abdominal aorta were 19.2±5.1 and 36.5±13.9 for non-linear blending group, while they were 12.4±3.8 and 22.6±7.0 for linear blending group. There were statistically

  6. Nature of the Schwinger term in spinor electrodynamics. [Dispersion formulation,dimensions,green functions,c-number,linear unitarity condition

    Nishijima, K; Sasaki, R [Tokyo Univ. (Japan). Dept. of Physics

    1975-06-01

    On the basis of the dispersion formulation of field theories the Schwinger term in spinor electrodynamics is shown to be a c-number. The essence of the proof consists in the dimensional argument and the characteristic features of the linear unitarity condition for a set of Green's functions involving the Schwinger term.

  7. Pancreatic beta cell function increases in a linear dose-response manner following exercise training in adults with prediabetes

    Malin, Steven K; Solomon, Thomas; Blaszczak, Alecia

    2013-01-01

    While some studies suggest that a linear dose-response relationship exists between exercise and insulin sensitivity, the exercise dose required to enhance pancreatic beta-cell function is unknown. Thirty-five older, obese adults with prediabetes underwent a progressive 12-week supervised exercise...

  8. The Effects of the Use of Microsoft Math Tool (Graphical Calculator) Instruction on Students' Performance in Linear Functions

    Kissi, Philip Siaw; Opoku, Gyabaah; Boateng, Sampson Kwadwo

    2016-01-01

    The aim of the study was to investigate the effect of Microsoft Math Tool (graphical calculator) on students' achievement in the linear function. The study employed Quasi-experimental research design (Pre-test Post-test two group designs). A total of ninety-eight (98) students were selected for the study from two different Senior High Schools…

  9. Substituting random forest for multiple linear regression improves binding affinity prediction of scoring functions: Cyscore as a case study.

    Li, Hongjian; Leung, Kwong-Sak; Wong, Man-Hon; Ballester, Pedro J

    2014-08-27

    State-of-the-art protein-ligand docking methods are generally limited by the traditionally low accuracy of their scoring functions, which are used to predict binding affinity and thus vital for discriminating between active and inactive compounds. Despite intensive research over the years, classical scoring functions have reached a plateau in their predictive performance. These assume a predetermined additive functional form for some sophisticated numerical features, and use standard multivariate linear regression (MLR) on experimental data to derive the coefficients. In this study we show that such a simple functional form is detrimental for the prediction performance of a scoring function, and replacing linear regression by machine learning techniques like random forest (RF) can improve prediction performance. We investigate the conditions of applying RF under various contexts and find that given sufficient training samples RF manages to comprehensively capture the non-linearity between structural features and measured binding affinities. Incorporating more structural features and training with more samples can both boost RF performance. In addition, we analyze the importance of structural features to binding affinity prediction using the RF variable importance tool. Lastly, we use Cyscore, a top performing empirical scoring function, as a baseline for comparison study. Machine-learning scoring functions are fundamentally different from classical scoring functions because the former circumvents the fixed functional form relating structural features with binding affinities. RF, but not MLR, can effectively exploit more structural features and more training samples, leading to higher prediction performance. The future availability of more X-ray crystal structures will further widen the performance gap between RF-based and MLR-based scoring functions. This further stresses the importance of substituting RF for MLR in scoring function development.

  10. Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

    Bastian Ebeling

    2011-03-01

    Full Text Available When linear polytrithiocarbonates as Reversible Addition-Fragmentation chain Transfer (RAFT agents are employed in a radical polymerization, the resulting macromolecules consist of several homogeneous polymer blocks, interconnected by the functional groups of the respective RAFT agent. Via a second polymerization with another monomer, multiblock copolymers—polymers with alternating segments of both monomers—can be prepared. This strategy was examined mechanistically in detail based on subsequent RAFT polymerizations of styrene and butyl acrylate. Size-exclusion chromatography (SEC of these polymers showed that the examined method yields low-disperse products. In some cases, resolved peaks for molecules with different numbers of blocks (polymer chains separated by the trithiocarbonate groups could be observed. Cleavage of the polymers at the trithiocarbonate groups and SEC analysis of the products showed that the blocks in the middle of the polymers are longer than those at the ends and that the number of blocks corresponds to the number of functional groups in the initial RAFT agent. Furthermore, the produced multiblock copolymers were analyzed via differential scanning calorimetry (DSC. This work underlines that the examined methodology is very well suited for the synthesis of well-defined multiblock copolymers.

  11. Poly(ortho-phenylenediamine-co-aniline) based copolymer with improved capacitance

    Olmedo-Martínez, Jorge L.; Farías-Mancilla, Bárbara I.; Vega-Rios, Alejandro; Zaragoza-Contreras, E. Armando

    2017-10-01

    A poly(ortho-phenylenediamine-co-aniline) copolymer is synthesized via the oxidative route, using a 1:1 M ratio of aniline to ortho-phenylenediamine (oPDA) and ammonium persulfate as the oxidizing agent. Infrared spectroscopy indicates that the copolymer contains the functional groups typically present in polyaniline and poly(ortho-phenylenediamine); whereas UV-vis-NIR spectroscopy shows that the copolymer adopts a phenazine-type structure. Cyclic voltammetry evidences the copolymer synthesis, as a redox peak at -65 mV, different from those exhibited by polyaniline (160 mV and 600 mV) or poly(o-phenylenediamine) (-240 mV) is observed. Finally, electrochemical impedance spectroscopy and the charge/discharge test provide support to propose the copolymer application in electrodes for supercapacitors.

  12. Lignin poly(lactic acid) copolymers

    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.

  13. Polymers and block copolymers of fluorostyrenes by ATRP

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian

    2002-01-01

    Fully or partly fluorinated polymers have many desirable and intriguing properties. In the framework of a larger program on design and control of new functional block copolymers we recently employed the Atom Transfer Radical Polymerization (ATRP) protocol on 2,3,4,5,6-pentafluorostyrene (FS). We...... materials based on 2,3,5,6-tetrafiuoro-4-methoxy-styrene (TFMS). TFMS homopolymers as well as diblock copolymers with FS are produced by ATRP. Both types of novel polymers were subsequently demethylated and different side chains introduced on the resulting hydroxy sites....

  14. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    Flynn, Nicholas; Topal, Ç. Özge; Hikkaduwa Koralege, Rangika S.; Hartson, Steve; Ranjan, Ashish; Liu, Jing; Pope, Carey; Ramsey, Joshua D.

    2016-01-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

  15. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    Flynn, Nicholas [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Topal, Ç. Özge [School of Mechanical and Aerospace Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hikkaduwa Koralege, Rangika S. [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hartson, Steve [Department of Biochemistry and Molecular Biology, Oklahoma State University, Stillwater, OK 74078 (United States); Ranjan, Ashish; Liu, Jing; Pope, Carey [Department of Physiological Sciences, Oklahoma State University, Stillwater, OK 74078 (United States); Ramsey, Joshua D., E-mail: josh.ramsey@okstate.edu [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States)

    2016-05-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

  16. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation.

  17. Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

    Kenji Michiue

    2015-11-01

    Full Text Available In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’2]ZrCl2 (Indenyl’ = generic substituted indenyl, after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenylzirconium dichloride (1, rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl] zirconium dichloride (2, rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl]zirconium dichloride (3, rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl zirconium dichloride (4, rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthylindenyl]zirconium dichloride (5, rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenylindenyl][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenylindenyl]zirconium dichloride (6, rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthrylindenyl]zirconium dichloride (7, and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthrylindenyl]zirconium dichloride (8. We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.

  18. Characterization of the interaction between two food aroma components, alpha-pinene and ethyl butyrate, and ethylene-vinyl alcohol copolymer (EVOH) packaging films as a function of environmental humidity.

    López-Carballo, Gracia; Cava, David; Lagarón, Jose M; Catalá, Ramón; Gavara, Rafael

    2005-09-07

    The ethylene-vinyl alcohol copolymers (EVOHs) are well-known high oxygen barrier materials that are being used successfully in the design of packaging structures for oxygen-sensitive food or pharmaceutical products. Recently, there has been increasing interest in using EVOH materials to provide a high barrier to organic compounds as a means to reduce food aroma scalping. However, the barrier function of this family of materials diminishes significantly in humid environments, and it is supposed that so does the organic vapor barrier. In this work, a new sorption-based method to characterize the interaction between food aroma and polymer films for packaging as a function of relative humidity is presented and is used to determine the barrier to ethyl butyrate and alpha-pinene of EVOH at 23 degrees C. The results show that although EVOH is an excellent barrier to food aroma when dry, a property that even improves at low relative humidity (RH), the solubility and diffusivity of the compounds tested increase dramatically with humidity at medium to high water activities. However, even in the worst case (100% RH), EVOH outperforms low-density polyethylene (LDPE) as a barrier to organic vapors at least 500,000-fold.

  19. Compact and accurate linear and nonlinear autoregressive moving average model parameter estimation using laguerre functions

    Chon, K H; Cohen, R J; Holstein-Rathlou, N H

    1997-01-01

    A linear and nonlinear autoregressive moving average (ARMA) identification algorithm is developed for modeling time series data. The algorithm uses Laguerre expansion of kernals (LEK) to estimate Volterra-Wiener kernals. However, instead of estimating linear and nonlinear system dynamics via moving...... average models, as is the case for the Volterra-Wiener analysis, we propose an ARMA model-based approach. The proposed algorithm is essentially the same as LEK, but this algorithm is extended to include past values of the output as well. Thus, all of the advantages associated with using the Laguerre...

  20. A note on the relationship between the emittance, the beta function and the energy in a linear collider

    Rees, J.

    1986-11-01

    Scaling laws for linear colliders are considered for the case of laterally round Gaussian beams and for the case that mutual pinching of the beams can be ignored. Based on these assumptions, the relationship is found between the interaction area, beta function, beam emittance, and energy for a linear collider in order to show the need for substantial improvements in the feasible values of accelerator parameters to reach a center of mass energy of 0.7 TeV. Pinch is then taken into account

  1. Confirmation of linear system theory prediction: Changes in Herrnstein's k as a function of changes in reinforcer magnitude.

    McDowell, J J; Wood, H M

    1984-03-01

    Eight human subjects pressed a lever on a range of variable-interval schedules for 0.25 cent to 35.0 cent per reinforcement. Herrnstein's hyperbola described seven of the eight subjects' response-rate data well. For all subjects, the y-asymptote of the hyperbola increased with increasing reinforcer magnitude and its reciprocal was a linear function of the reciprocal of reinforcer magnitude. These results confirm predictions made by linear system theory; they contradict formal properties of Herrnstein's account and of six other mathematical accounts of single-alternative responding.

  2. Canonical-ensemble extended Lagrangian Born-Oppenheimer molecular dynamics for the linear scaling density functional theory.

    Hirakawa, Teruo; Suzuki, Teppei; Bowler, David R; Miyazaki, Tsuyoshi

    2017-10-11

    We discuss the development and implementation of a constant temperature (NVT) molecular dynamics scheme that combines the Nosé-Hoover chain thermostat with the extended Lagrangian Born-Oppenheimer molecular dynamics (BOMD) scheme, using a linear scaling density functional theory (DFT) approach. An integration scheme for this canonical-ensemble extended Lagrangian BOMD is developed and discussed in the context of the Liouville operator formulation. Linear scaling DFT canonical-ensemble extended Lagrangian BOMD simulations are tested on bulk silicon and silicon carbide systems to evaluate our integration scheme. The results show that the conserved quantity remains stable with no systematic drift even in the presence of the thermostat.

  3. Commentary on the statistical properties of noise and its implication on general linear models in functional near-infrared spectroscopy.

    Huppert, Theodore J

    2016-01-01

    Functional near-infrared spectroscopy (fNIRS) is a noninvasive neuroimaging technique that uses low levels of light to measure changes in cerebral blood oxygenation levels. In the majority of NIRS functional brain studies, analysis of this data is based on a statistical comparison of hemodynamic levels between a baseline and task or between multiple task conditions by means of a linear regression model: the so-called general linear model. Although these methods are similar to their implementation in other fields, particularly for functional magnetic resonance imaging, the specific application of these methods in fNIRS research differs in several key ways related to the sources of noise and artifacts unique to fNIRS. In this brief communication, we discuss the application of linear regression models in fNIRS and the modifications needed to generalize these models in order to deal with structured (colored) noise due to systemic physiology and noise heteroscedasticity due to motion artifacts. The objective of this work is to present an overview of these noise properties in the context of the linear model as it applies to fNIRS data. This work is aimed at explaining these mathematical issues to the general fNIRS experimental researcher but is not intended to be a complete mathematical treatment of these concepts.

  4. Asymmetric block copolymers confined in a thin film

    Huinink, HP; Brokken-Zijp, JCM; van Dijk, MA; Sevink, GJA

    2000-01-01

    We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A(n)B(m)(f(A) = 1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads.

  5. Multiple ordered phases in a block copolymer melt

    Almdal, K.; Koppi, K.A.; Bates, F.S.

    1992-01-01

    A poly(ethylenepropylene)-poly(ethylethylene) (PEP-PEE) diblock copolymer containing 65% by volume PEP was investigated using small-angle neutron scattering (SANS) and rheological measurements. Four distinct phases have been identified as a function of temperature: three ordered phases at low...

  6. Styrene-divinylbenzene copolymer grafted with phosphonic acid dialkylesters

    SMARANDA ILIESCU

    2004-12-01

    Full Text Available The functionalization of a crosslinked chloromethylated polystyrene 8% divinylbenzene copolymer with phosphonic ester groups is detailed. The reacton conditions were studied in order to determine the optimal conditions for obtaining only diesters. A statistical method for the calculation of the fraction of repetive units for the inited and final resin is proposed.

  7. Solving the Fully Fuzzy Bilevel Linear Programming Problem through Deviation Degree Measures and a Ranking Function Method

    Aihong Ren

    2016-01-01

    Full Text Available This paper is concerned with a class of fully fuzzy bilevel linear programming problems where all the coefficients and decision variables of both objective functions and the constraints are fuzzy numbers. A new approach based on deviation degree measures and a ranking function method is proposed to solve these problems. We first introduce concepts of the feasible region and the fuzzy optimal solution of a fully fuzzy bilevel linear programming problem. In order to obtain a fuzzy optimal solution of the problem, we apply deviation degree measures to deal with the fuzzy constraints and use a ranking function method of fuzzy numbers to rank the upper and lower level fuzzy objective functions. Then the fully fuzzy bilevel linear programming problem can be transformed into a deterministic bilevel programming problem. Considering the overall balance between improving objective function values and decreasing allowed deviation degrees, the computational procedure for finding a fuzzy optimal solution is proposed. Finally, a numerical example is provided to illustrate the proposed approach. The results indicate that the proposed approach gives a better optimal solution in comparison with the existing method.

  8. Metallo-supramolecular block copolymer micelles

    Gohy, J.M.W.

    2009-01-01

    Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

  9. A non-linear regression analysis program for describing electrophysiological data with multiple functions using Microsoft Excel.

    Brown, Angus M

    2006-04-01

    The objective of this present study was to demonstrate a method for fitting complex electrophysiological data with multiple functions using the SOLVER add-in of the ubiquitous spreadsheet Microsoft Excel. SOLVER minimizes the difference between the sum of the squares of the data to be fit and the function(s) describing the data using an iterative generalized reduced gradient method. While it is a straightforward procedure to fit data with linear functions, and we have previously demonstrated a method of non-linear regression analysis of experimental data based upon a single function, it is more complex to fit data with multiple functions, usually requiring specialized expensive computer software. In this paper we describe an easily understood program for fitting experimentally acquired data, in this case the stimulus-evoked compound action potential from the mouse optic nerve, with multiple Gaussian functions. The program is flexible and can be applied to describe data with a wide variety of user-input functions.

  10. On linearity of pan-integral and pan-integrable functions space

    Ouyang, Y.; Li, J.; Mesiar, Radko

    2017-01-01

    Roč. 90, č. 1 (2017), s. 307-318 ISSN 0888-613X Institutional support: RVO:67985556 Keywords : linearity * monotone measure * Pan-integrable space Subject RIV: BA - General Mathematics OBOR OECD: Pure mathematics Impact factor: 2.845, year: 2016 http://library.utia.cas.cz/separaty/2017/E/mesiar-0477549.pdf

  11. On the rank 1 convexity of stored energy functions of physically linear stress-strain relations

    Šilhavý, Miroslav; Bertram, A.; Böhlke, T.

    2007-01-01

    Roč. 86, č. 3 (2007), s. 235-243 ISSN 0374-3535 Institutional research plan: CEZ:AV0Z10190503 Keywords : generalized linear elastic law s * generalized strain measures * rank 1 convexity Subject RIV: BA - General Mathematics Impact factor: 0.743, year: 2007

  12. Acetate and phosphate anion adsorption linear sweep voltammograms simulated using density functional theory

    Savizi, Iman Shahidi Pour; Janik, Michael J.

    2011-01-01

    ) electrode potential. Four models of the electrode potential are used including a simple vacuum slab model, an applied electric field model with and without the inclusion of a solvating water bi-layer, and the double reference model. The linear sweep

  13. Molecular Mobility in Phase Segregated Bottlebrush Block Copolymer Melts

    Yavitt, Benjamin; Gai, Yue; Song, Dongpo; Winter, H. Henning; Watkins, James

    We investigate the linear viscoelastic behavior of poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) brush block copolymer (BBCP) materials over a range of vol. fractions and with side chain lengths below the entanglement molecular weights. The high chain mobility of the brush architecture results in rapid micro-phase segregation of the brush copolymer segments, which occurs during thermal annealing at mild temperatures. Master curves of the dynamic moduli were obtained by time-temperature superposition. The reduced degree of chain entanglements leads to a unique liquid-like rheology similar to that of bottlebrush homopolymers, even in the phase segregated state. We also explore the alignment of phase segregated domains at exceptionally low strain amplitudes (γ = 0.01) and mild processing temperatures using small angle X-ray scattering (SAXS). Domain orientation occurred readily at strains within the linear viscoelastic regime without noticeable effect on the moduli. This interplay of high molecular mobility and rapid phase segregation that are exhibited simultaneously in BBCPs is in contrast to the behavior of conventional linear block copolymer (LBCP) analogs and opens up new possibilities for processing BBCP materials for a wide range of nanotechnology applications. NSF Center for Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-1025020).

  14. Comparison of multiple linear regression and artificial neural network in developing the objective functions of the orthopaedic screws.

    Hsu, Ching-Chi; Lin, Jinn; Chao, Ching-Kong

    2011-12-01

    Optimizing the orthopaedic screws can greatly improve their biomechanical performances. However, a methodical design optimization approach requires a long time to search the best design. Thus, the surrogate objective functions of the orthopaedic screws should be accurately developed. To our knowledge, there is no study to evaluate the strengths and limitations of the surrogate methods in developing the objective functions of the orthopaedic screws. Three-dimensional finite element models for both the tibial locking screws and the spinal pedicle screws were constructed and analyzed. Then, the learning data were prepared according to the arrangement of the Taguchi orthogonal array, and the verification data were selected with use of a randomized selection. Finally, the surrogate objective functions were developed by using either the multiple linear regression or the artificial neural network. The applicability and accuracy of those surrogate methods were evaluated and discussed. The multiple linear regression method could successfully construct the objective function of the tibial locking screws, but it failed to develop the objective function of the spinal pedicle screws. The artificial neural network method showed a greater capacity of prediction in developing the objective functions for the tibial locking screws and the spinal pedicle screws than the multiple linear regression method. The artificial neural network method may be a useful option for developing the objective functions of the orthopaedic screws with a greater structural complexity. The surrogate objective functions of the orthopaedic screws could effectively decrease the time and effort required for the design optimization process. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  15. Natural excitation orbitals from linear response theories : Time-dependent density functional theory, time-dependent Hartree-Fock, and time-dependent natural orbital functional theory

    Van Meer, R.; Gritsenko, O. V.; Baerends, E. J.

    2017-01-01

    Straightforward interpretation of excitations is possible if they can be described as simple single orbital-to-orbital (or double, etc.) transitions. In linear response time-dependent density functional theory (LR-TDDFT), the (ground state) Kohn-Sham orbitals prove to be such an orbital basis. In

  16. Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

    Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

    2015-08-07

    A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

  17. Molecular changes in copolymers of styrene and methyl methacrylate caused by radiation

    Busfield, W.K.; O'Donnell, J.H.; Smith, C.A.

    1976-01-01

    Homopolymers of styrene and methyl methacrylate and copolymers of these monomers were irradiated in vacuo at room temperature using 60 Co γ-radiation to various doses. The gaseous radiolysis products of the polymers were analysed by gas chromatography. The radiation chemical yield, G values, of the gaseous and liquid products were calculated for the homopolymers and copolymers. The G values obtained for the homopolymers were compared with those obtained by previous workers. The graphs of G value versus composition (% Styrene) showed a marked deviation from linearity which indicated that the styrene in the copolymer had a greater effect on the behaviour than did the methyl methacrylate units. It has been postulated that the benzene ring on the styrene unit acts in some way as an energy sink, and hence protects the copolymer from radiation damage in an analogous way to that suggested for hydrocarbon mixtures. Mechanisms for the process are discussed. (author)

  18. Main-chain supramolecular block copolymers.

    Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

    2011-01-01

    Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

  19. Responsive copolymers for enhanced petroleum recovery. Second annual report

    McCormick, C.; Hester, R.

    1995-05-01

    The authors describe second year efforts in synthesis, characterization, and rheology to develop polymers with significantly improved efficiency in mobility control and conformance. These advanced polymer systems would maintain high viscosities or behave as virtual gels under low shear conditions and at elevated electrolyte concentrations. At high fluid shear rates, associates would deaggregate yielding low viscosity solutions, reducing problems of shear degradation or face plugging during injection. Polymeric surfactants were also developed with potential for use in higher salt, higher temperature reservoirs for mobilization of entrapped oil. Chapters include: Ampholytic terpolymers of acrylamide with sodium 3-acrylamido-3-methylbutanoate and 2-acrylamido-2-methylpropanetrimethylammonium chloride; Hydrophilic sulfobetaine copolymers of acrylamide and 3-(2-acrylamido-methylpropane-dimethylammonio)-1-propanesulfonate; Copolymerization of maleic anhydride and N-vinylformamide; Reactivity ratio of N-vinylformamide with acrylamide, sodium acrylate, and n-butyl acrylate; Effect of the distribution of the hydrophobic cationic monomer dimethyldodecyl(2-acrylamidoethyl)ammonium bromide on the solution behavior of associating acrylamide copolymers; Effect of surfactants on the solution properties of amphipathic copolymers of acrylamide and N,N-dimethyl-N-dodecyl-N-(2-acrylamidoethyl)ammonium bromide; Associative interactions and photophysical behavior of amphiphilic terpolymers prepared by modification of maleic anhydride/ethyl vinyl ether copolymers; Copolymer compositions of high-molecular-weight functional acrylamido water-soluble polymers using direct-polarization magic-angle spinning {sup 13}C NMR; Use of factorial experimental design in static and dynamic light scattering characterization of water soluble polymers; and Porous medium elongational rheometer studies of NaAMB/AM copolymer solutions.

  20. Legendre-tau approximation for functional differential equations. II - The linear quadratic optimal control problem

    Ito, Kazufumi; Teglas, Russell

    1987-01-01

    The numerical scheme based on the Legendre-tau approximation is proposed to approximate the feedback solution to the linear quadratic optimal control problem for hereditary differential systems. The convergence property is established using Trotter ideas. The method yields very good approximations at low orders and provides an approximation technique for computing closed-loop eigenvalues of the feedback system. A comparison with existing methods (based on averaging and spline approximations) is made.

  1. Legendre-tau approximation for functional differential equations. Part 2: The linear quadratic optimal control problem

    Ito, K.; Teglas, R.

    1984-01-01

    The numerical scheme based on the Legendre-tau approximation is proposed to approximate the feedback solution to the linear quadratic optimal control problem for hereditary differential systems. The convergence property is established using Trotter ideas. The method yields very good approximations at low orders and provides an approximation technique for computing closed-loop eigenvalues of the feedback system. A comparison with existing methods (based on averaging and spline approximations) is made.

  2. Amphiphilic block copolymers for drug delivery.

    Adams, Monica L; Lavasanifar, Afsaneh; Kwon, Glen S

    2003-07-01

    Amphiphilic block copolymers (ABCs) have been used extensively in pharmaceutical applications ranging from sustained-release technologies to gene delivery. The utility of ABCs for delivery of therapeutic agents results from their unique chemical composition, which is characterized by a hydrophilic block that is chemically tethered to a hydrophobic block. In aqueous solution, polymeric micelles are formed via the association of ABCs into nanoscopic core/shell structures at or above the critical micelle concentration. Upon micellization, the hydrophobic core regions serve as reservoirs for hydrophobic drugs, which may be loaded by chemical, physical, or electrostatic means, depending on the specific functionalities of the core-forming block and the solubilizate. Although the Pluronics, composed of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide), are the most widely studied ABC system, copolymers containing poly(L-amino acid) and poly(ester) hydrophobic blocks have also shown great promise in delivery applications. Because each ABC has unique advantages with respect to drug delivery, it may be possible to choose appropriate block copolymers for specific purposes, such as prolonging circulation time, introduction of targeting moieties, and modification of the drug-release profile. ABCs have been used for numerous pharmaceutical applications including drug solubilization/stabilization, alteration of the pharmacokinetic profile of encapsulated substances, and suppression of multidrug resistance. The purpose of this minireview is to provide a concise, yet detailed, introduction to the use of ABCs and polymeric micelles as delivery agents as well as to highlight current and past work in this area. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association

  3. Phase behavior of diblock copolymer/star-shaped polymer thin film mixtures.

    Zhao, Junnan; Sakellariou, Georgios; Green, Peter F

    2016-05-07

    We investigated the phase behavior of thin film, thickness h≈ 100 nm, mixtures of a polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer with star-shaped polystyrene (SPS) molecules of varying functionalities f, where 4 ≤f≤ 64, and molecular weights per arm Marm. The miscibility of the system and the surface composition varied appreciably with Marm and f. For large values of Marm, regardless of f, the miscibility of the system was qualitatively similar to that of linear chain PS/PS-b-P2VP mixtures - the copolymer chains aggregate to form micelles, each composed of an inner P2VP core and PS corona, which preferentially segregate to the free surface. On the other hand, for large f and small Marm, SPS molecules preferentially resided at the free surface. Moreover, blends containing SPS molecules with the highest values of f and lowest values of Marm were phase separated. These observations are rationalized in terms of competing entropic interactions and the dependence of the surface tension of the star-shaped molecules on Marm and f.

  4. The radiation crosslinking of ethylene copolymers

    Burns, N.M.

    1979-01-01

    The enhanced radiation crosslinking tendency of ethylene-vinyl acetate and ethylene-ethyl acrylate copolymers over ethylene homopolymer is proportional to the comonomer content. This is caused by an increase in the amorphous polymer content and by structure-related factors. The copolymers crosslink by a random process that for ethylene-vinyl acetate copolymer involves some crosslinking through the acetoxy group of the comonomer. While knowledge of the process for the crosslinking of ethylene-ethyl acrylate copolymer is less certain, it is currently believed to occur primarily at the branch point on the polymer backbone. Data relating comonomer content and the molecular weight of the copolymers to the radiation crosslinking levels realized were developed to aid in resin selection by the formulator. Triallyl cyanurate cure accelerator was found to be less effective in ethylene-vinyl acetate copolymer than in homopolymer and to have no effect on gel development in ethylene-ethyl acrylate copolymer. (author)

  5. One-Year Linear Trajectories of Symptoms, Physical Functioning, Cognitive Functioning, Emotional Well-being, and Spiritual Well-being Among Patients Receiving Dialysis.

    Song, Mi-Kyung; Paul, Sudeshna; Ward, Sandra E; Gilet, Constance A; Hladik, Gerald A

    2018-01-25

    This study evaluated 1-year linear trajectories of patient-reported dimensions of quality of life among patients receiving dialysis. Longitudinal observational study. 227 patients recruited from 12 dialysis centers. Sociodemographic and clinical characteristics. Participants completed an hour-long interview monthly for 12 months. Each interview included patient-reported outcome measures of overall symptoms (Edmonton Symptom Assessment System), physical functioning (Activities of Daily Living/Instrumental Activities of Daily Living), cognitive functioning (Patient's Assessment of Own Functioning Inventory), emotional well-being (Center for Epidemiologic Studies Depression Scale, State Anxiety Inventory, and Positive and Negative Affect Schedule), and spiritual well-being (Functional Assessment of Chronic Illness Therapy-Spiritual Well-Being Scale). For each dimension, linear and generalized linear mixed-effects models were used. Linear trajectories of the 5 dimensions were jointly modeled as a multivariate outcome over time. Although dimension scores fluctuated greatly from month to month, overall symptoms, cognitive functioning, emotional well-being, and spiritual well-being improved over time. Older compared with younger participants reported higher scores across all dimensions (all Pspiritual well-being compared with their white counterparts (P<0.01). Clustering analysis of dimension scores revealed 2 distinctive clusters. Cluster 1 was characterized by better scores than those of cluster 2 in nearly all dimensions at baseline and by gradual improvement over time. Study was conducted in a single region of the United States and included mostly patients with high levels of function across the dimensions of quality of life studied. Multidimensional patient-reported quality of life varies widely from month to month regardless of whether overall trajectories improve or worsen over time. Additional research is needed to identify the best approaches to incorporate

  6. Effects of Supported ( n BuCp) 2 ZrCl 2 Catalyst Active-Center Distribution on Ethylene–1-Hexene Copolymer Backbone Heterogeneity and Thermal Behaviors

    Atiqullah, Muhammad

    2013-07-10

    Two catalysts, denoted as catalyst 1 [silica/MAO/(nBuCp) 2ZrCl2] and catalyst 2 [silica/nBuSnCl 3/MAO/(nBuCp)2ZrCl2] were synthesized and subsequently used to prepare, without separate feeding of methylaluminoxane (MAO), ethylene homopolymer 1 and homopolymer 2, respectively, and ethylene-1-hexene copolymer 1 and copolymer 2, respectively. Gel permeation chromatography (GPC), Crystaf, differential scanning calorimetry (DSC) [conventional and successive self-nucleation and annealing (SSA)], and 13C nuclear magnetic resonance (NMR) polymer characterization results were used, as appropriate, to model the catalyst active-center distribution, ethylene sequence (equilibrium crystal) distribution, and lamellar thickness distribution (both continuous and discrete). Five different types of active centers were predicted in each catalyst, as corroborated by the SSA experiments and complemented by an extended X-ray absorption fine structure (EXAFS) report published in the literature. 13C NMR spectroscopy also supported this active-center multiplicity. Models combined with experiments effectively illustrated how and why the active-center distribution and the variance in the design of the supported MAO anion, having different electronic and steric effects and coordination environments, influence the concerned copolymerization mechanism and polymer properties, including inter- and intrachain compositional heterogeneity and thermal behaviors. Copolymerization occurred according to the first-order Markovian terminal model, producing fairly random copolymers with minor skewedness toward blocky character. For each copolymer, the theoretical most probable ethylene sequences, nE MPDSC-GT and n E MPNMR-Flory, as well as the weight-average lamellar thicknesses, Lwav DSC-GT and Lwav SSA DSC, were found to be comparable. To the best of our knowledge, such a match has not previously been reported. The percentage crystallinities of the homo- and copolymers increased linearly as a function of

  7. A Quasi-Dynamic Optimal Control Strategy for Non-Linear Multivariable Processes Based upon Non-Quadratic Objective Functions

    Jens G. Balchen

    1984-10-01

    Full Text Available The problem of systematic derivation of a quasi-dynamic optimal control strategy for a non-linear dynamic process based upon a non-quadratic objective function is investigated. The wellknown LQG-control algorithm does not lead to an optimal solution when the process disturbances have non-zero mean. The relationships between the proposed control algorithm and LQG-control are presented. The problem of how to constrain process variables by means of 'penalty' - terms in the objective function is dealt with separately.

  8. Linear response calculation using the canonical-basis TDHFB with a schematic pairing functional

    Ebata, Shuichiro; Nakatsukasa, Takashi; Yabana, Kazuhiro

    2011-01-01

    A canonical-basis formulation of the time-dependent Hartree-Fock-Bogoliubov (TDHFB) theory is obtained with an approximation that the pair potential is assumed to be diagonal in the time-dependent canonical basis. The canonical-basis formulation significantly reduces the computational cost. We apply the method to linear-response calculations for even-even nuclei. E1 strength distributions for proton-rich Mg isotopes are systematically calculated. The calculation suggests strong Landau damping of giant dipole resonance for drip-line nuclei.

  9. Modeling of emulsion copolymer microstructure

    van Doremaele, G.H.J.; Herk, van A.M.; German, A.L.

    1992-01-01

    A model is developed to describe stages II and III of batch emulsion copolymn., and its predictive capabilities are investigated by application to the system styrene-Me acrylate. The main reaction site is the monomer-swollen polymer particle. Copolymn. rate and copolymer microstructure (molar

  10. Polyether-polyester graft copolymer

    Bell, Vernon L. (Inventor)

    1987-01-01

    Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

  11. Thermo-responsive block copolymers

    Mocan Cetintas, Merve

    2017-01-01

    Block copolymers (BCPs) are remarkable materials because of their self-assembly behavior into nano-sized regular structures and high tunable properties. BCPs are in used various applications such as surfactants, nanolithography, biomedicine and nanoporous membranes. In these thesis, we aimed to

  12. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  13. Linear algebra

    Said-Houari, Belkacem

    2017-01-01

    This self-contained, clearly written textbook on linear algebra is easily accessible for students. It begins with the simple linear equation and generalizes several notions from this equation for the system of linear equations and introduces the main ideas using matrices. It then offers a detailed chapter on determinants and introduces the main ideas with detailed proofs. The third chapter introduces the Euclidean spaces using very simple geometric ideas and discusses various major inequalities and identities. These ideas offer a solid basis for understanding general Hilbert spaces in functional analysis. The following two chapters address general vector spaces, including some rigorous proofs to all the main results, and linear transformation: areas that are ignored or are poorly explained in many textbooks. Chapter 6 introduces the idea of matrices using linear transformation, which is easier to understand than the usual theory of matrices approach. The final two chapters are more advanced, introducing t...

  14. Non-linear corrections to the time-covariance function derived from a multi-state chemical master equation.

    Scott, M

    2012-08-01

    The time-covariance function captures the dynamics of biochemical fluctuations and contains important information about the underlying kinetic rate parameters. Intrinsic fluctuations in biochemical reaction networks are typically modelled using a master equation formalism. In general, the equation cannot be solved exactly and approximation methods are required. For small fluctuations close to equilibrium, a linearisation of the dynamics provides a very good description of the relaxation of the time-covariance function. As the number of molecules in the system decrease, deviations from the linear theory appear. Carrying out a systematic perturbation expansion of the master equation to capture these effects results in formidable algebra; however, symbolic mathematics packages considerably expedite the computation. The authors demonstrate that non-linear effects can reveal features of the underlying dynamics, such as reaction stoichiometry, not available in linearised theory. Furthermore, in models that exhibit noise-induced oscillations, non-linear corrections result in a shift in the base frequency along with the appearance of a secondary harmonic.

  15. Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

    Giovannitti, Alexander

    2018-02-23

    Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

  16. Redox-Stability of Alkoxy-BDT Copolymers and their Use for Organic Bioelectronic Devices

    Giovannitti, Alexander; Thorley, Karl J.; Nielsen, Christian B.; Li, Jun; Donahue, Mary J.; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    Organic semiconductors can be employed as the active layer in accumulation mode organic electrochemical transistors (OECTs), where redox stability in aqueous electrolytes is important for long-term recordings of biological events. It is observed that alkoxy-benzo[1,2-b:4,5-b′]dithiophene (BDT) copolymers can be extremely unstable when they are oxidized in aqueous solutions. The redox stability of these copolymers can be improved by molecular design of the copolymer where it is observed that the electron rich comonomer 3,3′-dimethoxy-2,2′-bithiophene (MeOT2) lowers the oxidation potential and also stabilizes positive charges through delocalization and resonance effects. For copolymers where the comonomers do not have the same ability to stabilize positive charges, irreversible redox reactions are observed with the formation of quinone structures, being detrimental to performance of the materials in OECTs. Charge distribution along the copolymer from density functional theory calculations is seen to be an important factor in the stability of the charged copolymer. As a result of the stabilizing effect of the comonomer, a highly stable OECT performance is observed with transconductances in the mS range. The analysis of the decomposition pathway also raises questions about the general stability of the alkoxy-BDT unit, which is heavily used in donor-acceptor copolymers in the field of photovoltaics.

  17. Block copolymer morphologies confined by square-shaped particle: Hard and soft confinement

    Zhang Qiyi; Yang Wenyan; Hu Kaiyan

    2016-01-01

    The self-assembly of diblock copolymers confined around one square-shaped particle is studied systematically within two-dimensional self-consistent field theory (SCFT). In this model, we assume that the thin block copolymer film is confined in the vicinity of a square-shaped particle by a homopolymer melt, which is equivalent to the poor solvents. Multiple sequences of square-shaped particle-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of the particle size, the structural portion of the copolymer, and the volume fraction of the copolymer. A rich variety of aggregates are found with complex internal self-assembled morphologies including complex structures of the vesicle, with one or several inverted micelle surrounded by the outer monolayer with the particle confined in the core. These results demonstrate that the assemblies of diblock copolymers formed around the square-shaped particle in poor solvents are of immediate interest to the assembly of copolymer and the morphology of biomembrane in the confined environment, as well as to the transitions of vesicles to micelles. (paper)

  18. A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface

    Mishra, Pramod Kumar

    2010-01-01

    A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

  19. A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface.

    Mishra, Pramod Kumar

    2010-04-21

    A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

  20. Do Quercus ilex woodlands undergo abrupt non-linear functional changes in response to human disturbance along a climatic gradient?

    Bochet, Esther; García-Fayos, Patricio; José Molina, Maria; Moreno de las Heras, Mariano; Espigares, Tíscar; Nicolau, Jose Manuel; Monleon, Vicente

    2017-04-01

    Theoretical models predict that drylands are particularly prone to suffer critical transitions with abrupt non-linear changes in their structure and functions as a result of the existing complex interactions between climatic fluctuations and human disturbances. However, so far, few studies provide empirical data to validate these models. We aim at determining how holm oak (Quercus ilex) woodlands undergo changes in their functions in response to human disturbance along an aridity gradient (from semi-arid to sub-humid conditions), in eastern Spain. For that purpose, we used (a) remote-sensing estimations of precipitation-use-efficiency (PUE) from enhanced vegetation index (EVI) observations performed in 231x231 m plots of the Moderate Resolution Imaging Spectroradiometer (MODIS); (b) biological and chemical soil parameter determinations (extracellular soil enzyme activity, soil respiration, nutrient cycling processes) from soil sampled in the same plots; (c) vegetation parameter determinations (ratio of functional groups) from vegetation surveys performed in the same plots. We analyzed and compared the shape of the functional change (in terms of PUE and soil and vegetation parameters) in response to human disturbance intensity for our holm oak sites along the aridity gradient. Overall, our results evidenced important differences in the shape of the functional change in response to human disturbance between climatic conditions. Semi-arid areas experienced a more accelerated non-linear decrease with an increasing disturbance intensity than sub-humid ones. The proportion of functional groups (herbaceous vs. woody cover) played a relevant role in the shape of the functional response of the holm oak sites to human disturbance.

  1. Study of the therapeutic benefit of cationic copolymer administration to vascular endothelium under mechanical stress

    Giantsos-Adams, Kristina; Lopez-Quintero, Veronica; Kopeckova, Pavla; Kopecek, Jindrich; Tarbell, John M.; Dull, Randal

    2015-01-01

    Pulmonary edema and the associated increases in vascular permeability continue to represent a significant clinical problem in the intensive care setting, with no current treatment modality other than supportive care and mechanical ventilation. Therapeutic compound(s) capable of attenuating changes in vascular barrier function would represent a significant advance in critical care medicine. We have previously reported the development of HPMA-based copolymers, targeted to endothelial glycocalyx that are able to enhance barrier function. In this work, we report the refinement of copolymer design and extend our physiological studies todemonstrate that the polymers: 1) reduce both shear stress and pressure-mediated increase in hydraulic conductivity, 2) reduce nitric oxide production in response to elevated hydrostatic pressure and, 3) reduce the capillary filtration coefficient (Kfc) in an isolated perfused mouse lung model. These copolymers represent an important tool for use in mechanotransduction research and a novel strategy for developing clinically useful copolymers for the treatment of vascular permeability. PMID:20932573

  2. Phase transition of LB films of mixed diblock copolymer at the air/water interface

    Seo, Y. S.; Kim, K. S.; Samuilov, V.; Rafailovich, M. H.; Sokolov, J.; Lammertink, Rob G. H.; Vancso, G. J.

    2000-03-01

    We have studied the morphology of Langmuir blodgett films at the air/water interface of mixed diblock copolymer films. Solutions of poly(styrene-b-ferrocenyldimethylsilane) and PS-b-P2VP mixed in a ratio of 20/80 in chloroform were spread at the air/water interface. The morphology of the films was studied with AFM as a function of the surface pressure and the diblock copolymer molecular weight. The results show that the two diblock copolymers can be induced to mix at the air/water interface with increasing surface pressure. A reversible transition from spherical to cylindrical morphologies is induced in the mixture which can not be observed in films formed of the two components separately. The effective surface phase diagram as a function of block copolymer composition and pressure will be presented.

  3. Surface dynamics of micellar diblock copolymer films

    Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

    2011-03-01

    We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

  4. The log-linear response function of the bounded number-line task is unrelated to the psychological representation of quantity.

    Cohen, Dale J; Quinlan, Philip T

    2018-02-01

    The bounded number-line task has been used extensively to assess the numerical competence of both children and adults. One consistent finding has been that young children display a logarithmic response function, whereas older children and adults display a more linear response function. Traditionally, these log-linear functions have been interpreted as providing a transparent window onto the nature of the participants' psychological representations of quantity (termed here a direct response strategy). Here we show that the direct response strategy produces the log-linear response function regardless of whether the psychological representation of quantity is compressive or expansive. Simply put, the log-linear response function results from task constraints rather than from the psychological representation of quantities. We also demonstrate that a proportion/subtraction response strategy produces response patterns that almost perfectly correlate with the psychological representation of quantity. We therefore urge researchers not to interpret the log-linear response pattern in terms of numerical representation.

  5. Nucleon-nucleon scattering in the functional quantum theory of the non-linear spinor field

    Philipp, W.

    1975-01-01

    The nucleon-nucleon and nucleon-antinucleon scattering cross sections are calculated in the frame of the functional quantum field theory by means of two different approximation methods: averaging by integration of indefinite integrals and pulse averaging. The results for nucleon-nucleon scattering are compared with experimental data, with calculations using a modified functional scalar product and with results in first order perturbation theory (V-A-coupling). As for elastic nucleon-antinucleon scattering, the S matrix is investigated for crossing symmetry. Scattering of 'nucleons' of different mass results in different cross sections even in the lowest-order approximation. (BJ) [de

  6. Variational Iteration Method for Volterra Functional Integrodifferential Equations with Vanishing Linear Delays

    Ali Konuralp

    2014-01-01

    Full Text Available Application process of variational iteration method is presented in order to solve the Volterra functional integrodifferential equations which have multi terms and vanishing delays where the delay function θ(t vanishes inside the integral limits such that θ(t=qt for 0

  7. Block copolymer-nanoparticle hybrid self-assembly

    Hoheisel, Tobias N.; Hur, Kahyun; Wiesner, Ulrich B.

    2015-01-01

    © 2014 Published by Elsevier Ltd. Polymer-inorganic hybrid materials provide exciting opportunities as they may display favorable properties from both constituents that are desired in applications including catalysis and energy conversion and storage. For the preparation of hybrid materials with well-defined morphologies, block copolymer-directed nanoparticle hybrids present a particularly promising approach. As will be described in this review, once the fundamental characteristics for successful nanostructure formation at or close to the thermodynamic equilibrium of these nanocomposites are identified, the approach can be generalized to various materials classes. In addition to the discussion of recent materials developments based on the use of AB diblock copolymers as well as ABC triblock terpolymers, this review will therefore emphasize progress in the fundamental understanding of the underlying formation mechanisms of such hybrid materials. To this end, critical experiments for, as well as theoretical progress in the description of these nanostructured block copolymer-based hybrid materials will be discussed. Rather than providing a comprehensive overview, the review will emphasize work by the Wiesner group at Cornell University, US, on block copolymer-directed nanoparticle assemblies as well as their use in first potential application areas. The results provide powerful design criteria for wet-chemical synthesis methodologies for the generation of functional nanomaterials for applications ranging from microelectronics to catalysis to energy conversion and storage.

  8. Synthesis of hydrazone functionalized epoxy polymers for non-linear optical device applications

    Singh, Rajendra K.

    A series of twelve, thermally crosslinkable, epoxy polymers bearing covalently attached NLO-active hydrazone chromophores were synthesized. The primary focus was on the synthesis of two series of NLO-active hydroxy functionalized hydrazone chromophores. The first series, called the monohydroxy series (Hydrazones I--VI) comprised of six monohydroxy functionalized hydrazones and the second series consisted of six dihydroxy functionalized hydrazones (Hydrazones VII--XII). These hydrazone chromophores were then grafted, via the hydroxy functionality, on to a commercial epoxy polymer to obtain twelve NLO-active soluble prepolymers. The grafting reaction yields multiple secondary hydroxyl sites due to opening of the epoxide rings and these hydroxyl groups were used for further crosslinking by formulating the prepolymers with a blocked polyisocyanate commercial crosslinker. This formulation was spin coated on glass slides to form 2--2.5 m m thick uniform, defect free, transparent films. The films were corona poled, above their Tg, to align the chromophores in a noncentrosymmetric fashion and simultaneously complete the thermal cure that results in a highly crosslinked network. Finally the thermal characteristics of the second order nonlinearity of the twelve polymers are compared to illustrate the key structure-property relationships underlying the performance of the films.

  9. Optimizing Linear Functions with Randomized Search Heuristics - The Robustness of Mutation

    Witt, Carsten

    2012-01-01

    The analysis of randomized search heuristics on classes of functions is fundamental for the understanding of the underlying stochastic process and the development of suitable proof techniques. Recently, remarkable progress has been made in bounding the expected optimization time of the simple (1...

  10. Determination of linear optics functions from turn-by-turn data

    Alexahin, Y; Gianfelice-Wendt, E, E-mail: alexahin@fnal.gov [Fermi National Accelerator Laboratory, P.O. Box 500, Batavia, Illinois 60510 (United States)

    2011-10-15

    A method for evaluation of coupled optics functions, detection of strong perturbing elements, determination of BPM calibration errors and tilts using turn-by-turn (TBT) data is presented as well as the new version of the Hamiltonian perturbation theory of betatron oscillations the method is based upon. An example of application of the considered method to the Tevatron is given.

  11. Bounds for the probability distribution function of the linear ACD process

    Fernandes, Marcelo

    2003-01-01

    Rio de Janeiro This paper derives both lower and upper bounds for the probability distribution function of stationary ACD(p, q) processes. For the purpose of illustration, I specialize the results to the main parent distributions in duration analysis. Simulations show that the lower bound is much tighter than the upper bound.

  12. On nonseparated three-point boundary value problems for linear functional differential equations

    Rontó, András; Rontó, M.

    2011-01-01

    Roč. 2011, - (2011), s. 326052 ISSN 1085-3375 Institutional research plan: CEZ:AV0Z10190503 Keywords : functional-differential equation * three-point boundary value problem * nonseparated boundary condition Subject RIV: BA - General Mathematics Impact factor: 1.318, year: 2011 http://www.hindawi.com/journals/ aaa /2011/326052/

  13. An Analysis of Piecewise-Linear and Convex Value Functions for Active Perception POMDPs

    Satsangi, Y.; Whiteson, S.; Spaan, M.T.J.

    2015-01-01

    In active perception tasks, an agent aims to select actions that reduce its uncertainty about a hidden state. While partially observable Markov decision processes (POMDPs) are a natural model for such problems, reward functions that directly penalize uncertainty in the agent's belief can remove the

  14. Equilibrium arrival times to queues with general service times and non-linear utility functions

    Breinbjerg, Jesper

    2017-01-01

    by a general utility function which is decreasing in the waiting time and service completion time of each customer. Applications of such queueing games range from people choosing when to arrive at a grand opening sale to travellers choosing when to line up at the gate when boarding an airplane. We develop...

  15. The effect of copolymers on the interfaces in incompatible homopolymers blend: Molecular dynamics study

    Ryu, Jiho; Lee, Won Bo

    2015-03-01

    Using molecular dynamics simulations the effect of copolymers as compatibilizer for reducing interfacial tension and enhancement of interfacial adhesion at the interface of thermodynamic unfavorable homopolymers blend is studied with block- and graft-copolymers. We have calculated local pressure tensor of system along the axis perpendicular to interface, varying bending potential energy of one part, which consist of just one kind of beads, of copolymer chain to examine the effect of stiffness of surfactin molecules. Here we consider symmetric diblock copolymer (f =1/2) having 1/2 N make of beads of type A and the other part made of beads of type B, and graft copolymer having backbone linear chain consist of 1/2 N beads of type of A and branched with two side-chain consist of 1/4 N beads of type B. All simulations were performed under the constant NPT ensemble at T* =1, ρ* ~0.85. Also we studied changes of effect of copolymers with increasing pairwise repulsive interaction potential between two beads of types A and B while homopolymers chain length are fixed, N =30. Chemical and Biomolecular Engineering, Sogang University, Seoul, South Korea.

  16. Interpolation problem for the solutions of linear elasticity equations based on monogenic functions

    Grigor'ev, Yuri; Gürlebeck, Klaus; Legatiuk, Dmitrii

    2017-11-01

    Interpolation is an important tool for many practical applications, and very often it is beneficial to interpolate not only with a simple basis system, but rather with solutions of a certain differential equation, e.g. elasticity equation. A typical example for such type of interpolation are collocation methods widely used in practice. It is known, that interpolation theory is fully developed in the framework of the classical complex analysis. However, in quaternionic analysis, which shows a lot of analogies to complex analysis, the situation is more complicated due to the non-commutative multiplication. Thus, a fundamental theorem of algebra is not available, and standard tools from linear algebra cannot be applied in the usual way. To overcome these problems, a special system of monogenic polynomials the so-called Pseudo Complex Polynomials, sharing some properties of complex powers, is used. In this paper, we present an approach to deal with the interpolation problem, where solutions of elasticity equations in three dimensions are used as an interpolation basis.

  17. CAVITATION PROPERTIES OF BLOCK COPOLYMER STABILIZED PHASE-SHIFT NANOEMULSIONS USED AS DRUG CARRIERS

    RAPOPORT, NATALYA; CHRISTENSEN, DOUGLAS A.; KENNEDY, ANNE M.; NAM, KWEONHO

    2010-01-01

    Cavitation properties of block copolymer stabilized perfluoropentane nanoemulsions have been investigated. The nanoemulsions were stabilized by two biodegradable amphiphilic block copolymers differing in the structure of the hydrophobic block, poly(ethylene oxide)-co-poly(L-lactide) (PEG-PLLA) and poly(ethylene oxide)-co-polycaprolactone (PEG-PCL). Cavitation parameters were measured in liquid emulsions and gels as a function of ultrasound pressure for unfocused or focused 1-MHz ultrasound. A...

  18. Linearly constrained minimax optimization

    Madsen, Kaj; Schjær-Jacobsen, Hans

    1978-01-01

    We present an algorithm for nonlinear minimax optimization subject to linear equality and inequality constraints which requires first order partial derivatives. The algorithm is based on successive linear approximations to the functions defining the problem. The resulting linear subproblems...

  19. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

    2015-08-30

    Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N{sup +} percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N{sup +} composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N{sup +} content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings.

  20. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

    2015-01-01

    Highlights: • QAS-containing fluorosilicone multi-block copolymers were synthesized. • The block length of PHFBMA in the copolymers was tailored via RAFT polymerization. • Surface roughness of the copolymers decreased with the increased PHFBMA content. • A certain length of PHFBMA block enhanced C−N + percentage on the surface. - Abstract: Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition–fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N + composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N + content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings

  1. Linear and nonlinear Biot waves in a noncohesive granular medium slab: transfer function, self-action, second harmonic generation.

    Legland, J-B; Tournat, V; Dazel, O; Novak, A; Gusev, V

    2012-06-01

    Experimental results are reported on second harmonic generation and self-action in a noncohesive granular medium supporting wave energy propagation both in the solid frame and in the saturating fluid. The acoustic transfer function of the probed granular slab can be separated into two main frequency regions: a low frequency region where the wave propagation is controlled by the solid skeleton elastic properties, and a higher frequency region where the behavior is dominantly due to the air saturating the beads. Experimental results agree well with a recently developed nonlinear Biot wave model applied to granular media. The linear transfer function, second harmonic generation, and self-action effect are studied as a function of bead diameter, compaction step, excitation amplitude, and frequency. This parametric study allows one to isolate different propagation regimes involving a range of described and interpreted linear and nonlinear processes that are encountered in granular media experiments. In particular, a theoretical interpretation is proposed for the observed strong self-action effect.

  2. Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

    Hedegård, Erik D.; Olsen, Jógvan Magnus Haugaard; Knecht, Stefan

    2015-01-01

    . To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality......We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE......-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory...

  3. Functional connectivity in resting-state fMRI: Is linear correlation sufficient?

    Hlinka, Jaroslav; Paluš, Milan; Vejmelka, Martin; Mantini, D.; Corbetta, M.

    2011-01-01

    Roč. 54, č. 3 (2011), s. 2218-2225 ISSN 1053-8119 R&D Projects: GA MŠk 7E08027 EU Projects: European Commission(XE) 200728 - BRAINSYNC Institutional research plan: CEZ:AV0Z10300504 Keywords : fMRI * functional connectivity * Gaussianity * nonlinearity * correlation * mutual information Subject RIV: FH - Neurology Impact factor: 5.895, year: 2011

  4. Application of the descriptive function on non-linear electromagnetic phenomena

    Silva, H.T.

    1982-01-01

    This paper presents the solution of the nonlinear plan wave equation in non-equilibrium dielectric medium. The descriptive function appears as a useful tool to describe the medium response when it is possible to consider intensive electromagnetic response. Despite it has been considered an ideal situation of a limitless nonlinear medium, the results constitute a solid basis to mold more complex processes, such as those which take place in the plasma physics

  5. Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

    Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

    2015-01-01

    Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis of Graft Copolymers Based on Poly(2‐Methoxyethyl Acrylate) and Investigation of the Associated Water Structure

    Javakhishvili, Irakli; Tanaka, Masaru; Ogura, Keiko

    2012-01-01

    Graft copolymers composed of poly(2‐methoxyethyl acrylate) are prepared employing controlled radical polymerization techniques. Linear backbones bearing atom transfer radical polymerization (ATRP) initiating sites are obtained by reversible addition–fragmentation chain transfer copolymerization...... polydispersity indices (1.17–1.38) are attained. Thermal investigations of the graft copolymers indicate the presence of the freezing bound water, and imply that the materials may exhibit blood compatibility....

  7. Action of the complex Monge-Ampère operator on piecewise-linear functions and exponential tropical varieties

    Kazarnovskii, B Ya

    2014-01-01

    We consider exponential tropical varieties, which appear as analogues of algebraic tropical varieties when we pass from algebraic varieties to varieties given by zero sets of systems of exponential sums. We describe a construction of exponential tropical varieties arising from the action of the complex Monge-Ampère operator on piecewise-linear functions and show that every such variety can be obtained in this way. As an application, we deduce a criterion for the vanishing of the value of the mixed Monge-Ampère operator. This is an analogue and generalization of the criterion for the vanishing of the mixed volume of convex bodies

  8. An efficient method for minimizing a convex separable logarithmic function subject to a convex inequality constraint or linear equality constraint

    2006-01-01

    Full Text Available We consider the problem of minimizing a convex separable logarithmic function over a region defined by a convex inequality constraint or linear equality constraint, and two-sided bounds on the variables (box constraints. Such problems are interesting from both theoretical and practical point of view because they arise in some mathematical programming problems as well as in various practical problems such as problems of production planning and scheduling, allocation of resources, decision making, facility location problems, and so forth. Polynomial algorithms are proposed for solving problems of this form and their convergence is proved. Some examples and results of numerical experiments are also presented.

  9. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86

  10. Lowest excited states and optical absorption spectra of donor–acceptor copolymers for organic photovoltaics: a new picture emerging from tuned long-range corrected density functionals

    Pandey, Laxman; Doiron, Curtis; Sears, John S.; Bré das, Jean-Luc

    2012-01-01

    Polymers with low optical gaps are of importance to the organic photovoltaics community due to their potential for harnessing a large portion of the solar energy spectrum. The combination along their backbones of electron-rich and electron-deficient fragments contributes to the presence of low-lying excited states that are expected to display significant charge-transfer character. While conventional hybrid functionals are known to provide unsatisfactory results for charge-transfer excitations at the time-dependent DFT level, long-range corrected (LRC) functionals have been reported to give improved descriptions in a number of systems. Here, we use such LRC functionals, considering both tuned and default range-separation parameters, to characterize the absorption spectra of low-optical-gap systems of interest. Our results indicate that tuned LRC functionals lead to simulated optical-absorption properties in good agreement with experimental data. Importantly, the lowest-lying excited states (excitons) are shown to present a much more localized nature than initially anticipated. © 2012 the Owner Societies.

  11. SAN-b-P4VP block copolymer synthesis by chain extension from RAFT-functional poly(4-vinylpyridine) in solution and in emulsion

    Bozovic, J.S.; Tello Manon, H.M; Meuldijk, J.; Koning, C.E.; Klumperman, B.

    2007-01-01

    Reversible addition fragmentation chain transfer (RAFT)-mediated polymerization was successfully applied for the synthesis of poly(4-vinylpyridine) (P4VP) polymers of predetermined molar mass and of low polydispersity index. These RAFT end-functionalized polymers were then used as macro-RAFT agents

  12. Impact of molecular weight and degree of conjugation on the thermodynamics of DNA complexation and stability of polyethylenimine-graft-poly(ethylene glycol) copolymers.

    Smith, Ryan J; Beck, Rachel W; Prevette, Lisa E

    2015-01-01

    Poly(ethylene glycol) (PEG) is often conjugated to polyethylenimine (PEI) to provide colloidal stability to PEI-DNA polyplexes and shield charge leading to toxicity. Here, a library of nine cationic copolymers was synthesized by grafting three molecular weights (750, 2000, 5000Da) of PEG to linear PEI at three conjugation ratios. Using isothermal titration calorimetry, we have quantified the thermodynamics of the associations between the copolymers and DNA and determined the extent to which binding is hindered as a function of PEG molecular weight and conjugation ratio. Low conjugation ratios of 750Da PEG to PEI resulted in little decrease in DNA affinity, but a significant decrease-up to two orders of magnitude-was found for the other copolymers. We identified limitations in determination of affinity using indirect assays (electrophoretic mobility shift and ethidium bromide exclusion) commonly used in the field. Dynamic light scattering of the DNA complexes at physiological ionic strength showed that PEI modifications that did not reduce DNA affinity also did not confer significant colloidal stability, a finding that was supported by calorimetric data on the aggregation process. These results quantify the DNA interaction thermodynamics of PEGylated polycations for the first time and indicate that there is an optimum PEG chain length and degree of substitution in the design of agents that have desirable properties for effective in vivo gene delivery. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Facile synthesis of linear-dendritic cholesteryl-poly(epsilon-caprolactone)-b-(L-lysine)(G2) by thiol-ene and azide-alkyne "click" reactions

    Javakhishvili, Irakli; Binder, W.H.; Tanner, S.

    2010-01-01

    The construction of a linear-dendritic block copolymer consisting of terminal cholesteryl moiety, poly(epsilon-caprolactone), and a second generation L-lysine dendron has been accomplished by the combination of copper(I) catalyzed azide-alkyne and UV-triggered thiol-ene "click" reactions. Ring-op...... and thiocholesterol. Near to quantitative functionalization of the intermediate and final products has been attained as confirmed by NMR spectroscopy and MALDI-TOF spectrometry....

  14. Linear algebra

    Liesen, Jörg

    2015-01-01

    This self-contained textbook takes a matrix-oriented approach to linear algebra and presents a complete theory, including all details and proofs, culminating in the Jordan canonical form and its proof. Throughout the development, the applicability of the results is highlighted. Additionally, the book presents special topics from applied linear algebra including matrix functions, the singular value decomposition, the Kronecker product and linear matrix equations. The matrix-oriented approach to linear algebra leads to a better intuition and a deeper understanding of the abstract concepts, and therefore simplifies their use in real world applications. Some of these applications are presented in detailed examples. In several ‘MATLAB-Minutes’ students can comprehend the concepts and results using computational experiments. Necessary basics for the use of MATLAB are presented in a short introduction. Students can also actively work with the material and practice their mathematical skills in more than 300 exerc...

  15. Copolymers of fluorinated polydienes and sulfonated polystyrene

    Mays, Jimmy W [Knoxville, TN; Gido, Samuel P [Hadley, MA; Huang, Tianzi [Knoxville, TN; Hong, Kunlun [Knoxville, TN

    2009-11-17

    Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.

  16. Synthesis of biodegradable styrene copolymers

    Gevers, Dries; Kobben, Stephan; Junkers, Tanja; Copinet, Alain; Buntinx, Mieke; Peeters, Roos

    2017-01-01

    Polystyrene (PS), a versatile polymer with many applications (e.g. packaging) representing about 10% of the total annual polymer consumption, shows practically no biodegradability. In this study a styrene (ST) based copolymer is synthesized and examined regarding its ability to degrade in a composting test. As second monomer, to introduce biodegradable ester groups, 5,6-benzo-2-metylene-dioxepane (BMDO) has been used in radical copolymerization reactions performed in inert and stirred 10 m...

  17. Finite-time convergent recurrent neural network with a hard-limiting activation function for constrained optimization with piecewise-linear objective functions.

    Liu, Qingshan; Wang, Jun

    2011-04-01

    This paper presents a one-layer recurrent neural network for solving a class of constrained nonsmooth optimization problems with piecewise-linear objective functions. The proposed neural network is guaranteed to be globally convergent in finite time to the optimal solutions under a mild condition on a derived lower bound of a single gain parameter in the model. The number of neurons in the neural network is the same as the number of decision variables of the optimization problem. Compared with existing neural networks for optimization, the proposed neural network has a couple of salient features such as finite-time convergence and a low model complexity. Specific models for two important special cases, namely, linear programming and nonsmooth optimization, are also presented. In addition, applications to the shortest path problem and constrained least absolute deviation problem are discussed with simulation results to demonstrate the effectiveness and characteristics of the proposed neural network.

  18. Van der Waals potentials between metal clusters and helium atoms obtained with density functional theory and linear response methods

    Liebrecht, M.

    2014-01-01

    The importance of van der Waals interactions in many diverse research fields such as, e. g., polymer science, nano--materials, structural biology, surface science and condensed matter physics created a high demand for efficient and accurate methods that can describe van der Waals interactions from first principles. These methods should be able to deal with large and complex systems to predict functions and properties of materials that are technologically and biologically relevant. Van der Waals interactions arise due to quantum mechanical correlation effects and finding appropriate models an numerical techniques to describe this type of interaction is still an ongoing challenge in electronic structure and condensed matter theory. This thesis introduces a new variational approach to obtain intermolecular interaction potentials between clusters and helium atoms by means of density functional theory and linear response methods. It scales almost linearly with the number of electrons and can therefore be applied to much larger systems than standard quantum chemistry techniques. The main focus of this work is the development of an ab-initio method to account for London dispersion forces, which are purely attractive and dominate the interaction of non--polar atoms and molecules at large distances. (author) [de

  19. Position transitions of polymer-grafted nanoparticles in diblock-copolymer nanocomposites

    2011-04-01

    Full Text Available Self-assembly of block copolymer/nanoparticle blends has promising applications in the design and fabrication of novel functional nanomaterials. Precise control of the spatial positions of nanoparticles within block copolymer-based nanomaterials is crucial to achieve some special physical properties and functions. Here, we employ the self-consistent field method to theoretically investigate the self-assembly of polymer grafted-nanoparticles in a diblock copolymer. It is found that by varying the size and selectivity of nanoparticles, one can not only produce various self-assembled nanostructures but also modulate the spatial positions of the nanoparticles, either at the copolymer interfaces or in the center of one copolymer phase, within the nanostructures. A denser grafted polymer brush plays a role of shielding effect on nanoparticles and can position them into the center of one copolymer phase. The nanostructural transition we observed is dictated by the competition between entropy and enthalpy. On the basis of a number of simulations, two phase diagrams of self-assembled nanostructures are constructed. This study may be helpful for optimal design of advanced materials with desired nanostructures and enhanced performance.

  20. Self-assembly of block copolymer-based ionic supramolecules based upon multi-tail amphiphiles

    Asad Ayoubi, M.; Almdal, Kristoffer; Zhu, K.

    2015-01-01

    Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly...

  1. A Stream Function Theory Based Calculation of Wave Kinematics for Very Steep Waves Using a Novel Non-linear Stretching Technique

    Stroescu, Ionut Emanuel; Sørensen, Lasse; Frigaard, Peter Bak

    2016-01-01

    A non-linear stretching method was implemented for stream function theory to solve wave kinematics for physical conditions close to breaking waves in shallow waters, with wave heights limited by the water depth. The non-linear stretching method proves itself robust, efficient and fast, showing good...

  2. Electrospun poly(vinylidene fluoride) copolymer/octahydroxy-polyhedral oligomeric silsesquioxane nanofibrous mats as ionic liquid host: enhanced salt dissociation and its function in electrochromic device

    Zhou, Rui; Pramoda, Kumari Pallathadka; Liu, Wanshuang; Zhou, Dan; Ding, Guoqiang; He, Chaobin; Leong, Yew Wei; Lu, Xuehong

    2014-01-01

    Highlights: • The well dispersed POSS-OH promotes the dissociation of both LiClO 4 and BMIM + BF 4 − . • POSS-OH significantly increases the ionic conductivity and lithium transference number. • POSS-OH containing electrolyte improves the optical contrast of electrochromic device. - Abstract: Electrospun polymer nanofibrous mats loaded with ionic liquids (ILs) and lithium salts are promising non-volatile electrolytes owing to their high ionic conductivities. However, the large cations of ILs are difficult to diffuse into solid electrodes, whereas the lithium ions in ILs tend to form anionic complexes with the IL anions, reducing the number of free lithium ions. To address these issues, octa(3-hydroxy-3-methylbutyldimethylsiloxy) polyhedral oligomeric silsesquioxane (POSS-OH), which has large specific surface area and functionality number, is incorporated into electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) nanofibrous mats, and the mats are used to host LiClO 4 /1-butyl-3-methylimidazolium tetrafluoroborate (BMIM + BF 4 − ). It is found that POSS-OH can significantly increase both ionic conductivity and lithium transference number of the electrolytes owing to the Lewis acid-base interactions of POSS-OH with ClO 4 − and BF 4 − . The electrochromic device using the hybrid mat (with 5 wt% POSS-OH) loaded with LiClO 4 /BMIM + BF 4 − as the electrolyte shows significantly improved transmittance contrast and switching time, as a result of increased number of free lithium ions

  3. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    2010-04-01

    ... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended for... are available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug...

  4. Radiation resistance of ethylene-styrene copolymers

    Matsumoto, Kaoru; Ikeda, Masaaki; Ohki, Yoshimichi; Kusama, Yasuo; Harashige, Masahiro; Yazaki, Fumihiko.

    1988-01-01

    In this paper, the radiation resistance of ethylene-styrene copolymer, a polymeric resin developed newly by the authors, is reported. Resin examined were five kinds of ethylene-styrene copolymers: three random and two graft copolymers with different styrene contents. Low-density polyethylene was used as a reference. The samples were irradiated by 60 Co γ-rays to total absorbed doses up to 10 MGy. The mechanical properties of the smaples were examined. Infrared spectroscopy, differential scanning calorimetry and X-ray scattering techniques were used to examine the morphology of the samples. The random copolymers are soft and easy to extend, because benzene rings which exisist highly at random hinder the crystallization. As for the radiation resistance, they are highly resistant to γ-rays in the aspects of carbonyl group formation, gel formation, and elongation. Further, they show even better radiation resistance when proper additives were compounded in. The graft copolymers are hard to extend, because they consist of segregated polystyrene and polyethylene regions which are connected with each other. The tensile strength of irradiated graft copolymers does not decrease below that of unirradiated copolymers, up to a total dose of 10 MGy. As a consequence, it can be said that ethylene-styrene copolymers have good radiation resistance owing to the so-called 'sponge' effect of benzene rings. (author)

  5. Copolymers at the solid - liquid interface

    Wijmans, C.M.

    1994-01-01

    Copolymers consisting of both adsorbing and nonadsorbing segments can show an adsorption behaviour which is very different from that of homopolymers. We have mainly investigated the adsorption of AB diblock copolymers, which have one adsorbing block (anchor) and one nonadsorbing block

  6. Amphiphilic copolymers for fouling-release coatings

    Noguer, Albert Camós; Olsen, Stefan Møller; Hvilsted, Søren

    of the coatings [9,10,11]. This work shows the effect of an amphiphilic copolymer that induces hydrophilicity on the surface of the silicone-based fouling release coatings. The behaviour of these copolymers within the coating upon immersion and the interaction of these surface-active additives with other...

  7. Poly(ferrocenylsilane)-block-Polylactide Block Copolymers

    Roerdink, M.; van Zanten, Thomas S.; Hempenius, Mark A.; Zhong, Zhiyuan; Feijen, Jan; Vancso, Gyula J.

    2007-01-01

    A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS-b-PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and

  8. Molecular and vibrational structure of diphenylether and its 4,4' -dibromo derivative. Infrared linear dichroism spectroscopy and density functional theory calculations

    Eriksen, Troels K; Karlsen, Eva; Spanget-Larsen, Jens

    2015-01-01

    The title compounds were investigated by means of Linear Dichroism (LD) IR spectroscopy on samples partially aligned in uniaxially stretched low-density polyethylene and by density functional theory calculations. Satisfactory overall agreement between observed and calculated vibrational wavenumbers...

  9. New exact solutions of the Tzitzéica-type equations in non-linear optics using the expa function method

    Hosseini, K.; Ayati, Z.; Ansari, R.

    2018-04-01

    One specific class of non-linear evolution equations, known as the Tzitzéica-type equations, has received great attention from a group of researchers involved in non-linear science. In this article, new exact solutions of the Tzitzéica-type equations arising in non-linear optics, including the Tzitzéica, Dodd-Bullough-Mikhailov and Tzitzéica-Dodd-Bullough equations, are obtained using the expa function method. The integration technique actually suggests a useful and reliable method to extract new exact solutions of a wide range of non-linear evolution equations.

  10. Confirmation of linear system theory prediction: Rate of change of Herrnstein's κ as a function of response-force requirement

    McDowell, J. J; Wood, Helena M.

    1985-01-01

    Four human subjects worked on all combinations of five variable-interval schedules and five reinforcer magnitudes (¢/reinforcer) in each of two phases of the experiment. In one phase the force requirement on the operandum was low (1 or 11 N) and in the other it was high (25 or 146 N). Estimates of Herrnstein's κ were obtained at each reinforcer magnitude. The results were: (1) response rate was more sensitive to changes in reinforcement rate at the high than at the low force requirement, (2) κ increased from the beginning to the end of the magnitude range for all subjects at both force requirements, (3) the reciprocal of κ was a linear function of the reciprocal of reinforcer magnitude for seven of the eight data sets, and (4) the rate of change of κ was greater at the high than at the low force requirement by an order of magnitude or more. The second and third findings confirm predictions made by linear system theory, and replicate the results of an earlier experiment (McDowell & Wood, 1984). The fourth finding confirms a further prediction of the theory and supports the theory's interpretation of conflicting data on the constancy of Herrnstein's κ. PMID:16812408

  11. Confirmation of linear system theory prediction: Rate of change of Herrnstein's kappa as a function of response-force requirement.

    McDowell, J J; Wood, H M

    1985-01-01

    Four human subjects worked on all combinations of five variable-interval schedules and five reinforcer magnitudes ( cent/reinforcer) in each of two phases of the experiment. In one phase the force requirement on the operandum was low (1 or 11 N) and in the other it was high (25 or 146 N). Estimates of Herrnstein's kappa were obtained at each reinforcer magnitude. The results were: (1) response rate was more sensitive to changes in reinforcement rate at the high than at the low force requirement, (2) kappa increased from the beginning to the end of the magnitude range for all subjects at both force requirements, (3) the reciprocal of kappa was a linear function of the reciprocal of reinforcer magnitude for seven of the eight data sets, and (4) the rate of change of kappa was greater at the high than at the low force requirement by an order of magnitude or more. The second and third findings confirm predictions made by linear system theory, and replicate the results of an earlier experiment (McDowell & Wood, 1984). The fourth finding confirms a further prediction of the theory and supports the theory's interpretation of conflicting data on the constancy of Herrnstein's kappa.

  12. Spectroscopic investigations using density functional theory on 2-methoxy- 4(phenyliminomethyl)phenol: A non linear optical material

    Hijas, K. M.; Madan Kumar, S.; Byrappa, K.; Geethakrishnan, T.; Jeyaram, S.; Nagalakshmi, R.

    2018-03-01

    Single crystals of 2-methoxy-4(phenyliminomethyl)phenol were grown from ethanol by slow evaporation solution growth technique. Single crystal X-ray diffraction experiment reveals the crystallization in orthorhombic system having non-centrosymmetric space group C2221. Geometrical optimization by density functional theory method was carried out using Gaussian program and compared with experimental results. Detailed experimental and theoretical vibrational analyses were carried out and the results were correlated to find close agreement. Thermal analyses show the material is thermally stable with a melting point of 159 °C. Natural bond orbital analysis was carried out to explain charge transfer interactions through hydrogen bonding. Relatively smaller HOMO-LUMO band gap favors the non linear optical activity of the molecule. Natural population analysis and molecular electrostatic potential calculations visualize the charge distribution in an isolated molecule. Calculated first-order molecular hyperpolarizability and preliminary second harmonic generation test carried out using Kurtz-Perry technique establish 2-methoxy-4(phenyliminomethyl)phenol crystal as a good non linear optical material. Z-scan proposes the material for reverse saturable absorption.

  13. Comparison of x ray computed tomography number to proton relative linear stopping power conversion functions using a standard phantom.

    Moyers, M F

    2014-06-01

    Adequate evaluation of the results from multi-institutional trials involving light ion beam treatments requires consideration of the planning margins applied to both targets and organs at risk. A major uncertainty that affects the size of these margins is the conversion of x ray computed tomography numbers (XCTNs) to relative linear stopping powers (RLSPs). Various facilities engaged in multi-institutional clinical trials involving proton beams have been applying significantly different margins in their patient planning. This study was performed to determine the variance in the conversion functions used at proton facilities in the U.S.A. wishing to participate in National Cancer Institute sponsored clinical trials. A simplified method of determining the conversion function was developed using a standard phantom containing only water and aluminum. The new method was based on the premise that all scanners have their XCTNs for air and water calibrated daily to constant values but that the XCTNs for high density/high atomic number materials are variable with different scanning conditions. The standard phantom was taken to 10 different proton facilities and scanned with the local protocols resulting in 14 derived conversion functions which were compared to the conversion functions used at the local facilities. For tissues within ±300 XCTN of water, all facility functions produced converted RLSP values within ±6% of the values produced by the standard function and within 8% of the values from any other facility's function. For XCTNs corresponding to lung tissue, converted RLSP values differed by as great as ±8% from the standard and up to 16% from the values of other facilities. For XCTNs corresponding to low-density immobilization foam, the maximum to minimum values differed by as much as 40%. The new method greatly simplifies determination of the conversion function, reduces ambiguity, and in the future could promote standardization between facilities. Although it

  14. Linear regression

    Olive, David J

    2017-01-01

    This text covers both multiple linear regression and some experimental design models. The text uses the response plot to visualize the model and to detect outliers, does not assume that the error distribution has a known parametric distribution, develops prediction intervals that work when the error distribution is unknown, suggests bootstrap hypothesis tests that may be useful for inference after variable selection, and develops prediction regions and large sample theory for the multivariate linear regression model that has m response variables. A relationship between multivariate prediction regions and confidence regions provides a simple way to bootstrap confidence regions. These confidence regions often provide a practical method for testing hypotheses. There is also a chapter on generalized linear models and generalized additive models. There are many R functions to produce response and residual plots, to simulate prediction intervals and hypothesis tests, to detect outliers, and to choose response trans...

  15. Evolution of Wigner function in laser process under the action of linear resonance force and its application

    Dao-ming, Lu

    2018-05-01

    The negativity of Wigner function (WF) is one of the important symbols of non-classical properties of light field. Therefore, it is of great significance to study the evolution of WF in dissipative process. The evolution formula of WF in laser process under the action of linear resonance force is given by virtue of thermo entangled state representation and the technique of integration within an ordered product of operator. As its application, the evolution of WF of thermal field and that of single-photon-added coherent state are discussed. The results show that the WF of thermal field maintains its original character. On the other hand, the negative region size and the depth of negativity of WF of single- photon-added coherent state decrease until it vanishes with dissipation. This shows that the non-classical property of single-photon-added coherent state is weakened, until it disappears with dissipation time increasing.

  16. Linearization and Control of Series-Series Compensated Inductive Power Transfer System Based on Extended Describing Function Concept

    Kunwar Aditya

    2016-11-01

    Full Text Available The extended describing function (EDF is a well-known method for modelling resonant converters due to its high accuracy. However, it requires complex mathematical formulation effort. This paper presents a simplified non-linear mathematical model of series-series (SS compensated inductive power transfer (IPT system, considering zero-voltage switching in the inverter. This simplified mathematical model permits the user to derive the small-signal model using the EDF method, with less computational effort, while maintaining the accuracy of an actual physical model. The derived model has been verified using a frequency sweep method in PLECS. The small-signal model has been used to design the voltage loop controller for a SS compensated IPT system. The designed controller was implemented on a 3.6 kW experimental setup, to test its robustness.

  17. Multistability of neural networks with discontinuous non-monotonic piecewise linear activation functions and time-varying delays.

    Nie, Xiaobing; Zheng, Wei Xing

    2015-05-01

    This paper is concerned with the problem of coexistence and dynamical behaviors of multiple equilibrium points for neural networks with discontinuous non-monotonic piecewise linear activation functions and time-varying delays. The fixed point theorem and other analytical tools are used to develop certain sufficient conditions that ensure that the n-dimensional discontinuous neural networks with time-varying delays can have at least 5(n) equilibrium points, 3(n) of which are locally stable and the others are unstable. The importance of the derived results is that it reveals that the discontinuous neural networks can have greater storage capacity than the continuous ones. Moreover, different from the existing results on multistability of neural networks with discontinuous activation functions, the 3(n) locally stable equilibrium points obtained in this paper are located in not only saturated regions, but also unsaturated regions, due to the non-monotonic structure of discontinuous activation functions. A numerical simulation study is conducted to illustrate and support the derived theoretical results. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Abnormal Functional Connectivity of Resting State Network Detection Based on Linear ICA Analysis in Autism Spectrum Disorder.

    Bi, Xia-An; Zhao, Junxia; Xu, Qian; Sun, Qi; Wang, Zhigang

    2018-01-01

    Some functional magnetic resonance imaging (fMRI) researches in autism spectrum disorder (ASD) patients have shown that ASD patients have significant impairment in brain response. However, few researchers have studied the functional structure changes of the eight resting state networks (RSNs) in ASD patients. Therefore, research on statistical differences of RSNs between 42 healthy controls (HC) and 50 ASD patients has been studied using linear independent component analysis (ICA) in this paper. Our researches showed that there was abnormal functional connectivity (FC) of RSNs in ASD patients. The RSNs with the decreased FC and increased FC in ASD patients included default mode network (DMN), central executive network (CEN), core network (CN), visual network (VN), self-referential network (SRN) compared to HC. The RSNs with the increased FC in ASD patients included auditory network (AN), somato-motor network (SMN). The dorsal attention network (DAN) in ASD patients showed the decreased FC. Our findings indicate that the abnormal FC in RSNs extensively exists in ASD patients. Our results have important contribution for the study of neuro-pathophysiological mechanisms in ASD patients.

  19. A new enhanced bat-inspired algorithm for finding linear supply function equilibrium of GENCOs in the competitive electricity market

    Niknam, Taher; Sharifinia, Sajjad; Azizipanah-Abarghooee, Rasoul

    2013-01-01

    Highlights: • Present optimal bidding strategies of Generating Companies (GENCOs) in a network-constrained electricity market. • Present new enhanced bat-inspired algorithm. • Consider the bi level optimization problem. • Present a linear supply function model. - Abstract: This paper proposes a new enhanced bat-inspired algorithm to find out linear supply function equilibrium of Generating Companies (GENCOs) in a network-constrained electricity market where they have incomplete information about other rivals. The model enables a GENCO to link its bidding price with the bidding quantity of its product. In this regard, the social welfare maximization is applied to clearing the market and nodal pricing mechanism is utilized to calculate the GENCO’s profit. It is formulated as a bi level optimization problem, where the higher level problem maximizes GENCO’s payoff and the lower level problem solves the independent system operator’s market clearing problem based on the maximization of social welfare. Due to non-convexity nature of the proposed bi level optimization problem, the mathematical-based optimization approach is incapable to solve the problem and obtain the nearly global optima. In order to overcome the obstacle of the conventional approaches, this study suggests a new meta-heuristic Bat-inspired Algorithm (BA) to achieve the nearly global solution of the bi level optimization problem. In addition a novel self-adaptive learning mechanism is utilized on the original BA to improve the population diversity and global searching capability. Numerical examples are applied to three test systems in order to evaluate the performances of the presented framework

  20. Field-theoretic simulations of block copolymer nanocomposites in a constant interfacial tension ensemble.

    Koski, Jason P; Riggleman, Robert A

    2017-04-28

    Block copolymers, due to their ability to self-assemble into periodic structures with long range order, are appealing candidates to control the ordering of functionalized nanoparticles where it is well-accepted that the spatial distribution of nanoparticles in a polymer matrix dictates the resulting material properties. The large parameter space associated with block copolymer nanocomposites makes theory and simulation tools appealing to guide experiments and effectively isolate parameters of interest. We demonstrate a method for performing field-theoretic simulations in a constant volume-constant interfacial tension ensemble (nVγT) that enables the determination of the equilibrium properties of block copolymer nanocomposites, including when the composites are placed under tensile or compressive loads. Our approach is compatible with the complex Langevin simulation framework, which allows us to go beyond the mean-field approximation. We validate our approach by comparing our nVγT approach with free energy calculations to determine the ideal domain spacing and modulus of a symmetric block copolymer melt. We analyze the effect of numerical and thermodynamic parameters on the efficiency of the nVγT ensemble and subsequently use our method to investigate the ideal domain spacing, modulus, and nanoparticle distribution of a lamellar forming block copolymer nanocomposite. We find that the nanoparticle distribution is directly linked to the resultant domain spacing and is dependent on polymer chain density, nanoparticle size, and nanoparticle chemistry. Furthermore, placing the system under tension or compression can qualitatively alter the nanoparticle distribution within the block copolymer.

  1. Polydimethylsiloxane-polymethacrylate block copolymers tethering quaternary ammonium salt groups for antimicrobial coating

    Qin, Xiaoshuai; Li, Yancai; Zhou, Fang; Ren, Lixia; Zhao, Yunhui, E-mail: zhaoyunhui@tju.edu.cn; Yuan, Xiaoyan

    2015-02-15

    Highlights: • A series of PDMS-b-QPDMAEMA block copolymers were synthesized via RAFT polymerization. • The composition and morphology of the copolymer films strongly depended on the content of QPDMAEMA. • Migration of QPDMAEMA blocks toward surface was promoted when contacting with water. • Heterogeneous film surfaces with higher N{sup +} content exhibited more obvious antimicrobial activity. - Abstract: Block copolymers PDMS-b-PDMAEMA were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization involving N,N-dimethylaminoethyl methacrylate (DMAEMA) by using poly(dimethylsiloxane) (PDMS) macro-chain transfer agent. And, the tertiary amino groups in PDMAEMA were quaternized with n-octyliodide to provide quaternary ammonium salts (QPDMAEMA). The well-defined copolymers generated composition variation and morphology evolvement on film surfaces, which were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle measurements. The results indicated that the enrichment of QPDMAEMA brought about lower elemental ratios of Si/N on the film surfaces. The surface morphologies evolved with the variations of QPDMAEMA content, and the variation trend of film roughness was exactly opposite to that of water contact angle hysteresis. With regard to structure-antimicrobial relationships, the copolymer films had more evident antimicrobial activity against Gram-positive, Bacillus subtilis, and the surfaces with heterogeneous morphology and higher N{sup +} content presented better antimicrobial activity. The functionalized copolymers based PDMS and quaternary ammonium salts materials have the potential applications as antimicrobial coatings.

  2. Mesoscopic multiphase structures and the interfaces of block and graft copolymers in bulk

    Matsushita, Yushu

    1996-01-01

    Microphase-separated structures of copolymers with various architectures and their polymer/polymer interfaces were studied. They are SP diblock, PSP triblock, and SPP graft copolymers, where S and P denote polystyrene and poly(2-vinylpyridine), respectively. Morphological observations were carried out by means of transmission electron microscopy and small-angle X-ray scattering. Chain dimensions of component polymers were measured by small-angle neutron scattering and microphase-separated interfaces were observed by neutron reflectivity measurements using deuterium-labeled samples. It was clarified that morphological phase transitions among thermodynamically equilibrium structures for SP diblock and PSP triblock copolymers occur at almost the same compositions; however, those of SPP graft copolymers tend to occur at higher volume fraction of polystyrene, φ s , than those for block copolymers. As for alternating lamellar structures it turned out to be clear that lamellar domain spacings, D's, were scaled as the 2/3 power of the molecular weight of polymers irrespective of their architectures. S block chains of SP diblock and PSP triblock copolymers in lamellar structures were both confirmed to be deformed toward the direction perpendicular to the lamellar interfaces, but it revealed that their volumes were preserved. Further, S/P interfacial thicknesses of SP and PSP were essentially the same to each other and the values defined as the FWHM of the error functions which express the segment density distributions of the interfaces were determined to be about 4 nm. (author)

  3. Photoacoustic Monitoring of Internal Plastification in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate Copolymers: Measurements of Thermal Parameters

    Sanchez Ruben R.

    1999-01-01

    Full Text Available Basic data on thermophysical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate copolymers poly(3HB-co-3HV were investigated with the aim of understanding the role of 3-hydroxyvalerate monomeric units (3HV incorporated during random copolymerization. The results show strong evidence that internal plastification is produced by the introduction of 3HV units in the copolymer. It was observed that copolymer thermal conductivity increased approximately linearly with the 3HV content. On the other hand, thermal diffusivity was very sensitive to the change in the copolymer composition showing a sudden rise that attained a saturation plateau. Amplitude-frequency plots indicate that a thermoelastic bending mechanism is operating. In this paper a new photoacoustic arrangement for the measurement of thermal effusivity is presented.

  4. Dissipative particle dynamics of triblock copolymer melts: A midblock conformational study at moderate segregation

    Tallury, Syamal S.; Spontak, Richard J.; Pasquinelli, Melissa A.

    2014-12-01

    As thermoplastic elastomers, triblock copolymers constitute an immensely important class of shape-memory soft materials due to their unique ability to form molecular networks stabilized by physical, rather than chemical, cross-links. The extent to which such networks develop in triblock and higher-order multiblock copolymers is sensitive to the formation of midblock bridges, which serve to connect neighboring microdomains. In addition to bridges, copolymer molecules can likewise form loops and dangling ends upon microphase separation or they can remain unsegregated. While prior theoretical and simulation studies have elucidated the midblock bridging fraction in triblock copolymer melts, most have only considered strongly segregated systems wherein dangling ends and unsegregated chains become relatively insignificant. In this study, simulations based on dissipative particle dynamics are performed to examine the self-assembly and networkability of moderately segregated triblock copolymers. Utilizing a density-based cluster-recognition algorithm, we demonstrate how the simulations can be analyzed to extract information about microdomain formation and permit explicit quantitation of the midblock bridging, looping, dangling, and unsegregated fractions for linear triblock copolymers varying in chain length, molecular composition, and segregation level. We show that midblock conformations can be sensitive to variations in chain length, molecular composition, and bead repulsion, and that a systematic investigation can be used to identify the onset of strong segregation where the presence of dangling and unsegregated fractions are minimal. In addition, because this clustering approach is robust, it can be used with any particle-based simulation method to quantify network formation of different morphologies for a wide range of triblock and higher-order multiblock copolymer systems.

  5. The effect of breed and parity on curves of body condition during lactation estimated using a non-linear function.

    Friggens, N C; Badsberg, J H

    2007-05-01

    The objectives of this study were to see if the body condition score curve during lactation could be described using a model amenable to biological interpretation, a non-linear function assuming exponential rates of change in body condition with time, and to quantify the effect of breed and parity on curves of body condition during lactation. Three breeds were represented: Danish Holstein (n = 112), Danish Red (n = 97) and Jerseys (n = 8). Cows entered the experiment at the start of first lactation and were studied during consecutive lactations (average number of lactations 2, minimum 1, maximum 3). They remained on the same dietary treatment throughout. Body condition was scored to the nearest half unit on the Danish scale (see Kristensen (1986); derived from the Lowman et al. (1976) system) from 1 to 5 on days: 2, 14, 28, 42, 56, 84, 112, 168, 224 after calving. Additionally, condition score was recorded on the day of drying off the cow, 35, 21, and 7 days before expected calving and finally on the day of calving. All condition scores were made by the trained personal on the research farm, where the same person made 92% of the scores. The temporal patterns in condition score were modelled as consisting of two underlying processes, one related to days from calving, referred to as lactation only, the other to days from (subsequent) conception, referred to as pregnancy. Both processes were assumed to be exponential functions of time. Each process was modelled separately using exponential functions, i.e. one model for lactation only and one for pregnancy, and then a combined model for both lactation only and pregnancy was fitted. The data set contained 467 lactation periods and 378 pregnancy periods. The temporal patterns in condition score of cows kept under stable and sufficient nutritional conditions were successfully described using a two component non-linear function. First lactation cows had shallower curves, they had greater condition scores at the nadir

  6. Rapid self-assembly of block copolymers to photonic crystals

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  7. Self-Assembly of Narrowly Dispersed Brush Diblock Copolymers with Domain Spacing more than 100 nm

    Gu, Weiyin; Sveinbjornsson, Benjamin; Hong, Sung Woo; Grubbs, Robert; Russell, Thomas

    2012-02-01

    Self-assembled structures of high molecular weight (MW), narrow molecular weight distribution brush block copolymers containing polylactic acid (PLA) and polystyrene (PS) side chains with similar MWs were studied in both the melt and thin films. The polynorbornene-backbone-based brush diblock copolymers containing approximately equal volume fractions of each block self-assembled into highly ordered lamellae with domain spacing over 100 nm, as revealed by SAXS, GISAXS and AFM. The domain size increased approximately linearly with backbone length, which indicated an extended conformation of the backbone in the ordered state. The length of side chains also played a significant role in terms of controlling the domain size. As the degree of polymerization (DP) increased, the symmetric brush diblock copolymers with longer side chains tended to form larger lamellar microdomains in comparison to those that have the same DP but shorter side chains.

  8. Highχ block copolymers for directed self-assembly patterning without the need for topcoat or solvent annealing

    Xu, Kui; Hockey, Mary Ann; Calderas, Eric; Guerrero, Douglas; Sweat, Daniel; Fiehler, Jeffrey

    2017-03-01

    High-χ block copolymers for directed self-assembly (DSA) patterning that do not need topcoat or solvent annealing have been developed. A variety of functionalities have been successfully added into the block copolymers, such as balanced surface energy between the polymer blocks, outstandingly high χ, tunable glass transition temperature (Tg), and selective crosslinking. Perpendicular orientation control, as desired for patterning, of the block copolymers can be simply achieved by thermal annealing due to the equal surface energy of the polymer blocks at the annealing temperatures, which allows avoiding solvent annealing or top-coat. The χ value can be tuned up to achieve L0 as low as 8-10 nm for lamellar-structured block copolymers and hole/pillar size as small as 5-6 nm for cylinder-structured block copolymers. The Tg of the block copolymers can be tuned to improve the kinetics of thermal annealing by enhancing the polymer chain mobility. Block-selective crosslinking facilitates the pattern transfer by mitigating pattern collapse during wet etching and improving oxygen plasma etching selectivity between the polymer blocks. This paper provides an introductory review of our high-χ block copolymer materials with various functionalities for achieving improved DSA performance.

  9. Physical properties of metallocenes propene-higher α-olefins copolymers

    Lovisi, Humberto; Santa Maria, Luiz Claudio de; Coutinho, Fernanda M.B.

    2001-01-01

    In this work, new copolymers of propene/1-hexene (PHC) and propene/1-octene (POC) were synthesized by using a highly iso specific metallocenes catalyst system based on rac-Me 2 Si(2-ethyl,4-phenyl,1-indenyl) 2 ZrCl 2 , in the homogeneous and heterogeneous forms, methylaluminoxane (MAO) activated. An investigation about the copolymerization of propene with 1-hexene and 1-octene using this catalyst system illustrates the potential for the tailoring of propene/higher α-olefin copolymers with controlled thermal and mechanical properties by varying the comonomer concentration in the polymerization feed. Both catalyst systems showed high activity and produced random copolymers with very low or no detectable crystallinity. It was observed that properties such as enthalpy of crystallization (ΔHc), crystallization temperature (Tc), melting temperature (Tm), glass transition temperature (Tg) and elastic modulus (E') decreased in a linear pattern with increasing comonomer content in the copolymer. The effect of the short chain branch length was also investigated and it was observed that, compared to 1-hexene, much less 1-octene was necessary to disrupt the crystalline structure and impart rubbery behaviour to the copolymers. (author)

  10. Application of the principal fractional meta-trigonometric functions for the solution of linear commensurate-order time-invariant fractional differential equations.

    Lorenzo, C F; Hartley, T T; Malti, R

    2013-05-13

    A new and simplified method for the solution of linear constant coefficient fractional differential equations of any commensurate order is presented. The solutions are based on the R-function and on specialized Laplace transform pairs derived from the principal fractional meta-trigonometric functions. The new method simplifies the solution of such fractional differential equations and presents the solutions in the form of real functions as opposed to fractional complex exponential functions, and thus is directly applicable to real-world physics.

  11. Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

    Kwak, Jongheon; Han, Sunghyun; Kim, Jin Kon

    2014-03-01

    A binary mixture of two block copolymers whose blocks are capable of forming the hydrogen bonding allows one to obtain various microdomains that could not be expected for neat block copolymer. For instance, the binary blend of symmetric polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) and polystyrene-block-polyhydroxystyrene copolymer (PS-b-PHS) blends where the hydrogen bonding occurred between P2VP and PHS showed hexagonally packed (HEX) cylindrical and body centered cubic (BCC) spherical microdomains. To know the exact location of short block copolymer chains at the interface, we synthesized deuterated polystyrene-block-polyhydroxystyrene copolymer (dPS-b-PHS) and prepared a binary mixture with PS-b-P2VP. We investigate, via small angle X-ray scattering (SAXS) and neutron reflectivity (NR), the exact location of shorter dPS block chain near the interface of the microdomains.

  12. Proton conducting graft copolymers with tunable length and density of phosphonated side chains for fuel cell membranes

    Dimitrov, Ivaylo; Takamuku, Shogo; Jankova Atanasova, Katja

    2014-01-01

    Polysulfones functionalized with highly phosphonated poly(pentafluorostyrene) side chains of different lengths were synthesized applying controlled polymerization and modification methods. The graft copolymers' thermal properties were evaluated by differential scanning calorimetry and thermal...... gravimetrical analyses. The proton conductivity of membrane prepared from the graft copolymer with the shortest phosphonated side chains was 134 mS cm(-1) at 100 degrees C under fully immersed conditions. The graft copolymer TEM image shows a nanophase separation of ion-rich segments within the polysulfone...

  13. Micellization and Dynamics of a Block Copolymer

    Hvidt, Søren

    2006-01-01

    and copolymer mixtures, and evidence in favor of a multi-equilibria unimer-micelle model will be presented. Results obtained by liquid chromatographic methods will be shown and it will be demonstrated that commercial EPE copolymers are inhomogeneous at several levels and many of their unusual properties reflect...... ratios and temperature. The micellization process with increasing temperature has been followed by a number of techniques including differential scanning calorimetry, liquid chromatography, and surface tension measurements. Different micellization models have been tested for purified copolymers...

  14. PEO-related block copolymer surfactants

    Mortensen, K.

    2001-01-01

    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems...... of such PEG-based block copolymers in aqueous suspensions are reviewed. Based on scattering experiments using either X-ray or neutrons, the phase behavior is characterized, showing that the thermo-reversible gelation is a result of micellar ordering into mesoscopic crystalline phases of cubic, hexagonal...

  15. Controlled specific placement of nanoparticles into microdomains of block copolymer thin films

    Bae, Joonwon, E-mail: joonwonbae@gmail.com [Department of Applied Chemistry, Dongduk Women' s University, Seoul 136-714 (Korea, Republic of); Kim, Jungwook [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 121-742 (Korea, Republic of); Park, Jongnam, E-mail: jnpark@unist.ac.kr [Interdisciplinary School of Green Energy, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798 (Korea, Republic of)

    2014-07-01

    Conceptually attractive hybrid materials composed of nanoparticles and elegant block copolymers have become important for diverse applications. In this work, controlled specific placement of nanoparticles such as gold (Au) and titania (TiO{sub 2}) into microphase separated domains in poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films was demonstrated. The effect of nanoparticle surface functionality on the spatial location of particles inside polymer film was observed by transmission electron microscopy. It was revealed that the location of nanoparticles was highly dependent on the surface ligand property of nanoparticle. In addition, the microphase separation behavior of thin block copolymer film was also affected by the nanoparticle surface functional groups. This study might provide a way to understand the properties and behaviors of numerous block copolymer/nanoparticle hybrid systems. - Highlights: • Controlled location of nanoparticles in the block copolymer matrix • Tailoring surface functionality of metal nanocrystals • Fabrication of homogeneous nanocomposites using organic inorganic components • Possibility for the preparation of nanohybrids.

  16. Controlled specific placement of nanoparticles into microdomains of block copolymer thin films

    Bae, Joonwon; Kim, Jungwook; Park, Jongnam

    2014-01-01

    Conceptually attractive hybrid materials composed of nanoparticles and elegant block copolymers have become important for diverse applications. In this work, controlled specific placement of nanoparticles such as gold (Au) and titania (TiO 2 ) into microphase separated domains in poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films was demonstrated. The effect of nanoparticle surface functionality on the spatial location of particles inside polymer film was observed by transmission electron microscopy. It was revealed that the location of nanoparticles was highly dependent on the surface ligand property of nanoparticle. In addition, the microphase separation behavior of thin block copolymer film was also affected by the nanoparticle surface functional groups. This study might provide a way to understand the properties and behaviors of numerous block copolymer/nanoparticle hybrid systems. - Highlights: • Controlled location of nanoparticles in the block copolymer matrix • Tailoring surface functionality of metal nanocrystals • Fabrication of homogeneous nanocomposites using organic inorganic components • Possibility for the preparation of nanohybrids

  17. Formation and Characterization of Anisotropic Block Copolymer Gels

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  18. Ductile electroactive biodegradable hyperbranched polylactide copolymers enhancing myoblast differentiation.

    Xie, Meihua; Wang, Ling; Guo, Baolin; Wang, Zhong; Chen, Y Eugene; Ma, Peter X

    2015-12-01

    Myotube formation is crucial to restoring muscular functions, and biomaterials that enhance the myoblast differentiation into myotubes are highly desirable for muscular repair. Here, we report the synthesis of electroactive, ductile, and degradable copolymers and their application in enhancing the differentiation of myoblasts to myotubes. A hyperbranched ductile polylactide (HPLA) was synthesized and then copolymerized with aniline tetramer (AT) to produce a series of electroactive, ductile and degradable copolymers (HPLAAT). The HPLA and HPLAAT showed excellent ductility with strain to failure from 158.9% to 42.7% and modulus from 265.2 to 758.2 MPa. The high electroactivity of the HPLAAT was confirmed by UV spectrometer and cyclic voltammogram measurements. These HPLAAT polymers also showed improved thermal stability and controlled biodegradation rate compared to HPLA. Importantly, when applying these polymers for myotube formation, the HPLAAT significantly improved the proliferation of C2C12 myoblasts in vitro compared to HPLA. Furthermore, these polymers greatly promoted myogenic differentiation of C2C12 cells as measured by quantitative analysis of myotube number, length, diameter, maturation index, and gene expression of MyoD and TNNT. Together, our study shows that these electroactive, ductile and degradable HPLAAT copolymers represent significantly improved biomaterials for muscle tissue engineering compared to HPLA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Dynamics of Disordered PI-PtBS Diblock Copolymer

    Watanabe, Hiroshi

    2009-03-01

    Viscoelastic (G^*) and dielectric (ɛ'') data were examined for a LCST-type diblock copolymer composed of polyisoprene (PI; M = 53K) and poly(p-tert- butyl styrene) (PtBS; M = 42K) blocks disordered at T PtBS block at low T and the dynamic heterogeneity due to PtBS was effectively quenched to give a frictional nonuniformity for the PI block relaxation. The ɛ'' data were thermo-rheologically complex at low T, partly due to this nonuniformity. However, the block connectivity could have also led to the complexity. For testing this effect, the ɛ'' data were reduced at the iso- frictional state defined with respect to bulk PI. In this state, the ɛ'' data of the copolymer at low and high T, respectively, were close to the data for the star-branched and linear bulk PI. Thus, the PI block appeared to be effectively tethered in space at low T thereby behaving similarly to the star arm while the PI block tended to move cooperatively with the PtBS block at high T to behave similarly to the linear PI, which led to the complexity of the ɛ'' data. The PtBS block also exhibited the complexity (noted from the G^* data), which was well correlated with the complexity of the PI block.

  20. Nonaqueous Dispersion Formed by an Emulsion Solvent Evaporation Method Using Block-Random Copolymer Surfactant Synthesized by RAFT Polymerization.

    Ezaki, Naofumi; Watanabe, Yoshifumi; Mori, Hideharu

    2015-10-27

    As surfactants for preparation of nonaqueous microcapsule dispersions by the emulsion solvent evaporation method, three copolymers composed of stearyl methacrylate (SMA) and glycidyl methacrylate (GMA) with different monomer sequences (i.e., random, block, and block-random) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Despite having the same comonomer composition, the copolymers exhibited different functionality as surfactants for creating emulsions with respective dispersed and continuous phases consisting of methanol and isoparaffin solvent. The optimal monomer sequence for the surfactant was determined based on the droplet sizes and the stabilities of the emulsions created using these copolymers. The block-random copolymer led to an emulsion with better stability than obtained using the random copolymer and a smaller droplet size than achieved with the block copolymer. Modification of the epoxy group of the GMA unit by diethanolamine (DEA) further decreased the droplet size, leading to higher stability of the emulsion. The DEA-modified block-random copolymer gave rise to nonaqueous microcapsule dispersions after evaporation of methanol from the emulsions containing colored dyes in their dispersed phases. These dispersions exhibited high stability, and the particle sizes were small enough for application to the inkjet printing process.

  1. A guide to developing resource selection functions from telemetry data using generalized estimating equations and generalized linear mixed models

    Nicola Koper

    2012-03-01

    Full Text Available Resource selection functions (RSF are often developed using satellite (ARGOS or Global Positioning System (GPS telemetry datasets, which provide a large amount of highly correlated data. We discuss and compare the use of generalized linear mixed-effects models (GLMM and generalized estimating equations (GEE for using this type of data to develop RSFs. GLMMs directly model differences among caribou, while GEEs depend on an adjustment of the standard error to compensate for correlation of data points within individuals. Empirical standard errors, rather than model-based standard errors, must be used with either GLMMs or GEEs when developing RSFs. There are several important differences between these approaches; in particular, GLMMs are best for producing parameter estimates that predict how management might influence individuals, while GEEs are best for predicting how management might influence populations. As the interpretation, value, and statistical significance of both types of parameter estimates differ, it is important that users select the appropriate analytical method. We also outline the use of k-fold cross validation to assess fit of these models. Both GLMMs and GEEs hold promise for developing RSFs as long as they are used appropriately.

  2. Electrostatic interactions in finite systems treated with periodic boundary conditions: application to linear-scaling density functional theory.

    Hine, Nicholas D M; Dziedzic, Jacek; Haynes, Peter D; Skylaris, Chris-Kriton

    2011-11-28

    We present a comparison of methods for treating the electrostatic interactions of finite, isolated systems within periodic boundary conditions (PBCs), within density functional theory (DFT), with particular emphasis on linear-scaling (LS) DFT. Often, PBCs are not physically realistic but are an unavoidable consequence of the choice of basis set and the efficacy of using Fourier transforms to compute the Hartree potential. In such cases the effects of PBCs on the calculations need to be avoided, so that the results obtained represent the open rather than the periodic boundary. The very large systems encountered in LS-DFT make the demands of the supercell approximation for isolated systems more difficult to manage, and we show cases where the open boundary (infinite cell) result cannot be obtained from extrapolation of calculations from periodic cells of increasing size. We discuss, implement, and test three very different approaches for overcoming or circumventing the effects of PBCs: truncation of the Coulomb interaction combined with padding of the simulation cell, approaches based on the minimum image convention, and the explicit use of open boundary conditions (OBCs). We have implemented these approaches in the ONETEP LS-DFT program and applied them to a range of systems, including a polar nanorod and a protein. We compare their accuracy, complexity, and rate of convergence with simulation cell size. We demonstrate that corrective approaches within PBCs can achieve the OBC result more efficiently and accurately than pure OBC approaches.

  3. Barite formation in the presence of a commercial copolymer

    Ruiz-Agudo, Cristina; Putnis, Christine; Ruiz-Agudo, Encarnacion; Putnis, Andrew

    2015-04-01

    Fluid composition can significantly modify the mechanisms of mineral formation. Particularly, the presence of organic additives in the aqueous media has been shown to alter the precipitation of minerals substantially (e.g. calcium carbonate, barium carbonate and barium sulfate). Despite the numerous studies dealing with barite precipitation and the influence of organic additives (e.g. Benton et al. 1993, Qi et al., 2000, Wang and Cölfen, 2006, Mavredaki et al., 2011), the details of the mechanism of barite formation in the presence of organic additives, particularly at the early stages of this process, are yet to be fully resolved. Here, we present observations on the initial stages of barite formation from aqueous solutions, as well as the alterations induced by a commercial copolymer (maleic acid/allyl sulfonic acid copolymer with phosphonate groups), commonly used as a scale inhibitor in oil recovery. Most synthetic commercial additives contain the same functional groups (e.g. carboxylate, phosphonate and/or sulfonate groups). Thus our work may help to understand the mechanism by which copolymers modify crystallization processes and aid in the selection of the most appropriate inhibitors for hindering or controlling barite scale formation. Barite scaling is one of the main problems in many industrial processes (such as, paper-making, chemical manufacturing, cement operations, off-shore oil extraction, geothermal energy production). Using Atomic Force Microscopy (AFM), we show that barite growth is significantly influenced by the presence of the copolymer. In its absence, barium sulfate growth occurs by 2D island nucleation and spreading. The addition of small amounts (0.1 ppm and 0.5 ppm) of the copolymer enhances 2D nucleation but blocks growth. Just 1 ppm of inhibitor is enough to block barite nucleation and growth by adsorption of a copolymer layer onto the barite surface. Transmission electron microscopy (TEM) was also used to gain better insights into the

  4. Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

    Kim, Bumjoon J; Bang, Joona; Hawker, Craig J; Chiu, Julia J; Pine, David J; Jang, Se Gyu; Yang, Seung-Man; Kramer, Edward J

    2007-12-04

    A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles

  5. The Multiple Correspondence Analysis Method and Brain Functional Connectivity: Its Application to the Study of the Non-linear Relationships of Motor Cortex and Basal Ganglia.

    Rodriguez-Sabate, Clara; Morales, Ingrid; Sanchez, Alberto; Rodriguez, Manuel

    2017-01-01

    The complexity of basal ganglia (BG) interactions is often condensed into simple models mainly based on animal data and that present BG in closed-loop cortico-subcortical circuits of excitatory/inhibitory pathways which analyze the incoming cortical data and return the processed information to the cortex. This study was aimed at identifying functional relationships in the BG motor-loop of 24 healthy-subjects who provided written, informed consent and whose BOLD-activity was recorded by MRI methods. The analysis of the functional interaction between these centers by correlation techniques and multiple linear regression showed non-linear relationships which cannot be suitably addressed with these methods. The multiple correspondence analysis (MCA), an unsupervised multivariable procedure which can identify non-linear interactions, was used to study the functional connectivity of BG when subjects were at rest. Linear methods showed different functional interactions expected according to current BG models. MCA showed additional functional interactions which were not evident when using lineal methods. Seven functional configurations of BG were identified with MCA, two involving the primary motor and somatosensory cortex, one involving the deepest BG (external-internal globus pallidum, subthalamic nucleus and substantia nigral), one with the input-output BG centers (putamen and motor thalamus), two linking the input-output centers with other BG (external pallidum and subthalamic nucleus), and one linking the external pallidum and the substantia nigral. The results provide evidence that the non-linear MCA and linear methods are complementary and should be best used in conjunction to more fully understand the nature of functional connectivity of brain centers.

  6. Block Copolymers: Synthesis and Applications in Nanotechnology

    Lou, Qin

    This study is focused on the synthesis and study of (block) copolymers using reversible deactivation radical polymerizations (RDRPs), including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, two primary areas of study are undertaken: (1) a proof-of-concept application of lithographic block copolymers, and (2) the mechanistic study of the deposition of titania into block copolymer templates for the production of well-ordered titania nanostructures. Block copolymers have the ability to undergo microphase separation, with an average size of each microphase ranging from tens to hundreds of nanometers. As such, block copolymers have been widely considered for nanotechnological applications over the past two decades. The development of materials for various nanotechnologies has become an increasingly studied area as improvements in many applications, such as those found in the semiconductor and photovoltaic industries are constantly being sought. Significant growth in developments of new synthetic methods ( i.e. RDRPs) has allowed the production of block copolymers with molecular (and sometimes atomic) definition. In turn, this has greatly expanded the use of block copolymers in nanotechnology. Herein, we describe the synthesis of statistical and block copolymers of 193 nm photolithography methacrylate and acrylate resist monomers with norbornyl and adamantyl moieties using RAFT polymerization.. For these resist (block) copolymers, the phase separation behaviors were examined by atomic force microscopy (AFM). End groups were removed from the polymers to avoid complications during the photolithography since RAFT end groups absorb visible light. Poly(glycidyl methacrylate-block-polystyrene) (PGMA-b-PS) was synthesize by ATRP and demonstrated that this block copolymer acts as both a lithographic UV (365 nm) photoresist and a self-assembly material. The PGMA segments can undergo cationic

  7. Influence of chain microstructure on thermodegradative behavior of furfuryl methacrylate-N-vinylpyrrolidone random copolymers by thermogravimetry

    Peniche, C.; Zaldivar, D. (Univ. de la Habana, Havana (Cuba). Centro de Biomateriales); Bulay, A. (Plastmassi, Moscow (Russian Federation)); Roman, J.S. (CSIC, Madrid (Spain). Inst. de Ciencia y Tecnologia de Polimeros)

    1993-12-20

    The thermal behavior of random copolymers of furfuryl methacrylate (F) and N-vinyl-pyrrolidone (P) was studied by means of dynamic thermogravimetric analysis (TGA) in the range 100--600 C. The dynamic experiments show that these copolymers exhibit two degradation steps in the intervals 260--320 C and 350--520 C, respectively. The normalized weight loss in the low temperature interval increases as the mole fraction of F in the copolymer m[sub F] increases, whereas an inverted trend in the high temperature interval is observed. The apparent activation energy E[sub a] of the first degradation step for copolymers prepared with different composition, was obtained according to the treatment suggested by Broido. A plot of the values of E[sub a] versus the F dead molar fraction in the copolymer chains m[sub FF] gave a straight line that indicates that there is a direct relationship between the thermogravimetric behavior of these systems and their corresponding microstructure, that is, the distribution of comonomeric units along the copolymers chains. The first decomposition step was also studied by isothermal TGA and a good linearity for the variation of the weight loss percentage [Delta]W versus m[sub F] at least during the first 30 min of treatment was obtained.

  8. Responsive Copolymers for Enhanced Petroleum Recovery

    McCormick, C.; Hester, R.

    2001-02-27

    The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

  9. Reactivity Ratios for Organotin Copolymer Systems

    Mohamed H. El-Newehy

    2010-04-01

    Full Text Available Di(tri-n-butyltin itaconate (DTBTI and monoethyl tributyltin fumarate (METBTF were synthesized as organotin monomers. The organotin monomers were copolymerized with styrene (ST and methyl methacrylate (MMA via a free radical polymerization technique. The overall conversion was kept low (£15% wt/wt for all studied samples and the copolymer composition was determined from tin analysis. The synthesized monomers and copolymers were characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

  10. The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

    Angerman, HJ; ten Brinke, G

    The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock

  11. DUF1220 copy number is linearly associated with increased cognitive function as measured by total IQ and mathematical aptitude scores

    Davis, Jonathon M.; Searles, Veronica B.; Anderson, Nathan; Keeney, Jonathon; Raznahan, Armin; Horwood, L. John; Fergusson, David M.; Kennedy, Martin A.; Giedd, Jay

    2014-01-01

    DUF1220 protein domains exhibit the greatest human lineage-specific copy number expansion of any protein-coding sequence in the genome, and variation in DUF1220 copy number has been linked to both brain size in humans and brain evolution among primates. Given these findings, we examined associations between DUF1220 subtypes CON1 and CON2 and cognitive aptitude. We identified a linear association between CON2 copy number and cognitive function in two independent populations of European descent. In North American males, an increase in CON2 copy number corresponded with an increase in WISC IQ (R2 = 0.13, p = 0.02), which may be driven by males aged 6–11 (R2 = 0.42, p = 0.003). We utilized ddPCR in a subset as a confirmatory measurement. This group had 26–33 copies of CON2 with a mean of 29, and each copy increase of CON2 was associated with a 3.3-point increase in WISC IQ (R2 = 0.22, p = 0.045). In individuals from New Zealand, an increase in CON2 copy number was associated with an increase in math aptitude ability (R2 = 0.10 p = 0.018). These were not confounded by brain size. To our knowledge, this is the first study to report a replicated association between copy number of a gene coding sequence and cognitive aptitude. Remarkably, dosage variations involving DUF1220 sequences have now been linked to human brain expansion, autism severity and cognitive aptitude, suggesting that such processes may be genetically and mechanistically inter-related. The findings presented here warrant expanded investigations in larger, well-characterized cohorts. PMID:25287832

  12. MRI-based, wireless determination of the transfer function of a linear implant: Introduction of the transfer matrix.

    Tokaya, Janot P; Raaijmakers, Alexander J E; Luijten, Peter R; van den Berg, Cornelis A T

    2018-04-24

    We introduce the transfer matrix (TM) that makes MR-based wireless determination of transfer functions (TFs) possible. TFs are implant specific measures for RF-safety assessment of linear implants. The TF relates an incident tangential electric field on an implant to a scattered electric field at its tip that generally governs local heating. The TM extends this concept and relates an incident tangential electric field to a current distribution in the implant therewith characterizing the RF response along the entire implant. The TM is exploited to measure TFs with MRI without hardware alterations. A model of rightward and leftward propagating attenuated waves undergoing multiple reflections is used to derive an analytical expression for the TM. This allows parameterization of the TM of generic implants, e.g., (partially) insulated single wires, in a homogeneous medium in a few unknowns that simultaneously describe the TF. These unknowns can be determined with MRI making it possible to measure the TM and, therefore, also the TF. The TM is able to predict an induced current due to an incident electric field and can be accurately parameterized with a limited number of unknowns. Using this description the TF is determined accurately (with a Pearson correlation coefficient R ≥ 0.9 between measurements and simulations) from MRI acquisitions. The TM enables measuring of TFs with MRI of the tested generic implant models. The MR-based method does not need hardware alterations and is wireless hence making TF determination in more realistic scenarios conceivable. © 2018 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

  13. The conservation pattern of short linear motifs is highly correlated with the function of interacting protein domains

    Wang Yiguo

    2008-10-01

    Full Text Available Abstract Background Many well-represented domains recognize primary sequences usually less than 10 amino acids in length, called Short Linear Motifs (SLiMs. Accurate prediction of SLiMs has been difficult because they are short (often Results Our combined approach revealed that SLiMs are highly conserved in proteins from functional classes that are known to interact with a specific domain, but that they are not conserved in most other protein groups. We found that SLiMs recognized by SH2 domains were highly conserved in receptor kinases/phosphatases, adaptor molecules, and tyrosine kinases/phosphatases, that SLiMs recognized by SH3 domains were highly conserved in cytoskeletal and cytoskeletal-associated proteins, that SLiMs recognized by PDZ domains were highly conserved in membrane proteins such as channels and receptors, and that SLiMs recognized by S/T kinase domains were highly conserved in adaptor molecules, S/T kinases/phosphatases, and proteins involved in transcription or cell cycle control. We studied Tyr-SLiMs recognized by SH2 domains in more detail, and found that SH2-recognized Tyr-SLiMs on the cytoplasmic side of membrane proteins are more highly conserved than those on the extra-cellular side. Also, we found that SH2-recognized Tyr-SLiMs that are associated with SH3 motifs and a tyrosine kinase phosphorylation motif are more highly conserved. Conclusion The interactome of protein domains is reflected by the evolutionary conservation of SLiMs recognized by these domains. Combining scoring matrixes derived from peptide libraries and conservation analysis, we would be able to find those protein groups that are more likely to interact with specific domains.

  14. Relationship between linear and nonlinear dynamics of heart rate and impairment of lung function in COPD patients

    Mazzuco A

    2015-08-01

    capacity/total lung capacity ratio, and residual volume/total lung capacity ratio. Significant and moderate associations were also observed between LF/HF ratio versus total gas volume (%, r=0.53; LF/HF ratio versus residual volume, %, r=0.52; and HF versus total gas volume (%, r=-0.53 (P<0.05. Linear regression analysis revealed that ΔRRi supine-M-RSA was independently related to DLCO (r=-0.77, r2=0.43, P<0.05. Conclusion: Responses of HRV indices were more prominent during M-RSA in moderate to severe COPD. Moreover, greater lung function impairment was related to poorer heart rate dynamics. Finally, impaired lung diffusion capacity was related to an altered parasympathetic response in these patients. Keywords: lung diffusion capacity, static lung volumes, rest hyperinflation, COPD, heart rate variability, cardiac autonomic nervous system

  15. Sensitivity of Surface Temperature to Oceanic Forcing via q-Flux Green’s Function Experiments. Part I: Linear Response Function

    Liu, Fukai; Lu, Jian; Garuba, Oluwayemi A.; Leung, Lai-Yung; Luo, Yiyong; Wan, Xiuquan

    2018-05-01

    This paper explores the use of linear response function (LRF) to relate the mean sea surface temperature (SST) response to prescribed ocean heat convergence (q-flux) forcings. Two methods for constructing the LRF based on the fluctuation-dissipation theorem (FDT) and Green’s function (GRF) are examined. A 900-year preindustrial simulation from the Community Earth System Model with a slab ocean (CESM-SOM) is used to estimate the LRF using FDT. For GRF, 106 pairs of CESM-SOM simulations with warm and cold q-flux patches are performed. FDT is found to have skill in estimating the SST response to a q-flux forcing when the local SST response is strong, but it fails in inverse estimation of the q-flux forcing for a given SST pattern. In contrast, GRF is shown to be reasonably accurate in estimating both SST response and q-flux forcing. Possible degradation in FDT may be attributed to insufficient data sampling, significant departures of the SST data from Gaussian, and the non-normality of the constructed operator. The accurately estimated GRF-based LRF is used to (i) generate a global surface temperature sensitivity map that shows the q-flux forcing in higher latitudes to be three to four times more effective than in low latitudes in producing global surface warming; (ii) identify the most excitable SST mode (neutral vector) resembling Interdecadal Pacific Oscillation; and (iii) estimate a time-invariant q-flux forcing needed for maintaining the GHG-induced SST warming pattern. The GRF experiments will be used to construct LRF for other variables to further explore climate sensitivities and feedbacks.

  16. Radiation synthesis of a water-soluble temperature sensitive polymer, activated copolymer and applications in immobilization of proteins

    Zhai Maolin; Ha Hongfei; Wu Jilan

    1993-01-01

    In this work the radiation polymerization of N-isopropylacrylamide (NIPAAM) in aqueous solutions has been carried out and a water-soluble, temperature sensitive polymer and copolymer were obtained by using γ-rays from Co-60 source at room temperature. We have gained the optimum dose and dose-rate of radiation synthesis of linear polyNIPAAM through determining conversion yield and viscosity. In order to immobilize protein (BSA) and enzyme (HRP) into this water-soluble polymer, we prepared an activated copolymer, poly(N-isopropylacrylamide-co-N-acryloxysuccinimide). The BSA and HRP has been immobilized onto the activated copolymer. The BSA (HRP)/copolymer conjugates still kept the original thermally sensitive properties of the linear polyNIPAAM. The conjugation yield of BSA to the activated copolymer decreased with increasing dose. Immobilized HRP was stable at 0 o C for a long time and has, at least, 4 days stability at room temperature. Immobilized HRP activity was lowered when the temperature was raised. This phenomenon was reversible and the immobilized HRP regained activity. The optimum pH of the immobilized HRP shifted from ca.5 upward to ca. 7. (author)

  17. Slip-spring model of entangled rod-coil block copolymers

    Wang, Muzhou; Likhtman, Alexei E.; Olsen, Bradley D.

    2015-03-01

    Understanding the dynamics of rod-coil block copolymers is important for optimal design of functional nanostructured materials for organic electronics and biomaterials. Recently, we proposed a reptation theory of entangled rod-coil block copolymers, predicting the relaxation mechanisms of activated reptation and arm retraction that slow rod-coil dynamics relative to coil and rod homopolymers, respectively. In this work, we introduce a coarse-grained slip-spring model of rod-coil block copolymers to further explore these mechanisms. First, parameters of the coarse-grained model are tuned to match previous molecular dynamics simulation results for coils, rods, and block copolymers. For activated reptation, rod-coil copolymers are shown to disfavor configurations where the rod occupies curved portions of the entanglement tube of randomly varying curvature created by the coil ends. The effect of these barriers on diffusion is quantitatively captured by considering one-dimensional motion along an entanglement tube with a rough free energy potential. Finally, we analyze the crossover between the two mechanisms. The resulting dynamics from both mechanisms acting in combination is faster than from each one individually.

  18. Preparation and Characterization of Styrene Bearing Diethanolamine Side Group, Styrene Copolymer Systems, and Their Metal Complexes

    Aslışah Açıkses

    2018-01-01

    Full Text Available The two copolymer systems of styrene bearing diethanol amine side group and styrene were prepared by free radical polymerization method at 60°C in presence of 1,4-dioxane as solvent and AIBN as initiator. Their metal complexes were prepared by reaction of the copolymer used as ligand P(DEAMSt-co-StL′′ and Ni(II and Co(II metal ions, which was carried out in presence of ethanol and NaOH at 65°C for 48 h in pH = 7.5. The structures of the copolymers used as ligand and metal complexes were identified by FT-IR, 1H-NMR spectra, and elemental analysis. The properties of the copolymers used as ligand and metal complexes were characterized by SEM-EDX, AAS, DSC, TGA, and DTA techniques. Then, the electrical properties of the copolymers and metal complexes were examined as a function of the temperature and frequency, and the activation energies (Ea were estimated with conductivity measurements.

  19. A self-consistent field study of diblock copolymer/charged particle system morphologies for nanofiltration membranes

    Zhang, Bo; Ye, Xianggui; Edwards, Brian J.

    2013-01-01

    A combination of self-consistent field theory and density functional theory was used to examine the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Both neutral and interacting particles were examined, with and without favorable/unfavorable energetic potentials between the particles and the block segments. The phase diagrams of the various systems were constructed, allowing the identification of three types of ordered mesophases composed of lamellae, hexagonally packed cylinders, and spheroids. In particular, we examined the conditions under which the mesophases could be generated wherein the tethered particles were primarily located within the interface between the two blocks of the copolymer. Key factors influencing these properties were determined to be the particle position along the diblock chain, the interaction potentials of the blocks and particles, the block copolymer composition, and molecular weight of the copolymer

  20. Introducing PROFESS 2.0: A parallelized, fully linear scaling program for orbital-free density functional theory calculations

    Hung, Linda; Huang, Chen; Shin, Ilgyou; Ho, Gregory S.; Lignères, Vincent L.; Carter, Emily A.

    2010-12-01

    Orbital-free density functional theory (OFDFT) is a first principles quantum mechanics method to find the ground-state energy of a system by variationally minimizing with respect to the electron density. No orbitals are used in the evaluation of the kinetic energy (unlike Kohn-Sham DFT), and the method scales nearly linearly with the size of the system. The PRinceton Orbital-Free Electronic Structure Software (PROFESS) uses OFDFT to model materials from the atomic scale to the mesoscale. This new version of PROFESS allows the study of larger systems with two significant changes: PROFESS is now parallelized, and the ion-electron and ion-ion terms scale quasilinearly, instead of quadratically as in PROFESS v1 (L. Hung and E.A. Carter, Chem. Phys. Lett. 475 (2009) 163). At the start of a run, PROFESS reads the various input files that describe the geometry of the system (ion positions and cell dimensions), the type of elements (defined by electron-ion pseudopotentials), the actions you want it to perform (minimize with respect to electron density and/or ion positions and/or cell lattice vectors), and the various options for the computation (such as which functionals you want it to use). Based on these inputs, PROFESS sets up a computation and performs the appropriate optimizations. Energies, forces, stresses, material geometries, and electron density configurations are some of the values that can be output throughout the optimization. New version program summaryProgram Title: PROFESS Catalogue identifier: AEBN_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEBN_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 68 721 No. of bytes in distributed program, including test data, etc.: 1 708 547 Distribution format: tar.gz Programming language: Fortran 90 Computer

  1. Existence of 2m-1 Positive Solutions for Sturm-Liouville Boundary Value Problems with Linear Functional Boundary Conditions on the Half-Line

    Yanmei Sun

    2012-01-01

    Full Text Available By using the Leggett-Williams fixed theorem, we establish the existence of multiple positive solutions for second-order nonhomogeneous Sturm-Liouville boundary value problems with linear functional boundary conditions. One explicit example with singularity is presented to demonstrate the application of our main results.

  2. Ion Correlation Effects in Salt-Doped Block Copolymers

    Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M.

    2018-03-01

    We apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at the same coarse-grained level. We show good agreement with molecular dynamics simulations.

  3. Multiblock copolymers synthesized in aqueous dispersions using multifunctional RAFT agents

    Bussels, R.; Bergman-Göttgens, C.M.; Meuldijk, J.; Koning, C.E.

    2005-01-01

    Triblock copolymers were synthesized in aqueous dispersions in two polymerization steps using a low molar mass difunctional dithiocarbamate-based RAFT agent, and in merely one polymerization step using a macromolecular difunctional dithiocarbamate-based RAFT agent. Segmented block copolymers

  4. Polyamide copolymers having 2,5-furan dicarboxamide units

    Chisholm, Bret Ja; Samanta, Satyabrata

    2017-09-19

    Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

  5. Synthesis and characterization of the polystyrene - asphaltene graft copolymer BY FT-IR spectroscopy

    Leo, Adan Yovani; Salazar Ramiro

    2008-01-01

    The creation of new polymer compounds to be added to asphalt has drawn considerable attention because these substances have succeeded in modifying the asphalt rheological characteristics and physical properties for the enhancement of its behavior during the time of use. This work explains the synthesis of a new graft copolymer based on an asphalt fraction called asphaltene, modified with maleic anhydride. Polystyrene functionalization is conducted in a parallel fashion in order to obtain polybenzylamine resin with an amine - NH2 free group that reacts with the anhydride graft groups in the asphaltene, thus obtaining the new Polystyrene/Asphaltene graft copolymer

  6. Synthesis of click-reactive HPMA copolymers using RAFT polymerization for drug delivery applications

    Ebbesen, Morten F; Schaffert, D.H.; Crowley, Michael L

    2013-01-01

    This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well-defined, reactive copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N-(3......-azidopropyl)methacrylamide (AzMA) was synthesized and copolymerized with HPMA using RAFT polymerization to provide p(HPMA-co-AzMA) copolymers with high control of molecular weight (∼10–54 kDa) and polydispersity (≤1.06). The utility of the side-chain azide functionality by Cu(I)-catalyzed azide...

  7. Synthesis of Norbornene Derived Helical Copolymer by Simple Molecular Marriage Approach to Produce Smart Nanocarrier.

    Mane, Shivshankar R; Sathyan, Ashlin; Shunmugam, Raja

    2017-03-22

    A novel library of norbornene derived helical copolymer has been synthesized through the coupling of two homopolymers via Molecular Marriage Approach. The helicity is governed by the non-covalent interactions like hydrogen bonding, π-π stacking and the influence of hydrophobic and hydrophilic motifs. The detailed characterization of the copolymer (Copoly 1) has been provided and the super structures are confirmed through dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The observed size of the aggregates was about 200 nm. The density functional theory (DFT) is favorably supported for the formation of proposed structure of Copoly 1. Circular dichroism (CD) measurement has confirmed the one handed helical structure of the copolymer. Reservoir capability of this pH responsive polymer (Copoly 1) to encapsulate anti-cancer drug doxorubicin (DOX) warrants its potential applications in the field of bio-medical sciences.

  8. Tuning of Block Copolymer Membrane Morphology through Water Induced Phase Inversion Technique

    Madhavan, Poornima

    2016-06-01

    Isoporous membranes are attractive for the regulation and detection of transport at the molecular level. A well-defined asymmetric membranes from diblock copolymers with an ordered nanoporous membrane morphologies were fabricated by the combination of block copolymer self-assembly and non-solvent-induced phase separation (NIPS) technique. This is a straightforward and fast one step procedure to develop integrally anisotropic (“asymmetric”) membranes having isoporous top selective layer. Membranes prepared via this method exhibit an anisotropic cross section with a thin separation layer supported from underneath a macroporous support. These membrane poses cylindrical pore structure with ordered nanopores across the entire membrane surfaces with pore size in the range from 20 to 40 nm. Tuning the pore morphology of the block copolymer membranes before and after fabrication are of great interest. In this thesis, we first investigated the pore morphology tuning of asymmetric block copolymer membrane by complexing with small organic molecules. We found that the occurrence of hydrogen-bond formation between PS-b-P4VP block copolymer and –OH/ –COOH functionalized organic molecules significantly tunes the pore morphology of asymmetric nanoporous membranes. In addition, we studied the complexation behavior of ionic liquids with PS-b-P4VP block copolymer in solutions and investigated their effect on final membrane morphology during the non-solvent induced phase separation process. We found that non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ionic liquids led to a lamella-structured membrane. Secondly, we demonstrated the catalytic activity of the gold nanoparticle-enhanced hollow fiber membranes by the reduction of nitrophenol. Also, we systematically investigated the pore morphology of isoporous PS-b-P4VP using 3D imaging technique. Thirdly, we developed well-distributed silver nanoparticles on the

  9. Synthesis of DNA block copolymers with extended nucleic acid segments by enzymatic ligation : cut and paste large hybrid architectures

    Ayaz, Meryem S.; Kwak, Minseok; Alemdaroglu, Fikri E.; Wang, Jie; Berger, Ruediger; Herrmann, Andreas; Berger, Rüdiger

    2011-01-01

    Ultra-high molecular weight DNA/polymer hybrid materials were prepared employing molecular biology techniques. Nucleic acid restriction and ligation enzymes were used to generate linear DNA di- and triblock copolymers that contain up to thousands of base pairs in the DNA segments.

  10. Hierarchical self-assembly of two-length-scale multiblock copolymers

    Brinke, Gerrit ten; Loos, Katja; Vukovic, Ivana; Du Sart, Gerrit Gobius

    2011-01-01

    The self-assembly in diblock copolymer-based supramolecules, obtained by hydrogen bonding short side chains to one of the blocks, as well as in two-length-scale linear terpolymers results in hierarchical structure formation. The orientation of the different domains, e.g. layers in the case of a lamellar-in-lamellar structure, is determined by the molecular architecture, graft-like versus linear, and the relative magnitude of the interactions involved. In both cases parallel and perpendicular arrangements have been observed. The comb-shaped supramolecules approach is ideally suited for the preparation of nanoporous structures. A bicontinuous morphology with the supramolecular comb block forming the channels was finally achieved by extending the original approach to suitable triblock copolymer-based supramolecules.

  11. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Norton, C.J.; Falk, D.O.

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  12. Photo-Induced Micellization of Block Copolymers

    Satoshi Kuwayama

    2010-11-01

    Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

  13. Influence of chemical crosslinks on the elastic behavior of segmented block copolymers

    van der Schuur, J.M.; Gaymans, R.J.

    2005-01-01

    Polyether(ester–amide)s (PEEA) segmented block copolymers with di- and tri-functional poly(propylene oxide)s and amide segments were synthesized and the elastic properties studied. The difunctional polyether used had a molecular weight of 2300 g/mol end capped with 20 wt% ethylene oxide. The

  14. Thermoreversible cross-linking of maleated ethylene/propylene copolymers with diamines and amino-alcohols

    Mee, van der M.A.J.; Goossens, J.G.P.; Duin, van M.

    2008-01-01

    Maleated ethylene/propylene copolymers (MAn-g-EPM) were thermoreversibly cross-linked using diamines and amino-alcohols. Covalent cross-links are formed via the equilibrium reaction of the grafted anhydride groups with di-functional cross-linkers containing combinations of primary (1°) and secondary

  15. Supramolecular self-assembly and opto-electronic properties of semiconducting block copolymers

    Boer, Bert de; Stalmach, Ulf; Hutten, Paul F. van; Melzer, Christian; Krasnikov, Victor V.; Hadziioannou, Georges

    2001-01-01

    With continuous and nanometre-scale interpenetrating phases of electron donor and acceptor components, a novel diblock copolymer, in which one block is poly(p-phenylene vinylene) (PPV) and the other is a C60-functionalized polystyrene, is designed to be an efficient photovoltaic material. The

  16. The lamellar period in symmetric diblock copolymer thin films studied by neutron reflectivity and AFM

    Gadegaard, N.; Almdal, K.; Larsen, N.B.

    1999-01-01

    The lamellar structure of a symmetric diblock copolymer was studied as a function of temperature. We used dPEP-PDMS with a molecular weight of 8.3 kg/mol as model system. The polymer was dissolved in chloroform and spin-casted on silicon wafers into thin uniform films. The degree and direction...

  17. Synthesis of amylose-block-polystyrene rod-coil block copolymers

    Loos, Katja; Stadler, Reimund

    1997-01-01

    In the present communication we demonstrate the synthesis of a hybrid block copolymer based on the combination of a biopolymer (amylose) with a synthetic block (polystyrene). To obtain such materials, amino-functionalized polymers were modified with maltoheptaose moieties that serve as initiators

  18. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be safely...

  19. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be safely...

  20. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of articles...

  1. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

  2. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be safely...

  3. Copolymers of various architectures containing ethylene and 5-norbornen-2-yl derivatives

    Diamanti, Steve Jon

    Polyolefins are a class of materials with enormous economic impact. Tailoring of polyolefin bulk properties by synthetic control is a major focus of many industrial and academic research groups. Polar functionalities within the hydrophobic polyolefin backbone can change important properties, such as, toughness, adhesion, solvent resistance, blend compatibility with other functional polymers, and rheological properties. Functional polyolefin materials with block or graft architectures are the most desirable structures as the pure polyolefin block maintains its intrinsic properties. Our initial work elucidated a neutral nickel based catalyst system capable of catalyzing the "quasi-living" homopolymerization of ethylene and the "quasi-living" copolymerization of ethylene with 5-norbornen-2-yl acetate (NBA), a polar comonomer. Through testing the effect of several reaction variables on the copolymerization of ethylene with NBA it was found that changing ethylene pressure causes a large change in the content of NBA in the copolymer chain. This change in NBA content, in turn, drastically affects the physical and thermal properties of these polymers. Understanding the impact of such reaction variables on copolymer properties made it possible to design more sophisticated architectures. This catalytic system has since been used to synthesize block copolymers and tapered block copolymers of ethylene and NBA. Block copolymers of ethylene and NBA have been synthesized by a method utilizing ethylene pressure variation to create two distinct copolymeric blocks that are able to order into microphase-separated structures. The block structure of these materials has been proven by 1H-NMR spectroscopy, thermal analysis, GPC, AFM, and TEM. The synthesis, characterization, and bulk and thermal properties of tapered block copolymers containing ethylene and NBA, has also been performed. The final structure of the tapered block polymer is a polar amorphous chain (rich in NBA) on one

  4. Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures

    Kalogirou, Andreas; Gergidis, Leonidas N.; Moultos, Othonas; Vlahos, Costas

    2015-11-01

    The entropic effects in the comicellization behavior of amphiphilic A B copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

  5. Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer

    Ferreto, Helio Fernando Rodrigues

    2006-01-01

    The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

  6. Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

    Dagmar R. D'hooge

    2014-04-01

    Full Text Available Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000, optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP. Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation ( polymer property. Careful selection or fed-batch addition of the conventional radical initiator I2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1. Fed-batch addition of not only I2, but also comonomer and deactivator (50 ppm under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

  7. Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

    Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

    2018-03-01

    Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

  8. Donor–Acceptor Copolymers of Relevance for Organic Photovoltaics: A Theoretical Investigation of the Impact of Chemical Structure Modifications on the Electronic and Optical Properties

    Pandey, Laxman; Risko, Chad; Norton, Joseph E.; Bré das, Jean-Luc

    2012-01-01

    We systematically investigate at the density functional theory level how changes to the chemical structure of donor-acceptor copolymers used in a number of organic electronics applications influences the intrinsic geometric, electronic, and optical

  9. Statistical analysis of nitrogen-containing vinyl copolymers: radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone

    Peppas, N.A.; Gehr, T.W.B.

    1979-01-01

    Radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone was carried out at 5 0 C using γ-irradiation of 1450 rads/min. Copolymers prepared at conversions lower than 5% were analyzed by a saponification technique. Various linear and nonlinear statistical analysis techniques were used to determine the reactivity ratios of this system as r 1 = 0.348 and r 2 = 3.108. These data were examined and analyzed in relation to problems of elemental analysis involving nitrogen-containing copolymers and to discrepancies in the reactivity ratios obtained by previous investigators. The presence of oxygen and a higher dose rate did not affect the copolymer composition within statistical error. Hydrolyzed copolymers prepared by this method have potential applications as biocompatible materials

  10. Synthesis, characterizations and biocompatibility of novel biodegradable star block copolymers based on poly[(R)-3-hydroxybutyrate] and poly(epsilon-caprolactone)

    Wu, Linping; Wang, Liang; Wang, Xiaojuan

    2010-01-01

    Star block copolymers based on poly[(R)-3-hydroxybutyrate] (PHB) and poly(epsilon-caprolactone) (PCL), termed SPHBCL, were successfully synthesized with structural variation on arm numbers and lengths via coupling reactions and ring opening polymerizations. Arm numbers 3, 4 and 6 of SPHBCL were...... weights of the SPHBCL due to the discrepancy of star copolymer structures. The melting temperature of SPHBCL decreased with increasing degree of branching. Thermal decomposition temperature was revealed to be lower than that of linear block copolymer LPHBCL counterparts based on PHB and PCL. Films made...... from various SPHBCL copolymers had different porous or networking surface morphology, and all possessed improved biocompatibility in terms of less blood clotting and more osteoblast cell growth compared with their corresponding homopolymers PHB and PCL. Among them, it was found, however, that the 4-arm...

  11. Photoconductivity enhancement and charge transport properties in ruthenium-containing block copolymer/carbon nanotube hybrids.

    Lo, Kin Cheung; Hau, King In; Chan, Wai Kin

    2018-04-05

    Functional polymer/carbon nanotube (CNT) hybrid materials can serve as a good model for light harvesting systems based on CNTs. This paper presents the synthesis of block copolymer/CNT hybrids and the characterization of their photocurrent responses by both experimental and computational approaches. A series of functional diblock copolymers was synthesized by reversible addition-fragmentation chain transfer polymerizations for the dispersion and functionalization of CNTs. The block copolymers contain photosensitizing ruthenium complexes and modified pyrene-based anchoring units. The photocurrent responses of the polymer/CNT hybrids were measured by photoconductive atomic force microscopy (PCAFM), from which the experimental data were analyzed by vigorous statistical models. The difference in photocurrent response among different hybrids was correlated to the conformations of the hybrids, which were elucidated by molecular dynamics simulations, and the electronic properties of polymers. The photoresponse of the block copolymer/CNT hybrids can be enhanced by introducing an electron-accepting block between the photosensitizing block and the CNT. We have demonstrated that the application of a rigorous statistical methodology can unravel the charge transport properties of these hybrid materials and provide general guidelines for the design of molecular light harvesting systems.

  12. Dynamics of Block Copolymer Nanocomposites

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  13. Co-polymer Films for Sensors

    Ryan, Margaret A. (Inventor); Jewell, April D. (Inventor); Taylor, Charles (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Manatt, Kenneth S. (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor); Homer, Margie L. (Inventor); Shevade, Abhijit V. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  14. Ordering phenomena in ABA triblock copolymer gels

    Reynders, K.; Mischenko, N.; Kleppinger, R.

    1997-01-01

    Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network). The lat......Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network...

  15. Synthesis of PMMA-b-PU-b-PMMA tri-block copolymers through ARGET ATRP in the presence of air

    P. Krol

    2013-03-01

    Full Text Available ARGET (activators regenerated by electron transfer ATRP (atom transfer radical polymerization has been successfully performed (in flasks fitted with rubber septa without the need for use of Schlenk line in the presence of limited amount of air and with a very small (370 ppm amount of copper catalyst together with an appropriate reducing agent Cu(0. Novelty of this work is that the poly(methyl methacrylate-block-polyurethane-block-poly(methyl methacrylate triblock copolymers were synthesized for the first time through ARGET ATRP, by using tertiary bromine-terminated polyurethane as a macroinitiator (MBP-PU-MBP, CuBr2 or CuCl2 as a catalyst and N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA or 2,2'-bipyridine (Bpy as a complexing agent. As the polymerization time increases, both the monomer conversion and ln([M]0/[M] increased and the molecular weight of copolymer increases linearly with increasing conversion. Theoretical number-average molecular weight (Mn, th of the tri-block copolymers was found to be comparable with number-average molecular weight determined by GPC analyses (Mn, GPC. These results indicate that the formation of the tri-block copolymers was through atom transfer radical polymerization mechanism. 1H and 13C NMR spectral methods were employed to confirm chemical structures of synthesized macroinitiator and tri-block copolymers. Mole percentage of PMMA in the tri-block copolymers was calculated using 1H NMR spectroscopy and was found to be comparable with the GPC results. Additionally, the studies of surface properties (confocal microscopy and SFE of tri-block copolymer coatings confirmed the presence of MMA segments.

  16. Preparation, characterization, and in vitro activity evaluation of triblock copolymer-based polymersomes for drugs delivery

    Besada, Lucas N.; Peruzzo, Pablo; Cortizo, Ana M.; Cortizo, M. Susana

    2018-03-01

    Polymersomes are polymer-based vesicles that form upon hydration of amphiphilic block copolymers and display high stability and durability, due to their mechanical and physical properties. They have hydrophilic reservoirs as well as thick hydrophobic membranes; allowing to encapsulate both water-soluble bioactive agent and hydrophobic drugs. In this study, poly ethylene glycol (PEG3350 and PEG6000) were used as hydrophilic part and poly(vinyl benzoate) (PVBz) as hydrophobic block to synthesize amphiphilic triblock copolymers (PVBz- b-PEG- b-PVBz). Different proportions of hydrophilic/hydrophobic part were assayed in order to obtain polymersomes by solvent injection method. For the synthesis of the copolymers, the initial block of PEG was derived to obtain a macroinitiator through a xanthate functional group (PEGX3 or PEGX6) and the polymerization of vinyl benzoate was carried out through reversible addition-fragmentation chain transfer polymerization (RAFT). The structure of PEGX and copolymers was confirmed by Infrared, 1H-NMR and UV-Vis spectrometry, while the average molecular weight (Mw) and polydispersity index (PI) were determined by size exclusion chromatography (SEC). The structures adopted by the copolymers in aqueous solution by self-assembly were investigated using transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Both techniques confirm that polymersomes were obtained for a fraction of hydrophilic block ( f) ≈ 35 ± 10%, with a diameter of 38.3 ± 0.3 nm or 22.5 ± 0.7 nm, as determined by TEM and according to the M w of the precursor block copolymer. In addition, we analyzed the possible cytotoxicity in view of its potential application as biomedical nanocarrier. The results suggest that polymersomes seem not induce cytotoxicity during the periods of time tested.

  17. Loess clay based copolymer for removing Pb(II) ions

    He, Yu-Feng; Zhang, Ling; Wang, Rong-Min; Li, Hui-Ru; Wang, Yan

    2012-01-01

    Highlights: ► The loess clay based copolymer was prepared using functional monomers. ► Characterization of the polymer adsorbent and the raw material were carried out. ► The adsorption behavior of the complex for Pb(II) ions was evaluated. ► The removal rate of Pb(II) got to 99% and the adsorption capacity got to 356.9 mg/g. - Abstract: Functional monomers, such as acrylic acid and 2-hydroxyethyl methacrylate were supported into loess clay in situ polymerization, which afforded loess clay based copolymer (LC/PAAHM), a new kind of polymer adsorbent for removing Pb(II) ions from aqueous solution. Characterization of the polymer adsorbent was carried out by different sophisticated methods, such as Fourier transformation infrared spectrometry (FTIR), scanning electron microscopy (SEM), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), and Zetasizer. Batch experiments were carried out to evaluate the factors affecting the removal efficiency, in which the pH, the adsorbent dosage, temperature and initial Pb(II) concentration all found in positive relevance to the increase of Pb(II) removal efficiency. The removal rate of Pb(II) got to 99% at room temperature and the adsorption capacity got to 356.9 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data, and Langmuir and Freundlich models have been applied to study the adsorption equilibrium, respectively.

  18. Non-linear signal response functions and their effects on the statistical and noise cancellation properties of isotope ratio measurements by multi-collector plasma mass spectrometry

    Doherty, W.

    2013-01-01

    A nebulizer-centric response function model of the analytical inductively coupled argon plasma ion source was used to investigate the statistical frequency distributions and noise reduction factors of simultaneously measured flicker noise limited isotope ion signals and their ratios. The response function model was extended by assuming i) a single gaussian distributed random noise source (nebulizer gas pressure fluctuations) and ii) the isotope ion signal response is a parabolic function of the nebulizer gas pressure. Model calculations of ion signal and signal ratio histograms were obtained by applying the statistical method of translation to the non-linear response function model of the plasma. Histograms of Ni, Cu, Pr, Tl and Pb isotope ion signals measured using a multi-collector plasma mass spectrometer were, without exception, negative skew. Histograms of the corresponding isotope ratios of Ni, Cu, Tl and Pb were either positive or negative skew. There was a complete agreement between the measured and model calculated histogram skew properties. The nebulizer-centric response function model was also used to investigate the effect of non-linear response functions on the effectiveness of noise cancellation by signal division. An alternative noise correction procedure suitable for parabolic signal response functions was derived and applied to measurements of isotope ratios of Cu, Ni, Pb and Tl. The largest noise reduction factors were always obtained when the non-linearity of the response functions was taken into account by the isotope ratio calculation. Possible applications of the nebulizer-centric response function model to other types of analytical instrumentation, large amplitude signal noise sources (e.g., lasers, pumped nebulizers) and analytical error in isotope ratio measurements by multi-collector plasma mass spectrometry are discussed. - Highlights: ► Isotope ion signal noise is modelled as a parabolic transform of a gaussian variable. ► Flicker

  19. Influence of copolymer architectures on adhesion and compatibilization of polymers at interfaces

    Guo, Lantao

    -bonding mechanism than using a pure physical entanglement. In addition, the graft copolymer is directly in the interfacial region where its effectiveness is optimized. In chapter 4, it was shown that it is possible to improve the adhesive strength of the interface between blends of styrene-co-acrylonitrile (SAN) of differing AN content and polycarbonate. The segregation depends upon AN content and can lead to a component migrating to the interface which provides enhanced adhesive strength. In this way, one may maximize both the mechanical properties and the adhesion of the SAN. In Chapter 5, micromechanical behavior of the interface between polystyrene(PS) and polymethyl methacrylate(PMMA) is investigated experimentally. The interface is formed by adding a properly chosen PS-PMMA copolymer between two homopolymers. It is a very sharp interface due to the polymer chainlike structures. The glass transition temperatures of PS and PMMA differ by only 5% so that residual stresses produced by the bonding process are minimal. The Young's moduli and Poisson's ratios of these two polymers are approximately the same. However, their fracture behaviors are very different. This gives rise to a strong mode mixity effect due to different fracture processes. The interfacial fracture toughness of this material system under tension-dominated load states was measured. Fracture surfaces were examined by scanning electron microscope (SEM). In situ observation on the local failure behavior was performed by utilizing SEM's environmental function. The deformation field at small scale near the interface crack tip is mapped by an experimental micromechanics technique, speckle interferomtry with electron microscopy (SIEM).

  20. Onion-like microspheres with tricomponent from gelable triblock copolymers.

    Zhang, Ke; Gao, Lei; Chen, Yongming; Yang, Zhenzhong

    2010-06-01

    Onion-like functional microspheres with three alternate layers were obtained by aerosol-assisted self-assembly of a functional block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene-block-poly(2-vinylpyridine) (PTEPM-b-PS-b-P2VP). Through self-gelation reaction occurred in the PTEPM layers, organic/inorganic hybrid functional spheres with highly ordered concentric curved lamellar structure were prepared. Using these hybrid onion-like microspheres as templates, gold ions were entrapped into the P2VP layers and then gold nanoparticles located in each P2VP layers were formed by a reduction. By dispersing in acidic water, the onion-like polymeric spheres were broken and, as a result, sandwich-like nanoplates with curved morphology were obtained. Copyright © 2010 Elsevier Inc. All rights reserved.