Multi-index Stochastic Collocation Convergence Rates for Random PDEs with Parametric Regularity

KAUST Repository

Haji Ali, Abdul Lateef; Nobile, Fabio; Tamellini, Lorenzo; Tempone, Raul

2016-01-01

We analyze the recent Multi-index Stochastic Collocation (MISC) method for computing statistics of the solution of a partial differential equation (PDE) with random data, where the random coefficient is parametrized by means of a countable sequence of terms in a suitable expansion. MISC is a combination technique based on mixed differences of spatial approximations and quadratures over the space of random data, and naturally, the error analysis uses the joint regularity of the solution with respect to both the variables in the physical domain and parametric variables. In MISC, the number of problem solutions performed at each discretization level is not determined by balancing the spatial and stochastic components of the error, but rather by suitably extending the knapsack-problem approach employed in the construction of the quasi-optimal sparse-grids and Multi-index Monte Carlo methods, i.e., we use a greedy optimization procedure to select the most effective mixed differences to include in the MISC estimator. We apply our theoretical estimates to a linear elliptic PDE in which the log-diffusion coefficient is modeled as a random field, with a covariance similar to a Matérn model, whose realizations have spatial regularity determined by a scalar parameter. We conduct a complexity analysis based on a summability argument showing algebraic rates of convergence with respect to the overall computational work. The rate of convergence depends on the smoothness parameter, the physical dimensionality and the efficiency of the linear solver. Numerical experiments show the effectiveness of MISC in this infinite dimensional setting compared with the Multi-index Monte Carlo method and compare the convergence rate against the rates predicted in our theoretical analysis. © 2016 SFoCM

Multi-index Stochastic Collocation Convergence Rates for Random PDEs with Parametric Regularity

KAUST Repository

Haji Ali, Abdul Lateef

2016-08-26

We analyze the recent Multi-index Stochastic Collocation (MISC) method for computing statistics of the solution of a partial differential equation (PDE) with random data, where the random coefficient is parametrized by means of a countable sequence of terms in a suitable expansion. MISC is a combination technique based on mixed differences of spatial approximations and quadratures over the space of random data, and naturally, the error analysis uses the joint regularity of the solution with respect to both the variables in the physical domain and parametric variables. In MISC, the number of problem solutions performed at each discretization level is not determined by balancing the spatial and stochastic components of the error, but rather by suitably extending the knapsack-problem approach employed in the construction of the quasi-optimal sparse-grids and Multi-index Monte Carlo methods, i.e., we use a greedy optimization procedure to select the most effective mixed differences to include in the MISC estimator. We apply our theoretical estimates to a linear elliptic PDE in which the log-diffusion coefficient is modeled as a random field, with a covariance similar to a Matérn model, whose realizations have spatial regularity determined by a scalar parameter. We conduct a complexity analysis based on a summability argument showing algebraic rates of convergence with respect to the overall computational work. The rate of convergence depends on the smoothness parameter, the physical dimensionality and the efficiency of the linear solver. Numerical experiments show the effectiveness of MISC in this infinite dimensional setting compared with the Multi-index Monte Carlo method and compare the convergence rate against the rates predicted in our theoretical analysis. © 2016 SFoCM

Thermo-responsive block copolymers

NARCIS (Netherlands)

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

Polyether based segmented copolymers with uniform aramid units

NARCIS (Netherlands)

Niesten, M.C.E.J.

2000-01-01

Segmented copolymers with short, glassy or crystalline hard segments and long, amorphous soft segments (multi-block copolymers) are thermoplastic elastomers (TPE’s). The hard segments form physical crosslinks for the amorphous (rubbery) soft segments. As a result, this type of materials combines

Micellization and Dynamics of a Block Copolymer

DEFF Research Database (Denmark)

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...

Multi-task feature learning by using trace norm regularization

Directory of Open Access Journals (Sweden)

Jiangmei Zhang

2017-11-01

Full Text Available Multi-task learning can extract the correlation of multiple related machine learning problems to improve performance. This paper considers applying the multi-task learning method to learn a single task. We propose a new learning approach, which employs the mixture of expert model to divide a learning task into several related sub-tasks, and then uses the trace norm regularization to extract common feature representation of these sub-tasks. A nonlinear extension of this approach by using kernel is also provided. Experiments conducted on both simulated and real data sets demonstrate the advantage of the proposed approach.

Multi-omic data integration enables discovery of hidden biological regularities

DEFF Research Database (Denmark)

Ebrahim, Ali; Brunk, Elizabeth; Tan, Justin

2016-01-01

Rapid growth in size and complexity of biological data sets has led to the 'Big Data to Knowledge' challenge. We develop advanced data integration methods for multi- level analysis of genomic, transcriptomic, ribosomal profiling, proteomic and fluxomic data. First, we show that pairwise integration...... of primary omics data reveals regularities that tie cellular processes together in Escherichia coli: the number of protein molecules made per mRNA transcript and the number of ribosomes required per translated protein molecule. Second, we show that genome- scale models, based on genomic and bibliomic data......, enable quantitative synchronization of disparate data types. Integrating omics data with models enabled the discovery of two novel regularities: condition invariant in vivo turnover rates of enzymes and the correlation of protein structural motifs and translational pausing. These regularities can...

Decentralized formation of random regular graphs for robust multi-agent networks

KAUST Repository

Yazicioglu, A. Yasin

2014-12-15

Multi-agent networks are often modeled via interaction graphs, where the nodes represent the agents and the edges denote direct interactions between the corresponding agents. Interaction graphs have significant impact on the robustness of networked systems. One family of robust graphs is the random regular graphs. In this paper, we present a locally applicable reconfiguration scheme to build random regular graphs through self-organization. For any connected initial graph, the proposed scheme maintains connectivity and the average degree while minimizing the degree differences and randomizing the links. As such, if the average degree of the initial graph is an integer, then connected regular graphs are realized uniformly at random as time goes to infinity.

Copolymers of N-cyclohexylacrylamide and n-butyl acrylate: synthesis, characterization, monomer reactivity ratios and mean sequence length

Directory of Open Access Journals (Sweden)

2007-06-01

Full Text Available Copolymerization of N-cyclohexylacrylamide (NCHA and n-butyl acrylate (BA was carried out in dimethylformamide at 55±1°C using azobisisobutyronitrile as a free radical initiator. The copolymers were characterized by 1H-NMR spectroscopy and the copolymer compositions were determined by 1H-NMR analysis. The reactivity ratios of the monomers were determined by both linear and non-linear methods. The reactivity ratios of monomers determined using linear methods like Fineman-Ross (r1 = 0.37 and r2 = 1.77 , Kelen-Tudos (r1 = 0.38 and r2 = 1.77, ext. Kelen-Tudos (r1 = 0.37 and r2 = 1.75 Yezrieler-Brokhina-Roskin (r1 = 0.37 and r2 = 1.77 and non-linear methods like Tidwell-Mortimer (r1 = 0.37 and r2 = 1.76, ProCop (r1 = 0.36 and r2 = 1.82. The Q and e values for NCHA are 0.67 and 0.68 respectively. Mean sequence lengths of copolymers are estimated from r1 and r2 values. It shows that the BA units increases in a linear fashion in the polymer chain as the concentration of BA increases in the monomer feed.

Mechanically compliant electrodes and dielectric elastomers from PEG-PDMS copolymers

DEFF Research Database (Denmark)

A Razak, Aliff Hisyam; Madsen, Frederikke Bahrt; Skov, Anne Ladegaard

2016-01-01

Soft conducting elastomers have been prepared from polydimethylsiloxane-polyethyleneglycol (PDMS-PEG) copolymer and surfactant-stabilized multi-walled carbon nanotubes (MWCNTs). The copolymer was chain-extended with PDMS of molecular weight 17.2 kg mol-1 in order to obtain a crosslinkable PDMS...... showed high conductivity combined with inherent softness. The high conductivity and softness, PDMS-PEG copolymers with incorporated MWCNTs hold great promises as compliant and highly stretchable electrodes for stretchable devices such as electro-mechanical transducers....

Interference by clustered regularly interspaced short palindromic repeat (CRISPR) RNA is governed by a seed sequence

NARCIS (Netherlands)

Semenova, E.V.; Jore, M.M.; Westra, E.R.; Oost, van der J.; Brouns, S.J.J.

2011-01-01

Prokaryotic clustered regularly interspaced short palindromic repeat (CRISPR)/Cas (CRISPR-associated sequences) systems provide adaptive immunity against viruses when a spacer sequence of small CRISPR RNA (crRNA) matches a protospacer sequence in the viral genome. Viruses that escape CRISPR/Cas

Monte Carlo simulation of AB-copolymers with saturating bonds

CERN Document Server

Chertovich, A V; Khokhlov, A R; Bohr, J

2003-01-01

Structural transitions in a single AB-copolymer chain where saturating bonds can be formed between A-and B-units are studied by means of Monte Carlo computer simulations using the bond fluctuation model. Three transitions are found, coil-globule, coil-hairpin and globule-hairpin, depending on the nature of a particular AB-sequence: statistical random sequence, diblock sequence and 'random-complementary' sequence (one-half of such an AB-sequence is random with Bernoulli statistics while the other half is complementary to the first one). The properties of random-complementary sequences are closer to those of diblock sequences than to the properties of random sequences. The model (although quite rough) is expected to represent some basic features of real RNA molecules, i.e. the formation of secondary structure of RNA due to hydrogen bonding of corresponding bases and stacking interactions of the base pairs in helixes. We introduce the notation of RNA-like copolymers and discuss in what sense the sequences studie...

Formation of Robust Multi-Agent Networks through Self-Organizing Random Regular Graphs

KAUST Repository

Yasin Yazicioǧlu, A.; Egerstedt, Magnus; Shamma, Jeff S.

2015-01-01

Multi-Agent networks are often modeled as interaction graphs, where the nodes represent the agents and the edges denote some direct interactions. The robustness of a multi-Agent network to perturbations such as failures, noise, or malicious attacks largely depends on the corresponding graph. In many applications, networks are desired to have well-connected interaction graphs with relatively small number of links. One family of such graphs is the random regular graphs. In this paper, we present a decentralized scheme for transforming any connected interaction graph with a possibly non-integer average degree of k into a connected random m-regular graph for some m ϵ [k+k ] 2. Accordingly, the agents improve the robustness of the network while maintaining a similar number of links as the initial configuration by locally adding or removing some edges. © 2015 IEEE.

Formation of Robust Multi-Agent Networks through Self-Organizing Random Regular Graphs

KAUST Repository

Yasin Yazicioǧlu, A.

2015-11-25

Multi-Agent networks are often modeled as interaction graphs, where the nodes represent the agents and the edges denote some direct interactions. The robustness of a multi-Agent network to perturbations such as failures, noise, or malicious attacks largely depends on the corresponding graph. In many applications, networks are desired to have well-connected interaction graphs with relatively small number of links. One family of such graphs is the random regular graphs. In this paper, we present a decentralized scheme for transforming any connected interaction graph with a possibly non-integer average degree of k into a connected random m-regular graph for some m ϵ [k+k ] 2. Accordingly, the agents improve the robustness of the network while maintaining a similar number of links as the initial configuration by locally adding or removing some edges. © 2015 IEEE.

Selective confinement of vibrations in composite systems with alternate quasi-regular sequences

International Nuclear Information System (INIS)

Montalban, A.; Velasco, V.R.; Tutor, J.; Fernandez-Velicia, F.J.

2007-01-01

We have studied the atom displacements and the vibrational frequencies of 1D systems formed by combinations of Fibonacci, Thue-Morse and Rudin-Shapiro quasi-regular stacks and their alternate ones. The materials are described by nearest-neighbor force constants and the corresponding atom masses, particularized to the Al, Ag systems. These structures exhibit differences in the frequency spectrum as compared to the original simple quasi-regular generations but the most important feature is the presence of separate confinement of the atom displacements in one of the sequences forming the total composite structure for different frequency ranges

Selective confinement of vibrations in composite systems with alternate quasi-regular sequences

Energy Technology Data Exchange (ETDEWEB)

Montalban, A. [Departamento de Ciencia y Tecnologia de Materiales, Division de Optica, Universidad Miguel Hernandez, 03202 Elche (Spain); Velasco, V.R. [Instituto de Ciencia de Materiales de Madrid, CSIC, Sor Juana Ines de la Cruz 3, 28049 Madrid (Spain)]. E-mail: vrvr@icmm.csic.es; Tutor, J. [Departamento de Fisica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Fernandez-Velicia, F.J. [Departamento de Fisica de los Materiales, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, Senda del Rey 9, 28080 Madrid (Spain)

2007-01-01

We have studied the atom displacements and the vibrational frequencies of 1D systems formed by combinations of Fibonacci, Thue-Morse and Rudin-Shapiro quasi-regular stacks and their alternate ones. The materials are described by nearest-neighbor force constants and the corresponding atom masses, particularized to the Al, Ag systems. These structures exhibit differences in the frequency spectrum as compared to the original simple quasi-regular generations but the most important feature is the presence of separate confinement of the atom displacements in one of the sequences forming the total composite structure for different frequency ranges.

Renewable Pentablock Copolymers Containing Bulky Natural Rosin for Tough Bioplastics

Science.gov (United States)

Rahman, Md Anisur; Ganewatta, Mitra S.; Lokupitiya, Hasala N.; Liang, Yuan; Stefik, Morgan; Tang, Chuanbing

Renewable polymers have received significant attention due to environmental concerns on petrochemical counterparts. One of the most abundant natural biomass is resin acids. However, most polymers derived from resin acids are low molecular weight and brittle because of the high chain entanglement molecular weight resulted from the bulky hydrophenanthrene pendant group. It is well established that the brittleness can be overcome by synthesizing multi-block copolymers with low entanglement molecular weight components. We investigated the effects of chain architecture and microdomain orientation on mechanical properties of both tri and pentablock copolymers. We synthesized rosin-containing A-B-A-B-A type pentablock and A-B-A type triblock copolymers to improve their mechanical properties. Pentablock copolymers showed higher strength and better toughness as compared to triblock copolymers, both superior to homopolymers. The greater toughness of pentablock copolymers is due to the presence of the rosin based midblock chains that act as bridging chains between two polynorbornene blocks.

L1-norm locally linear representation regularization multi-source adaptation learning.

Science.gov (United States)

Tao, Jianwen; Wen, Shiting; Hu, Wenjun

2015-09-01

In most supervised domain adaptation learning (DAL) tasks, one has access only to a small number of labeled examples from target domain. Therefore the success of supervised DAL in this "small sample" regime needs the effective utilization of the large amounts of unlabeled data to extract information that is useful for generalization. Toward this end, we here use the geometric intuition of manifold assumption to extend the established frameworks in existing model-based DAL methods for function learning by incorporating additional information about the target geometric structure of the marginal distribution. We would like to ensure that the solution is smooth with respect to both the ambient space and the target marginal distribution. In doing this, we propose a novel L1-norm locally linear representation regularization multi-source adaptation learning framework which exploits the geometry of the probability distribution, which has two techniques. Firstly, an L1-norm locally linear representation method is presented for robust graph construction by replacing the L2-norm reconstruction measure in LLE with L1-norm one, which is termed as L1-LLR for short. Secondly, considering the robust graph regularization, we replace traditional graph Laplacian regularization with our new L1-LLR graph Laplacian regularization and therefore construct new graph-based semi-supervised learning framework with multi-source adaptation constraint, which is coined as L1-MSAL method. Moreover, to deal with the nonlinear learning problem, we also generalize the L1-MSAL method by mapping the input data points from the input space to a high-dimensional reproducing kernel Hilbert space (RKHS) via a nonlinear mapping. Promising experimental results have been obtained on several real-world datasets such as face, visual video and object. Copyright © 2015 Elsevier Ltd. All rights reserved.

Gift from statistical learning: Visual statistical learning enhances memory for sequence elements and impairs memory for items that disrupt regularities.

Science.gov (United States)

Otsuka, Sachio; Saiki, Jun

2016-02-01

Prior studies have shown that visual statistical learning (VSL) enhances familiarity (a type of memory) of sequences. How do statistical regularities influence the processing of each triplet element and inserted distractors that disrupt the regularity? Given that increased attention to triplets induced by VSL and inhibition of unattended triplets, we predicted that VSL would promote memory for each triplet constituent, and degrade memory for inserted stimuli. Across the first two experiments, we found that objects from structured sequences were more likely to be remembered than objects from random sequences, and that letters (Experiment 1) or objects (Experiment 2) inserted into structured sequences were less likely to be remembered than those inserted into random sequences. In the subsequent two experiments, we examined an alternative account for our results, whereby the difference in memory for inserted items between structured and random conditions is due to individuation of items within random sequences. Our findings replicated even when control letters (Experiment 3A) or objects (Experiment 3B) were presented before or after, rather than inserted into, random sequences. Our findings suggest that statistical learning enhances memory for each item in a regular set and impairs memory for items that disrupt the regularity. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

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.

Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

KAUST Repository

Marques, Debora S.; Dorin, Rachel Mika; Wiesner, Ulrich B.; Smilgies, Detlef Matthias; Behzad, Ali Reza; Vainio, Ulla; Peinemann, Klaus-Viktor; Nunes, Suzana Pereira

2014-01-01

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84-87 nm for 14-20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100-130 nm (lattice constant 115-150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm. © 2014 Elsevier Ltd. All rights reserved.

Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

KAUST Repository

Marques, Debora S.

2014-03-01

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84-87 nm for 14-20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100-130 nm (lattice constant 115-150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm. © 2014 Elsevier Ltd. All rights reserved.

Role of monomer sequence and backbone chemistry in polypeptoid copolymers for marine antifouling coatings

Science.gov (United States)

Patterson, Anastasia; Wenning, Brandon; Rizis, Georgios; Calabrese, David; Finlay, John; Franco, Sofia; Clare, Anthony; Kramer, Edward; Ober, Christopher; Segalman, Rachel

The design rules elucidated in this work suggest that antifouling coatings bearing pendant peptoid side chains perform better overall in marine fouling tests than those with peptide side chains, with extremely low attachment of N. incerta and high removal of U. linza. This difference in performance is likely due to the lack of a hydrogen bond donor in the peptoid backbone. Furthermore, we show that the bulk polymer material of these hierarchical coatings (based on PEO or PDMS) plays a key role in determining both surface presentation and fouling release performance. We demonstrate these trends utilizing a modular coating based on a triblock copolymer consisting of polystyrene and a vinyl-containing midblock, to which sequence-defined pendant oligomers (peptides or peptoids with sequences of oligo-PEO and fluoroalkyl groups) are attached via thiol-ene ``click'' chemistry. Surface presentation was analyzed with X-ray photoelectron spectroscopy and captive bubble water contact angle, and antifouling performance was evaluated with attachment and removal bioassays of the marine macroalga U. linza and diatom N. incerta. NSF GRFP and ONR PECASE.

Variational multi-valued velocity field estimation for transparent sequences

DEFF Research Database (Denmark)

Ramírez-Manzanares, Alonso; Rivera, Mariano; Kornprobst, Pierre

2011-01-01

Motion estimation in sequences with transparencies is an important problem in robotics and medical imaging applications. In this work we propose a variational approach for estimating multi-valued velocity fields in transparent sequences. Starting from existing local motion estimators, we derive...... a variational model for integrating in space and time such a local information in order to obtain a robust estimation of the multi-valued velocity field. With this approach, we can indeed estimate multi-valued velocity fields which are not necessarily piecewise constant on a layer –each layer can evolve...

High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

Science.gov (United States)

Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

Substructural Regularization With Data-Sensitive Granularity for Sequence Transfer Learning.

Science.gov (United States)

Sun, Shichang; Liu, Hongbo; Meng, Jiana; Chen, C L Philip; Yang, Yu

2018-06-01

Sequence transfer learning is of interest in both academia and industry with the emergence of numerous new text domains from Twitter and other social media tools. In this paper, we put forward the data-sensitive granularity for transfer learning, and then, a novel substructural regularization transfer learning model (STLM) is proposed to preserve target domain features at substructural granularity in the light of the condition of labeled data set size. Our model is underpinned by hidden Markov model and regularization theory, where the substructural representation can be integrated as a penalty after measuring the dissimilarity of substructures between target domain and STLM with relative entropy. STLM can achieve the competing goals of preserving the target domain substructure and utilizing the observations from both the target and source domains simultaneously. The estimation of STLM is very efficient since an analytical solution can be derived as a necessary and sufficient condition. The relative usability of substructures to act as regularization parameters and the time complexity of STLM are also analyzed and discussed. Comprehensive experiments of part-of-speech tagging with both Brown and Twitter corpora fully justify that our model can make improvements on all the combinations of source and target domains.

Stark widths regularities within spectral series of sodium isoelectronic sequence

Science.gov (United States)

Trklja, Nora; Tapalaga, Irinel; Dojčinović, Ivan P.; Purić, Jagoš

2018-02-01

Stark widths within spectral series of sodium isoelectronic sequence have been studied. This is a unique approach that includes both neutrals and ions. Two levels of problem are considered: if the required atomic parameters are known, Stark widths can be calculated by some of the known methods (in present paper modified semiempirical formula has been used), but if there is a lack of parameters, regularities enable determination of Stark broadening data. In the framework of regularity research, Stark broadening dependence on environmental conditions and certain atomic parameters has been investigated. The aim of this work is to give a simple model, with minimum of required parameters, which can be used for calculation of Stark broadening data for any chosen transitions within sodium like emitters. Obtained relations were used for predictions of Stark widths for transitions that have not been measured or calculated yet. This system enables fast data processing by using of proposed theoretical model and it provides quality control and verification of obtained results.

Amino Acid Block Copolymers with Broad Antimicrobial Activity and Barrier Properties.

Science.gov (United States)

Bevilacqua, Michael P; Huang, Daniel J; Wall, Brian D; Lane, Shalyn J; Edwards, Carl K; Hanson, Jarrod A; Benitez, Diego; Solomkin, Joseph S; Deming, Timothy J

2017-10-01

Antimicrobial properties of a long-chain, synthetic, cationic, and hydrophobic amino acid block copolymer are reported. In 5 and 60 min time-kill assays, solutions of K 100 L 40 block copolymers (poly(l-lysine·hydrochloride) 100 -b-poly(l-leucine) 40 ) at concentrations of 10-100 µg mL -1 show multi-log reductions in colony forming units of Gram-positive and Gram-negative bacteria, as well as yeast, including multidrug-resistant strains. Driven by association of hydrophobic segments, K 100 L 40 copolymers form viscous solutions and self-supporting hydrogels in water at concentrations of 1 and 2 wt%, respectively. These K 100 L 40 preparations provide an effective barrier to microbial contamination of wounds, as measured by multi-log decreases of tissue-associated bacteria with deliberate inoculation of porcine skin explants, porcine open wounds, and rodent closed wounds with foreign body. Based on these findings, amino acid copolymers with the features of K 100 L 40 can combine potent, direct antimicrobial activity and barrier properties in one biopolymer for a new approach to prevention of wound infections. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predicting human splicing branchpoints by combining sequence-derived features and multi-label learning methods.

Science.gov (United States)

Zhang, Wen; Zhu, Xiaopeng; Fu, Yu; Tsuji, Junko; Weng, Zhiping

2017-12-01

Alternative splicing is the critical process in a single gene coding, which removes introns and joins exons, and splicing branchpoints are indicators for the alternative splicing. Wet experiments have identified a great number of human splicing branchpoints, but many branchpoints are still unknown. In order to guide wet experiments, we develop computational methods to predict human splicing branchpoints. Considering the fact that an intron may have multiple branchpoints, we transform the branchpoint prediction as the multi-label learning problem, and attempt to predict branchpoint sites from intron sequences. First, we investigate a variety of intron sequence-derived features, such as sparse profile, dinucleotide profile, position weight matrix profile, Markov motif profile and polypyrimidine tract profile. Second, we consider several multi-label learning methods: partial least squares regression, canonical correlation analysis and regularized canonical correlation analysis, and use them as the basic classification engines. Third, we propose two ensemble learning schemes which integrate different features and different classifiers to build ensemble learning systems for the branchpoint prediction. One is the genetic algorithm-based weighted average ensemble method; the other is the logistic regression-based ensemble method. In the computational experiments, two ensemble learning methods outperform benchmark branchpoint prediction methods, and can produce high-accuracy results on the benchmark dataset.

Stark width regularities within spectral series of the lithium isoelectronic sequence

Science.gov (United States)

Tapalaga, Irinel; Trklja, Nora; Dojčinović, Ivan P.; Purić, Jagoš

2018-03-01

Stark width regularities within spectral series of the lithium isoelectronic sequence have been studied in an approach that includes both neutrals and ions. The influence of environmental conditions and certain atomic parameters on the Stark widths of spectral lines has been investigated. This study gives a simple model for the calculation of Stark broadening data for spectral lines within the lithium isoelectronic sequence. The proposed model requires fewer parameters than any other model. The obtained relations were used for predictions of Stark widths for transitions that have not yet been measured or calculated. In the framework of the present research, three algorithms for fast data processing have been made and they enable quality control and provide verification of the theoretically calculated results.

Diffusion coefficients for periodically induced multi-step persistent walks on regular lattices

International Nuclear Information System (INIS)

Gilbert, Thomas; Sanders, David P

2012-01-01

We present a generalization of our formalism for the computation of diffusion coefficients of multi-step persistent random walks on regular lattices to walks which include zero-displacement states. This situation is especially relevant to systems where tracer particles move across potential barriers as a result of the action of a periodic forcing whose period sets the timescale between transitions. (paper)

Monte Carlo studies on the interfacial properties and interfacial structures of ternary symmetric blends with gradient copolymers.

Science.gov (United States)

Sun, Dachuan; Guo, Hongxia

2012-08-09

Using Monte Carlo simulation methods, the effects of the comonomer sequence distribution on the interfacial properties (including interfacial tension, interfacial thickness, saturated interfacial area per copolymer, and bending modulus) and interfacial structures (including chain conformations and comonomer distributions of the simulated copolymers at the interfaces) of a ternary symmetric blend containing two immiscible homopolymers and one gradient copolymer are investigated. We find that copolymers with a larger composition gradient width have a broader comonomer distribution along the interface normal, and hence more pronouncedly enlarge the interfacial thickness and reduce the interfacial tension. Furthermore, the counteraction effect, which arises from the tendency of heterogeneous segments in gradient copolymers to phase separate and enter their miscible phases to reduce the local enthalpy, decreases the stretching of copolymers along the interface normal direction. As a result, copolymers with a larger width of gradient composition can occupy a larger interfacial area and form softer monolayers at saturation and are more efficient in facilitating the formation of bicontinuous microemulsions. Additionally, chain length ratio, segregation strength, and interactions between homopolymers and copolymers can alter the interfacial character of gradient copolymers. There exists a strong coupling between the comonomer sequence distribution, chain conformation, and interfacial properties. Especially, bending modulus is mainly determined by the complicated interplay of interfacial copolymer density and interfacial chain conformation.

Temporal regularity of the environment drives time perception

OpenAIRE

van Rijn, H; Rhodes, D; Di Luca, M

2016-01-01

It’s reasonable to assume that a regularly paced sequence should be perceived as regular, but here we show that perceived regularity depends on the context in which the sequence is embedded. We presented one group of participants with perceptually regularly paced sequences, and another group of participants with mostly irregularly paced sequences (75% irregular, 25% regular). The timing of the final stimulus in each sequence could be var- ied. In one experiment, we asked whether the last stim...

Amphiphilic block copolymers for biomedical applications

Science.gov (United States)

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

PVDF-based copolymers, terpolymers and their multi-component material systems for capacitor applications

Science.gov (United States)

Chu, Baojin

at 1 kHz at room temperature), were further investigated for dielectric materials of high energy density. Due to the lower dielectric constant, the early polarization saturation was avoided and these polymers showed a very high breakdown field and energy density. For the P(VDF-CTFE) copolymer with 15 wt% CTFE, an energy density of higher than 24 J/cm 3 at an electric field higher than 650 MV/m could be obtained. Based on thermal and microstructure studies, the high energy density was found to be caused by the structural modification of PVDF by bulky CTFE or HFP, which also act as defects, similar to the terpolymers. The discharge behavior of the copolymers mainly relies on the load resistors, suggesting that the copolymers have lower equivalent series resistance. Multi-component material system based on current available materials was found to be a useful strategy to tailor and improve the performance of dielectric materials. Nanocomposites composed of the P(VDF-TrFE-CFE) terpolymers and ZrO2 or TiO2 nanoparticles were found to greatly enhance the polarization response and energy density of terpolymers (from 9 J/cm3 to 10.5 J/cm3). Based on comprehensive thermal, dielectric and microstructure studies, the enhancement was believed to be related to the large amount of interfaces in the nanocomposites. In the interfaces, the chain mobility is increased and the energy barrier between the polar and nonpolar phases is reduced, resulting in higher polarization response and energy density at a reduced electric field. The P(VDF-TrFE-CFE) terpolymer/P(VDF-CTFE) copolymer and the P(VDFTrFE-CFE) terpolymer/PMMA blends were also studied. It was found that the P(VDFTrFE-CFE) terpolymers could not be completely miscible with the P(VDF-CTFE) copolymer. In the P(VDF-TrFE-CFE) terpolymer/P(VDF-CTFE) copolymer blends, with a small amount of the copolymer (5 and 10 wt%) in the terpolymer, enhancement of the polarization response similar to that observed in the terpolymer/ZrO 2

Nonlinear analysis of sequence repeats of multi-domain proteins

Energy Technology Data Exchange (ETDEWEB)

Huang Yanzhao [Biomolecular Physics and Modeling Group, Department of Physics, Huazhong University of Science and Technology, Wuhan 430074, Hubei (China); Li Mingfeng [Biomolecular Physics and Modeling Group, Department of Physics, Huazhong University of Science and Technology, Wuhan 430074, Hubei (China); Xiao Yi [Biomolecular Physics and Modeling Group, Department of Physics, Huazhong University of Science and Technology, Wuhan 430074, Hubei (China)]. E-mail: lmf_bill@sina.com

2007-11-15

Many multi-domain proteins have repetitive three-dimensional structures but nearly-random amino acid sequences. In the present paper, by using a modified recurrence plot proposed by us previously, we show that these amino acid sequences have hidden repetitions in fact. These results indicate that the repetitive domain structures are encoded by the repetitive sequences. This also gives a method to detect the repetitive domain structures directly from amino acid sequences.

Enhancing relative permittivity by incorporating PDMS-PEG multi block copolymers in binary polymer blends

DEFF Research Database (Denmark)

A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts a possibil......Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts...... a possibility for substantial improvement of properties such as high permittivity, stretchability and non-conductivity – if carefully designed. The objective is to synthesize PDMS-PEG multiblock copolymer assembling into discontinuous morphologies in PEG based on variation of volume fractions of PDMS....... The utilized synthesis of PDMS-PEG multiblock copolymer is based on hydrosilylation reaction, which is amended from Klasner et al.1 and Jukarainen etal.2 Variation in the ratio between the two constituents introduces distinctive properties in terms of dielectric permittivity and rheological behaviour. PDMS...

Block copolymer morphologies confined by square-shaped particle: Hard and soft confinement

International Nuclear Information System (INIS)

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)

Manifold regularized matrix completion for multi-label learning with ADMM.

Science.gov (United States)

Liu, Bin; Li, Yingming; Xu, Zenglin

2018-05-01

Multi-label learning is a common machine learning problem arising from numerous real-world applications in diverse fields, e.g, natural language processing, bioinformatics, information retrieval and so on. Among various multi-label learning methods, the matrix completion approach has been regarded as a promising approach to transductive multi-label learning. By constructing a joint matrix comprising the feature matrix and the label matrix, the missing labels of test samples are regarded as missing values of the joint matrix. With the low-rank assumption of the constructed joint matrix, the missing labels can be recovered by minimizing its rank. Despite its success, most matrix completion based approaches ignore the smoothness assumption of unlabeled data, i.e., neighboring instances should also share a similar set of labels. Thus they may under exploit the intrinsic structures of data. In addition, the matrix completion problem can be less efficient. To this end, we propose to efficiently solve the multi-label learning problem as an enhanced matrix completion model with manifold regularization, where the graph Laplacian is used to ensure the label smoothness over it. To speed up the convergence of our model, we develop an efficient iterative algorithm, which solves the resulted nuclear norm minimization problem with the alternating direction method of multipliers (ADMM). Experiments on both synthetic and real-world data have shown the promising results of the proposed approach. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nonaqueous Dispersion Formed by an Emulsion Solvent Evaporation Method Using Block-Random Copolymer Surfactant Synthesized by RAFT Polymerization.

Science.gov (United States)

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.

Optimisation of Silicone-based Dielectric Elastomer Transducers by Means of Block Copolymers - Synthesis and Compounding

DEFF Research Database (Denmark)

A Razak, Aliff Hisyam

through the use of a multi-walled carbon nanotube (MWCNT) in a PDMS-PEG matrix as a compliant electrode of dielectric elastomers. The conductive PDMS-PEG copolymer was incorporated with surface-treated MWCNT, in order to obtain highly conductive elastomer. The prepared sample with 4 parts per hundred...... enhancing the electrical breakdown strength of silicone by using an aromatic voltage stabiliser. Here, polyphenylmethylsiloxane (PPMS), which contained aromatic voltage stabilisers, was bonded covalently to PDMS through a hydrosilylation reaction obtaining PDMS-PPMS copolymers. The synthesised copolymers...

Organisation and shape of micellar solutions of block copolymers

Science.gov (United States)

Gaspard, J. P.; Creutz, S.; Bouchat, Ph.; Jérôme, R.; Cohen Stuart, M.

1997-02-01

Diblock copolymers of polymethacrylic acid sodium salt, forming the hair, and styrene derivatives have been studied in aqueous solutions by SANS and SAXS. The influence of both the chemical nature and the length of the hydrophobic bloxk on the size and shape of micelles have been investigated. The micellar core size is in agreement with the theoretical evaluation for copolymers with a short hydrophobic sequence. In contrast, in case of larger hydrophobic blocks, the measured size is incompatible with a star-like model. Various hypotheses are presented for the latter.

Feature selection and multi-kernel learning for adaptive graph regularized nonnegative matrix factorization

KAUST Repository

Wang, Jim Jing-Yan

2014-09-20

Nonnegative matrix factorization (NMF), a popular part-based representation technique, does not capture the intrinsic local geometric structure of the data space. Graph regularized NMF (GNMF) was recently proposed to avoid this limitation by regularizing NMF with a nearest neighbor graph constructed from the input data set. However, GNMF has two main bottlenecks. First, using the original feature space directly to construct the graph is not necessarily optimal because of the noisy and irrelevant features and nonlinear distributions of data samples. Second, one possible way to handle the nonlinear distribution of data samples is by kernel embedding. However, it is often difficult to choose the most suitable kernel. To solve these bottlenecks, we propose two novel graph-regularized NMF methods, AGNMFFS and AGNMFMK, by introducing feature selection and multiple-kernel learning to the graph regularized NMF, respectively. Instead of using a fixed graph as in GNMF, the two proposed methods learn the nearest neighbor graph that is adaptive to the selected features and learned multiple kernels, respectively. For each method, we propose a unified objective function to conduct feature selection/multi-kernel learning, NMF and adaptive graph regularization simultaneously. We further develop two iterative algorithms to solve the two optimization problems. Experimental results on two challenging pattern classification tasks demonstrate that the proposed methods significantly outperform state-of-the-art data representation methods.

Consequences of block sequence on the orthogonal folding of triblock copolymers

NARCIS (Netherlands)

Hosono, N.; Stals, P.J.M.; Palmans, A.R.A.; Meijer, E.W.

2014-01-01

ABA- and BAB-type triblock copolymers possessing pendant, self-assembling motifs in the A and B blocks were synthesized, with 2-ureidopyrimidinone (UPy) and benzene-1,3,5-tricarboxamide (BTA) for the A and B block, respectively. They were investigated to assess if and how the polymer's

A Large-Scale Multi-Hop Localization Algorithm Based on Regularized Extreme Learning for Wireless Networks.

Science.gov (United States)

Zheng, Wei; Yan, Xiaoyong; Zhao, Wei; Qian, Chengshan

2017-12-20

A novel large-scale multi-hop localization algorithm based on regularized extreme learning is proposed in this paper. The large-scale multi-hop localization problem is formulated as a learning problem. Unlike other similar localization algorithms, the proposed algorithm overcomes the shortcoming of the traditional algorithms which are only applicable to an isotropic network, therefore has a strong adaptability to the complex deployment environment. The proposed algorithm is composed of three stages: data acquisition, modeling and location estimation. In data acquisition stage, the training information between nodes of the given network is collected. In modeling stage, the model among the hop-counts and the physical distances between nodes is constructed using regularized extreme learning. In location estimation stage, each node finds its specific location in a distributed manner. Theoretical analysis and several experiments show that the proposed algorithm can adapt to the different topological environments with low computational cost. Furthermore, high accuracy can be achieved by this method without setting complex parameters.

Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

Science.gov (United States)

Rissanou, Anastassia N.; Tzeli, Despoina S.; Anastasiadis, Spiros H.; Bitsanis, Ioannis A.

2014-05-01

Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (AnBn)m consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500-5000 units) and very differing energetic conditions for the two blocks (very good—almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks.

Segmented block copolymers with monodisperse aramide end-segments

NARCIS (Netherlands)

Araichimani, A.; Gaymans, R.J.

2008-01-01

Segmented block copolymers were synthesized using monodisperse diaramide (TT) as hard segments and PTMO with a molecular weight of 2 900 g · mol-1 as soft segments. The aramide: PTMO segment ratio was increased from 1:1 to 2:1 thereby changing the structure from a high molecular weight multi-block

The phase behavior of polydisperse multiblock copolymer melts: (a theoretical study)

OpenAIRE

Angerman, Hindrik Jan

1998-01-01

Summary The main theme of this thesis is the influence of polydispersity on the phase behavior of copolymer melts. With “polydispersity” we do not only refer to polydispersity in overall chain length, but also to polydispersity in the composition and the monomer sequence of the chains. Study of the influence of polydispersity is important because synthesizing purely monodisperse copolymers is very difficult, and for most polymerization techniques the occurrence of a certain degree of polydisp...

MultiSeq: unifying sequence and structure data for evolutionary analysis

Directory of Open Access Journals (Sweden)

Wright Dan

2006-08-01

Full Text Available Abstract Background Since the publication of the first draft of the human genome in 2000, bioinformatic data have been accumulating at an overwhelming pace. Currently, more than 3 million sequences and 35 thousand structures of proteins and nucleic acids are available in public databases. Finding correlations in and between these data to answer critical research questions is extremely challenging. This problem needs to be approached from several directions: information science to organize and search the data; information visualization to assist in recognizing correlations; mathematics to formulate statistical inferences; and biology to analyze chemical and physical properties in terms of sequence and structure changes. Results Here we present MultiSeq, a unified bioinformatics analysis environment that allows one to organize, display, align and analyze both sequence and structure data for proteins and nucleic acids. While special emphasis is placed on analyzing the data within the framework of evolutionary biology, the environment is also flexible enough to accommodate other usage patterns. The evolutionary approach is supported by the use of predefined metadata, adherence to standard ontological mappings, and the ability for the user to adjust these classifications using an electronic notebook. MultiSeq contains a new algorithm to generate complete evolutionary profiles that represent the topology of the molecular phylogenetic tree of a homologous group of distantly related proteins. The method, based on the multidimensional QR factorization of multiple sequence and structure alignments, removes redundancy from the alignments and orders the protein sequences by increasing linear dependence, resulting in the identification of a minimal basis set of sequences that spans the evolutionary space of the homologous group of proteins. Conclusion MultiSeq is a major extension of the Multiple Alignment tool that is provided as part of VMD, a structural

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

Science.gov (United States)

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)

Extended -Regular Sequence for Automated Analysis of Microarray Images

Directory of Open Access Journals (Sweden)

Jin Hee-Jeong

2006-01-01

Full Text Available Microarray study enables us to obtain hundreds of thousands of expressions of genes or genotypes at once, and it is an indispensable technology for genome research. The first step is the analysis of scanned microarray images. This is the most important procedure for obtaining biologically reliable data. Currently most microarray image processing systems require burdensome manual block/spot indexing work. Since the amount of experimental data is increasing very quickly, automated microarray image analysis software becomes important. In this paper, we propose two automated methods for analyzing microarray images. First, we propose the extended -regular sequence to index blocks and spots, which enables a novel automatic gridding procedure. Second, we provide a methodology, hierarchical metagrid alignment, to allow reliable and efficient batch processing for a set of microarray images. Experimental results show that the proposed methods are more reliable and convenient than the commercial tools.

Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

International Nuclear Information System (INIS)

Rissanou, Anastassia N.; Tzeli, Despoina S.; Anastasiadis, Spiros H.; Bitsanis, Ioannis A.

2014-01-01

Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (A n B n ) m consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500–5000 units) and very differing energetic conditions for the two blocks (very good—almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks

Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Rissanou, Anastassia N., E-mail: rissanou@tem.uoc.gr [Department of Mathematics and Applied Mathematics, University of Crete, GR-71003 Heraklion Crete, Greece and Archimedes Center for Analysis, Modeling and Computation, University of Crete, P.O. Box 2208, GR-71003 Heraklion Crete (Greece); Tzeli, Despoina S. [Department of Materials Science and Technology, University of Crete, GR-71003 Heraklion Crete (Greece); Anastasiadis, Spiros H. [Department of Chemistry, University of Crete, P.O. Box 2208, 710 03 Heraklion Crete (Greece); Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, GR-71110 Heraklion Crete (Greece); Bitsanis, Ioannis A. [Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, GR-71110 Heraklion Crete (Greece)

2014-05-28

Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (A{sub n}B{sub n}){sub m} consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500–5000 units) and very differing energetic conditions for the two blocks (very good—almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks.

Directing self-assembly of gold nanoparticles in diblock copolymer scaffold

Science.gov (United States)

Li, Qifang; He, Jinbo; Glogowski, Elizabeth; Emrick, Todd; Russell, Thomas

2007-03-01

A versatile hierarchical approach for directing self -assembly of gold nanostructures with size 2-3nm in diblock copolymer scaffolds is found. Diblock copolymer polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) is used to form a regular scaffold of highly anisotropic, stripe-like domains, and controlled differential wetting by dichloromethane and thermal annealing guides gold nanoparticles with half hydrophilic ligand to aggregate selectively along the scaffold, producing highly organized metal nanostructures. In as-cast block-copolymer and gold nanoparticles thin films, micelle structure and gold nanoparticles random distribution on scaffold are typically observed. However, samples annealed in dichloromethane exhibit well-defined short-range ordered nanostructure with gold nanoparticles located at the interface of PS and P2VP nanoscale domain. After annealing at 170 C, the gold nanoparticles at interface migrated into the middle of P2VP phase and exhibited long-range ordered hierarchical structures. Synergistic interactions between the gold nanoparticles and the PS-b-P2VP caused an orientation of the microdomains normal to the film surface.

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

Energy Technology Data Exchange (ETDEWEB)

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

2005-12-17

The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

OBJECT-SPACE MULTI-IMAGE MATCHING OF MOBILE-MAPPING-SYSTEM IMAGE SEQUENCES

Directory of Open Access Journals (Sweden)

Y. C. Chen

2012-07-01

Full Text Available This paper proposes an object-space multi-image matching procedure of terrestrial MMS (Mobile Mapping System image sequences to determine the coordinates of an object point automatically and reliably. This image matching procedure can be applied to find conjugate points of MMS image sequences efficiently. Conventional area-based image matching methods are not reliable to deliver accurate matching results for this application due to image scale variations, viewing angle variations, and object occlusions. In order to deal with these three matching problems, an object space multi-image matching is proposed. A modified NCC (Normalized Cross Correlation coefficient is proposed to measure the similarity of image patches. A modified multi-window matching procedure will also be introduced to solve the problem of object occlusion. A coarse-to-fine procedure with a combination of object-space multi-image matching and multi-window matching is adopted. The proposed procedure has been implemented for the purpose of matching terrestrial MMS image sequences. The ratio of correct matches of this experiment was about 80 %. By providing an approximate conjugate point in an overlapping image manually, most of the incorrect matches could be fixed properly and the ratio of correct matches was improved up to 98 %.

Dynamical decoupling sequences for multi-qubit dephasing suppression and long-time quantum memory

International Nuclear Information System (INIS)

Paz-Silva, Gerardo A; Lee, Seung-Woo; Green, Todd J; Viola, Lorenza

2016-01-01

We consider a class of multi-qubit dephasing models that combine classical noise sources and linear coupling to a bosonic environment, and are controlled by arbitrary sequences of dynamical decoupling pulses. Building on a general transfer filter-function framework for open-loop control, we provide an exact representation of the controlled dynamics for arbitrary stationary non-Gaussian classical and quantum noise statistics, with analytical expressions emerging when all dephasing sources are Gaussian. This exact characterization is used to establish two main results. First, we construct multi-qubit sequences that ensure maximum high-order error suppression in both the time and frequency domain and that can be exponentially more efficient than existing ones in terms of total pulse number. Next, we show how long-time multi-qubit storage may be achieved by meeting appropriate conditions for the emergence of a fidelity plateau under sequence repetition, thereby generalizing recent results for single-qubit memory under Gaussian dephasing. In both scenarios, the key step is to endow multi-qubit sequences with a suitable displacement anti-symmetry property, which is of independent interest for applications ranging from environment-assisted entanglement generation to multi-qubit noise spectroscopy protocols. (paper)

A soft and conductive PDMS-PEG block copolymer as a compliant electrode for dielectric elastomers

DEFF Research Database (Denmark)

A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

Conductive PDMS-PEG block copolymers (Mn = 3 – 5 kg/mol) were chain-extended (Mn = 30 – 45 kg/mol) using hydrosilylation reaction as presented in figure 1. Subsequently, the extended copolymers were added to a conductive nano-filler (multi-walled carbon nanotubes – MWCNTs) in order to enhance...... conductivity. The combination of soft chainextended PDMS-PEG block copolymers and conductive MWCNTs results in a soft and conductive block copolymer composite which potentially can be used as a compliant and highly stretchable electrode for dielectric elastomers. The addition of MWCNTs into the PDMS-PEG matrix...... MWCNTs is 10-3 S/cm compared to 10-1 S/cm of a non-stretchable reference conducting silicone elastomer (LR3162 from Wacker). Furthermore, PDMS-PEG block copolymer with 4 phr MWCNTs (Young’s modulus, Y = 0.26 MPa) is softer and more stretchable thanLR3162 (Y = 1.17 MPa)....

Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

KAUST Repository

O'Shea, John Paul; Solov'eva, Vera A.; Guo, Xianrong; Zhao, Junpeng; Hadjichristidis, Nikolaos; Rodionov, Valentin

2014-01-01

A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.

Silicon containing copolymers

CERN Document Server

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.

Using 3D spatial correlations to improve the noise robustness of multi component analysis of 3D multi echo quantitative T2 relaxometry data.

Science.gov (United States)

Kumar, Dushyant; Hariharan, Hari; Faizy, Tobias D; Borchert, Patrick; Siemonsen, Susanne; Fiehler, Jens; Reddy, Ravinder; Sedlacik, Jan

2018-05-12

We present a computationally feasible and iterative multi-voxel spatially regularized algorithm for myelin water fraction (MWF) reconstruction. This method utilizes 3D spatial correlations present in anatomical/pathological tissues and underlying B1 + -inhomogeneity or flip angle inhomogeneity to enhance the noise robustness of the reconstruction while intrinsically accounting for stimulated echo contributions using T2-distribution data alone. Simulated data and in vivo data acquired using 3D non-selective multi-echo spin echo (3DNS-MESE) were used to compare the reconstruction quality of the proposed approach against those of the popular algorithm (the method by Prasloski et al.) and our previously proposed 2D multi-slice spatial regularization spatial regularization approach. We also investigated whether the inter-sequence correlations and agreements improved as a result of the proposed approach. MWF-quantifications from two sequences, 3DNS-MESE vs 3DNS-gradient and spin echo (3DNS-GRASE), were compared for both reconstruction approaches to assess correlations and agreements between inter-sequence MWF-value pairs. MWF values from whole-brain data of six volunteers and two multiple sclerosis patients are being reported as well. In comparison with competing approaches such as Prasloski's method or our previously proposed 2D multi-slice spatial regularization method, the proposed method showed better agreements with simulated truths using regression analyses and Bland-Altman analyses. For 3DNS-MESE data, MWF-maps reconstructed using the proposed algorithm provided better depictions of white matter structures in subcortical areas adjoining gray matter which agreed more closely with corresponding contrasts on T2-weighted images than MWF-maps reconstructed with the method by Prasloski et al. We also achieved a higher level of correlations and agreements between inter-sequence (3DNS-MESE vs 3DNS-GRASE) MWF-value pairs. The proposed algorithm provides more noise

Design of Protein Multi-specificity Using an Independent Sequence Search Reduces the Barrier to Low Energy Sequences.

Directory of Open Access Journals (Sweden)

Alexander M Sevy

2015-07-01

Full Text Available Computational protein design has found great success in engineering proteins for thermodynamic stability, binding specificity, or enzymatic activity in a 'single state' design (SSD paradigm. Multi-specificity design (MSD, on the other hand, involves considering the stability of multiple protein states simultaneously. We have developed a novel MSD algorithm, which we refer to as REstrained CONvergence in multi-specificity design (RECON. The algorithm allows each state to adopt its own sequence throughout the design process rather than enforcing a single sequence on all states. Convergence to a single sequence is encouraged through an incrementally increasing convergence restraint for corresponding positions. Compared to MSD algorithms that enforce (constrain an identical sequence on all states the energy landscape is simplified, which accelerates the search drastically. As a result, RECON can readily be used in simulations with a flexible protein backbone. We have benchmarked RECON on two design tasks. First, we designed antibodies derived from a common germline gene against their diverse targets to assess recovery of the germline, polyspecific sequence. Second, we design "promiscuous", polyspecific proteins against all binding partners and measure recovery of the native sequence. We show that RECON is able to efficiently recover native-like, biologically relevant sequences in this diverse set of protein complexes.

Motif discovery in ranked lists of sequences

DEFF Research Database (Denmark)

Nielsen, Morten Muhlig; Tataru, Paula; Madsen, Tobias

2016-01-01

Motif analysis has long been an important method to characterize biological functionality and the current growth of sequencing-based genomics experiments further extends its potential. These diverse experiments often generate sequence lists ranked by some functional property. There is therefore...... advantage of the regular expression feature, including enrichments for combinations of different microRNA seed sites. The method is implemented and made publicly available as an R package and supports high parallelization on multi-core machinery....... a growing need for motif analysis methods that can exploit this coupled data structure and be tailored for specific biological questions. Here, we present an exploratory motif analysis tool, Regmex (REGular expression Motif EXplorer), which offers several methods to evaluate the correlation of motifs...

Thermodynamic interactions of water-soluble homopolymers and double-hydrophilic diblock copolymer

International Nuclear Information System (INIS)

Yazici, D. Topaloglu; Askin, A.; Buetuen, V.

2008-01-01

Thermodynamic interaction parameters of water-soluble poly[2-(dimethylamino)ethyl methacrylate] (DMA) and poly[2-(N-morpholino)ethyl methacrylate] (MEMA) homopolymers and their diblock copolymer (DMA-MEMA) were investigated at the temperatures above their glass-transition temperatures (T g ) by inverse gas chromatography (IGC) method. Sorption thermodynamic parameters of some aliphatic, alicyclic and aromatic hydrocarbons, weight fraction activity coefficients, Flory-Huggins interaction parameters, and solubility parameters for hydrocarbons and polymers were calculated. It was observed that sorption thermodynamic parameters on (co)polymers depend on the molecular structures of hydrocarbons. Evaluating both the calculated values of the weight fraction activity coefficients and Flory-Huggins interaction parameters, the solving ability of the hydrocarbons for DMA, MEMA homopolymers, and DMA-MEMA diblock copolymer decreased in the following sequence: Aromatic > alicyclic > aliphatic hydrocarbons

Multiple graph regularized protein domain ranking.

Science.gov (United States)

Wang, Jim Jing-Yan; Bensmail, Halima; Gao, Xin

2012-11-19

Protein domain ranking is a fundamental task in structural biology. Most protein domain ranking methods rely on the pairwise comparison of protein domains while neglecting the global manifold structure of the protein domain database. Recently, graph regularized ranking that exploits the global structure of the graph defined by the pairwise similarities has been proposed. However, the existing graph regularized ranking methods are very sensitive to the choice of the graph model and parameters, and this remains a difficult problem for most of the protein domain ranking methods. To tackle this problem, we have developed the Multiple Graph regularized Ranking algorithm, MultiG-Rank. Instead of using a single graph to regularize the ranking scores, MultiG-Rank approximates the intrinsic manifold of protein domain distribution by combining multiple initial graphs for the regularization. Graph weights are learned with ranking scores jointly and automatically, by alternately minimizing an objective function in an iterative algorithm. Experimental results on a subset of the ASTRAL SCOP protein domain database demonstrate that MultiG-Rank achieves a better ranking performance than single graph regularized ranking methods and pairwise similarity based ranking methods. The problem of graph model and parameter selection in graph regularized protein domain ranking can be solved effectively by combining multiple graphs. This aspect of generalization introduces a new frontier in applying multiple graphs to solving protein domain ranking applications.

Multi-label learning with fuzzy hypergraph regularization for protein subcellular location prediction.

Science.gov (United States)

Chen, Jing; Tang, Yuan Yan; Chen, C L Philip; Fang, Bin; Lin, Yuewei; Shang, Zhaowei

2014-12-01

Protein subcellular location prediction aims to predict the location where a protein resides within a cell using computational methods. Considering the main limitations of the existing methods, we propose a hierarchical multi-label learning model FHML for both single-location proteins and multi-location proteins. The latent concepts are extracted through feature space decomposition and label space decomposition under the nonnegative data factorization framework. The extracted latent concepts are used as the codebook to indirectly connect the protein features to their annotations. We construct dual fuzzy hypergraphs to capture the intrinsic high-order relations embedded in not only feature space, but also label space. Finally, the subcellular location annotation information is propagated from the labeled proteins to the unlabeled proteins by performing dual fuzzy hypergraph Laplacian regularization. The experimental results on the six protein benchmark datasets demonstrate the superiority of our proposed method by comparing it with the state-of-the-art methods, and illustrate the benefit of exploiting both feature correlations and label correlations.

Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

Science.gov (United States)

Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2014-02-01

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructural Analysis of Carbonyl Signal in the 13C NMR Spectra of Methyl Methacrylate - n-Butyl Acrylate Copolymer

International Nuclear Information System (INIS)

Bujak, P.; Matlengiewicz, M.

2005-01-01

Microstructural information on acrylic copolymers, i.e. distribution of the comonomers along the macromolecular chain and their stereochemical arrangement (tacticity) can be derived from 13 C NMR, analyzing the splitting of their carbonyl signal. In the 100 MHz 13 C NMR spectrum of poly(methyl methacrylate-co-n-butyl acrylate), PMMA-nBA, the carbonyl signal at 174-178,5 ppm is clearly split into the lines of configurational-compositional pentads. This splitting is slightly different in different solvents, hence, recording of the same sample in different solvents may reveal differences important to correct assignment of individual sequences, since their probabilities (intensities) remain the same, while the chemical shift can vary in different solvents. If we would like to perform a complete analysis at this level we have to determine the distribution of 272 individual pentads. The outermost lines in the carbonyl signal of the copolymer can be assigned to the sequences of pure composition by simple comparison with the spectra of respective homopolymers. The rest of the inner lines cannot be easily attributed, therefore, a series of copolymer samples of different composition were synthesized in order to observe the different heterosequences, since depending on copolymer composition, different signals representing individual sequences, assume different relative intensities. To confirm the correctness of proposed attribution a simulation of the carbonyl signal can be performed. It is therefore necessary to know the intensities and positions of individual signals, representing individual compositional-configurational pentads. Calculation of the intensity of the lines can be performed assuming Bernoullian and/or Markov statistics, separately for compositional and configurational sequences and verifying the overall distribution of the individual probabilities. The position of the individual lines cannot be straightforwardly determined, therefore, we have adopted an

Multiple graph regularized protein domain ranking

KAUST Repository

Wang, Jim Jing-Yan

2012-11-19

Background: Protein domain ranking is a fundamental task in structural biology. Most protein domain ranking methods rely on the pairwise comparison of protein domains while neglecting the global manifold structure of the protein domain database. Recently, graph regularized ranking that exploits the global structure of the graph defined by the pairwise similarities has been proposed. However, the existing graph regularized ranking methods are very sensitive to the choice of the graph model and parameters, and this remains a difficult problem for most of the protein domain ranking methods.Results: To tackle this problem, we have developed the Multiple Graph regularized Ranking algorithm, MultiG-Rank. Instead of using a single graph to regularize the ranking scores, MultiG-Rank approximates the intrinsic manifold of protein domain distribution by combining multiple initial graphs for the regularization. Graph weights are learned with ranking scores jointly and automatically, by alternately minimizing an objective function in an iterative algorithm. Experimental results on a subset of the ASTRAL SCOP protein domain database demonstrate that MultiG-Rank achieves a better ranking performance than single graph regularized ranking methods and pairwise similarity based ranking methods.Conclusion: The problem of graph model and parameter selection in graph regularized protein domain ranking can be solved effectively by combining multiple graphs. This aspect of generalization introduces a new frontier in applying multiple graphs to solving protein domain ranking applications. 2012 Wang et al; licensee BioMed Central Ltd.

Multiple graph regularized protein domain ranking

KAUST Repository

Wang, Jim Jing-Yan; Bensmail, Halima; Gao, Xin

2012-01-01

Background: Protein domain ranking is a fundamental task in structural biology. Most protein domain ranking methods rely on the pairwise comparison of protein domains while neglecting the global manifold structure of the protein domain database. Recently, graph regularized ranking that exploits the global structure of the graph defined by the pairwise similarities has been proposed. However, the existing graph regularized ranking methods are very sensitive to the choice of the graph model and parameters, and this remains a difficult problem for most of the protein domain ranking methods.Results: To tackle this problem, we have developed the Multiple Graph regularized Ranking algorithm, MultiG-Rank. Instead of using a single graph to regularize the ranking scores, MultiG-Rank approximates the intrinsic manifold of protein domain distribution by combining multiple initial graphs for the regularization. Graph weights are learned with ranking scores jointly and automatically, by alternately minimizing an objective function in an iterative algorithm. Experimental results on a subset of the ASTRAL SCOP protein domain database demonstrate that MultiG-Rank achieves a better ranking performance than single graph regularized ranking methods and pairwise similarity based ranking methods.Conclusion: The problem of graph model and parameter selection in graph regularized protein domain ranking can be solved effectively by combining multiple graphs. This aspect of generalization introduces a new frontier in applying multiple graphs to solving protein domain ranking applications. 2012 Wang et al; licensee BioMed Central Ltd.

Multiple graph regularized protein domain ranking

Directory of Open Access Journals (Sweden)

Wang Jim

2012-11-01

Full Text Available Abstract Background Protein domain ranking is a fundamental task in structural biology. Most protein domain ranking methods rely on the pairwise comparison of protein domains while neglecting the global manifold structure of the protein domain database. Recently, graph regularized ranking that exploits the global structure of the graph defined by the pairwise similarities has been proposed. However, the existing graph regularized ranking methods are very sensitive to the choice of the graph model and parameters, and this remains a difficult problem for most of the protein domain ranking methods. Results To tackle this problem, we have developed the Multiple Graph regularized Ranking algorithm, MultiG-Rank. Instead of using a single graph to regularize the ranking scores, MultiG-Rank approximates the intrinsic manifold of protein domain distribution by combining multiple initial graphs for the regularization. Graph weights are learned with ranking scores jointly and automatically, by alternately minimizing an objective function in an iterative algorithm. Experimental results on a subset of the ASTRAL SCOP protein domain database demonstrate that MultiG-Rank achieves a better ranking performance than single graph regularized ranking methods and pairwise similarity based ranking methods. Conclusion The problem of graph model and parameter selection in graph regularized protein domain ranking can be solved effectively by combining multiple graphs. This aspect of generalization introduces a new frontier in applying multiple graphs to solving protein domain ranking applications.

Theory of the Flower Micelle Formation of Amphiphilic Random and Periodic Copolymers in Solution

Directory of Open Access Journals (Sweden)

Takahiro Sato

2018-01-01

Full Text Available The mixing Gibbs energy Δgm for the flower-micelle phase of amphiphilic random and periodic (including alternating copolymers was formulated on the basis of the lattice model. The formulated Δgm predicts (1 the inverse proportionality of the aggregation number to the degree of polymerization of the copolymer, (2 the increase of the critical micelle concentration with decreasing the hydrophobe content, and (3 the crossover from the micellization to the liquid–liquid phase separation as the hydrophobe content increases. The transition from the uni-core flower micelle to the multi-core flower necklace as the degree of polymerization increases was also implicitly indicated by the theory. These theoretical results were compared with experimental results for amphiphilic random and alternating copolymers reported so far.

Olefin–Styrene Copolymers

OpenAIRE

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.

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

KAUST Repository

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

Electrochemical and visco metric studies on some copolymer/ homopolymer poly electrolytes and transition metal ion interaction

International Nuclear Information System (INIS)

Rajabi, F. H.; Frahani, B. V.

2003-01-01

Some random three-component copolymers have been prepared by condensing of formaldehyde with various aromatic amines. The compositions of the copolymers have been determined by known methods. selective complexation of copolymers have been carried out with PAA, PEI, PVP and some transition metal ions (e.g., Cu 2+ )by adding the components in various sequences. The relative complexation ability of different -NH 2 groups, associated with the various comonomer units, has been interpreted in terms of the these complexes has been studied by conductometry. potentiometry and viscometry techniques. A scheme has presented to explain the mode of interaction of the various components

Subtyping Salmonella enterica serovar enteritidis isolates from different sources by using sequence typing based on virulence genes and clustered regularly interspaced short palindromic repeats (CRISPRs).

Science.gov (United States)

Liu, Fenyun; Kariyawasam, Subhashinie; Jayarao, Bhushan M; Barrangou, Rodolphe; Gerner-Smidt, Peter; Ribot, Efrain M; Knabel, Stephen J; Dudley, Edward G

2011-07-01

Salmonella enterica subsp. enterica serovar Enteritidis is a major cause of food-borne salmonellosis in the United States. Two major food vehicles for S. Enteritidis are contaminated eggs and chicken meat. Improved subtyping methods are needed to accurately track specific strains of S. Enteritidis related to human salmonellosis throughout the chicken and egg food system. A sequence typing scheme based on virulence genes (fimH and sseL) and clustered regularly interspaced short palindromic repeats (CRISPRs)-CRISPR-including multi-virulence-locus sequence typing (designated CRISPR-MVLST)-was used to characterize 35 human clinical isolates, 46 chicken isolates, 24 egg isolates, and 63 hen house environment isolates of S. Enteritidis. A total of 27 sequence types (STs) were identified among the 167 isolates. CRISPR-MVLST identified three persistent and predominate STs circulating among U.S. human clinical isolates and chicken, egg, and hen house environmental isolates in Pennsylvania, and an ST that was found only in eggs and humans. It also identified a potential environment-specific sequence type. Moreover, cluster analysis based on fimH and sseL identified a number of clusters, of which several were found in more than one outbreak, as well as 11 singletons. Further research is needed to determine if CRISPR-MVLST might help identify the ecological origins of S. Enteritidis strains that contaminate chickens and eggs.

Gradient Architecture as Means of Phase Diagram Manipulation in Copolymers: Accessing Both LCOT and UCOT in High Molecular Weight Styrene/n-Butyl Acrylate Systems

Science.gov (United States)

Mok, Michelle; Burghardt, Wesley; Ellison, Christopher; Torkelson, John

2009-03-01

Traditionally, phase transitions of block copolymers could only be tuned through molecular weight and relative block length. Here, we introduce comonomer sequence design through gradient compositions as a means of further manipulating phase diagram boundaries. In such gradient copolymers, the reduced repulsion between chain segments allows access to phase transitions even at high molecular weights (MW). Rheological and x-ray scattering studies were performed to study the impact of comonomer sequence on phase behavior in styrene/n-butyl acrylate (S/nBA) systems. In S/nBA block copolymers, only upper critical ordering behavior was observed. In contrast, by using a gradient architecture of higher MW we observed both upper and lower ordering transitions similar to those seen in very weakly segregating S/n-butyl methacrylate block copolymers, where such dual ordering transitions were first detected by Russell et al. This is the first study to access a miscibility gap in gradient copolymers. Access to such behavior is very rare in blends and block copolymers, limited to low MW and/or very weakly segregating systems.

Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

NARCIS (Netherlands)

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

Formation of polystyrene/poly(methyl methacrylate) heteroarm star-like nanogels from complementarily reactive well-defined diblock copolymers

Energy Technology Data Exchange (ETDEWEB)

Amamoto, Y; Otsuka, H; Takahara, A, E-mail: otsuka@ms.ifoc.kyushu-u.ac.j [Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0385 (Japan)

2009-08-01

Formation of star-like nanogels with two different arms via cross-linking reaction of complementarily reactive diblock copolymers was successfully accomplished. The two types of diblock copolymers, consisting of poly(methyl methacrylate) (PMMA) or polystyrene (PSt) block and alkoxyamine-based cross-linkable block, were prepared by atom transfer radical polymerization (ATRP) methods. The cross-linking reactions were carried out by merely heating their mixture, and traced by gel permeation chromatography (GPC) and multi-angle light scattering (MALS) measurements. The diblock copolymers were reacted in complementarily reactive systems, showing that all star-like nanogels have necessarily two types of arms as PMMA and PSt chains.

Generalised Multi-sequence Shift-Register Synthesis using Module Minimisation

DEFF Research Database (Denmark)

Nielsen, Johan Sebastian Rosenkilde

2013-01-01

We show how to solve a generalised version of the Multi-sequence Linear Feedback Shift-Register (MLFSR) problem using minimisation of free modules over F[x]. We show how two existing algorithms for minimising such modules run particularly fast on these instances. Furthermore, we show how one...

Photoisomerization study of p-phenylazoacrylanilide and its homo- and copolymers

Science.gov (United States)

Rachkov, A.; Minoura, N.; Shimizu, T.

2003-01-01

To develop materials possessing intrinsic photoresponsive properties, a polymerizable derivative of azobenzene was synthesized. Condensation of acryloyl chloride with 4-phenylazoaniline was performed in THF with 100% conversion to the final product p-phenylazoacrylanilide. Its homopolymers and copolymers with methacrylic acid were prepared by free radical polymerization using 2,2 '-azobis (2,4-dimethylvaleronitrile) as an initiator. Copolymerization reactivity ratios showed clear preference to form short sequences of polymethacrylic acid alternated by individual p-phenylazoacrylanilide residues. Photochemical interconversion between trans and cis isomers of p-phenylazoacrylanilide under UV or visible light irradiation was shown to be reversible and reproducible for the monomer as well as for the homopolymers and the copolymers with methacrylic acid.

Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

Science.gov (United States)

Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Main-chain supramolecular block copolymers.

Science.gov (United States)

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.

A complicated biocomputing system based on multi-responsive P(NIPAM-co-APBA) copolymer film electrodes and electrocatalysis of NADH.

Science.gov (United States)

Liang, Jiying; Yu, Xue; Yang, Tiangang; Li, Menglu; Shen, Li; Jin, Yue; Liu, Hongyun

2017-08-23

In this paper, poly(N-isopropylacrylamide-co-3-aminophenylboronic acid) (P(NIPAM-co-APBA)) copolymer films were successfully electropolymerized on the Au electrode surface. The electroactive probe ferrocene carboxylic acid (FCA) in solution showed reversible thermal-, glucose- and pH-responsive on-off cyclic voltammetric (CV) behaviors at the film electrodes. The comparative experiments demonstrated that the thermo-responsive property of the film electrode was ascribed to the PNIPAM component of the films, whereas the glucose- and pH-sensitive behaviors came from the PAPBA constituent. The reduced form of nicotinamide adenine dinucleotide (NADH) could be electrocatalytically oxidized by FCA at the film electrodes, which would greatly amplify the multi-responsive CV signal difference between the on and off states. On the basis of these results, a binary 4-input/4-output logic circuit was fabricated with temperature, glucose, pH and NADH as inputs and the CV responses at 4 different levels as outputs. Moreover, a ternary CONSENSUS logic circuit was established on the same platform, which was the first report on the combination of ternary logic gate and bioelectrocatalysis without using enzymes. This work provided a novel idea for constructing complicated biocomputing systems by increasing the number of inputs/outputs with multi-sensitive interfaces and by designing new types of multi-valued logic gates on the basis of bioelectrocatalysis.

Metallo-supramolecular block copolymer micelles

NARCIS (Netherlands)

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,

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies.

Science.gov (United States)

Bartels, Jeremy W; Cauët, Solène I; Billings, Peter L; Lin, Lily Yun; Zhu, Jiahua; Fidge, Christopher; Pochan, Darrin J; Wooley, Karen L

2010-09-14

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA. Self assembly of the block copolymers in both water and decane was investigated and the resulting regular and inverse assemblies, respectively, were analyzed with DLS, AFM, and TEM to ascertain their dimensions and properties. Assembly of PEO-b-PIp block copolymers in aqueous solution resulted in well-defined micelles of varying sizes while the assembly in hydrophobic, organic solvent resulted in the formation of different morphologies including large aggregates and well-defined cylindrical and spherical structures.

The phase behavior of polydisperse multiblock copolymer melts : (a theoretical study)

NARCIS (Netherlands)

Angerman, Hindrik Jan

1998-01-01

Summary The main theme of this thesis is the influence of polydispersity on the phase behavior of copolymer melts. With “polydispersity” we do not only refer to polydispersity in overall chain length, but also to polydispersity in the composition and the monomer sequence of the chains. Study of the

The degree of doubly charged cation binding in solutions of (co)polymers of 2-acrylamido-2-methylpropanesulfonic acid salts

International Nuclear Information System (INIS)

Kurenkov, V.F.; Kolesnikova, I.Yu.; Antonovich, O.A.

2002-01-01

The degree of binding the ions of the alkaline-earth metals (M = Mg, Ca, Sr, Ba) by the polysulfate anions in the aqueous solutions of the polymers of the 2-acrylamido-2-methylpropanesulfonic acid (N-AMS) salts and their binary copolymers with the acrylamide (AA) and N-vinylpyrrolidone (VP) is quantitatively evaluated through the Terayama and Wall viscosimetric method. It is established, that the degree of binding decreases in the Sr>Ca>Mg sequence for the N-AMS polymer salts and in the reverse sequence (Mg>Ca>Sr(Ba)) for the binary copolymers of the N-AMS salts with AA and VP [ru

Characterisation of polyhydroxyalkanoate copolymers with controllable four-monomer composition.

Science.gov (United States)

Dai, Yu; Lambert, Lynette; Yuan, Zhiguo; Keller, Jurg

2008-03-20

Polyhydroxyalkanoate (PHA) copolymers comprising the four monomers 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 3-hydroxy-2-methylvalerate (3HMV) and 3-hydroxy-2-methylbutyrate (3HMB) were generated using the recently discovered Defluviicoccus vanus-related glycogen accumulating organisms (DvGAOs) under anaerobic conditions without applying any nutrient limitations. The composition could be manipulated in a defined range by modifying the ratio of propionate and acetate provided in the feed stream. The PHAs produced were characterised as random copolymers (from propionate alone) or a mixture of random copolymers (from mixture of propionate and acetate) through microstructure analysis using 13C NMR spectroscopy. The sequence distribution of all eight comonomer pairs in the carbonyl region of 3HB and 3HV was identified and assigned with confidence utilising two-dimensional heteronuclear multiple bond coherence (HMBC) spectroscopy. Weight average molecular weights were in the range 390-560 kg/mol. Differential scanning calorimetry (DSC) traces showed that the melting temperature (Tm) varied between 70 and 161 degrees C and glass transition temperature (Tg) ranged from -8 to 0 degrees C. The incorporation of considerable amounts of 3HMV and 3HMB monomer units introduced additional "defects" into the PHBV copolymer structure and hence greatly lowered the crystallinity. The data indicate the potential of these four-monomer PHAs to be employed for practical applications, considering their favourable properties and the cost-effective production process using a mixed culture and simple carbon sources.

Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

Science.gov (United States)

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.

Tadpole-Shaped POSS-Based Copolymers and the Aggregation Behavior at Air/Water Interface

Directory of Open Access Journals (Sweden)

Lin Zhu

2018-01-01

Full Text Available The aggregation behavior of three tadpole-shaped Polyhedral oligomeric silsesquioxane (POSS based block copolymers using different blocks poly(methyl methacrylate (PMMA and poly(trifluoroethyl methacrylate (PTFEMA with different block sequence and ratio (POSS-PTFEMA161-b-PMMA236, POSS-PMMA277-b-PTFEMA130, and POSS-PMMA466-b-PTFEMA172 was investigated on the air-water interface. The interfacial rheology of three block copolymers was studied by surface pressure isotherm, compression modulus measurements, and compression and expansion hysteresis analysis on the Langmuir trough. The block sequence and ratio play a great role in self-assembly behavior at the interface. Based on surface pressure isotherm analysis, a thin film with low elasticity was achieved for the POSS-PTFEMA161-b-PMMA236. Moreover, for the block copolymer with same segment sequence (POSS-PMMA2-b-PTFEMA, the thin film compression capability is increased with increasing the PMMA ratio. The morphology of the deposited LB thin film was illustrated by atomic force microscopy (AFM and X-ray photoelectron spectroscopy (XPS. We observed that a thin film was composed by crater-shaped quasi-2D micelles for POSS-PTFEMA-b-PMMA, while it was proved that only flaky texture was observed for both POSS-PMMA277-b-PTFEMA130 and POSS-PMMA466-b-PTFEMA172. The thickness and area of flaky aggregates were greatly related to PMMA ratio. The different interface self-assembly structure evolution was proposed based on the interfacial rheology and thin film morphology studies.

Selective molecular annealing: in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers.

Science.gov (United States)

Toolan, Daniel T W; Adlington, Kevin; Isakova, Anna; Kalamiotis, Alexis; Mokarian-Tabari, Parvaneh; Dimitrakis, Georgios; Dodds, Christopher; Arnold, Thomas; Terrill, Nick J; Bras, Wim; Hermida Merino, Daniel; Topham, Paul D; Irvine, Derek J; Howse, Jonathan R

2017-08-09

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

The radiation crosslinking of ethylene copolymers

International Nuclear Information System (INIS)

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)

Self-assembly in casting solutions of block copolymer membranes

KAUST Repository

Marques, Debora S.; Vainio, Ulla; Moreno Chaparro, Nicolas; Calo, Victor M.; Bezahd, Ali Reza; Pitera, Jed W.; Peinemann, Klaus; Nunes, Suzana Pereira

2013-01-01

Membranes with exceptional pore regularity and high porosity were obtained from block copolymer solutions. We demonstrate by small-angle X-ray scattering that the order which gives rise to the pore morphology is already incipient in the casting solution. Hexagonal order was confirmed in PS-b-P4VP 175k-b-65k solutions in DMF/THF/dioxane with concentrations as high as 24 wt%, while lamellar structures were obtained in more concentrated solutions in DMF or DMF/dioxane. The change in order has been understood with the support of dissipative particle dynamic modeling. © 2013 The Royal Society of Chemistry.

IMRT sequencing for a six-bank multi-leaf system

International Nuclear Information System (INIS)

Topolnjak, R; Heide, U A van der; Lagendijk, J J W

2005-01-01

In this study, we present a sequencer for delivering step-and-shoot IMRT using a six-bank multi-leaf system. Such a system was proposed earlier and combines a high-resolution field-shaping ability with a large field size. It consists of three layers of two opposing leaf banks with 1 cm leaves. The layers are rotated relative to each other at 60 0 . A low-resolution mode of sequencing is achieved by using one layer of leaves as primary MLC, while the other two are used to improve back-up collimation. For high-resolution sequencing, an algorithm is presented that creates segments shaped by all six banks. Compared to a hypothetical mini-MLC with 0.4 cm leaves, a similar performance can be achieved, but a trade-off has to be made between accuracy and the number of segments

Thermal Analysis, Structural Studies and Morphology of Spider Silk-like Block Copolymers

Science.gov (United States)

Huang, Wenwen

Spider silk is a remarkable natural block copolymer, which offers a unique combination of low density, excellent mechanical properties, and thermal stability over a wide range of temperature, along with biocompatibility and biodegrability. The dragline silk of Nephila clavipes, is one of the most well understood and the best characterized spider silk, in which alanine-rich hydrophobic blocks and glycine-rich hydrophilic blocks are linked together generating a functional block copolymer with potential uses in biomedical applications such as guided tissue repair and drug delivery. To provide further insight into the relationships among peptide amino acid sequence, block length, and physical properties, in this thesis, we studied synthetic proteins inspired by the genetic sequences found in spider dragline silks, and used these bioengineered spider silk block copolymers to study thermal, structural and morphological features. To obtain a fuller understanding of the thermal dynamic properties of these novel materials, we use a model to calculate the heat capacity of spider silk block copolymer in the solid or liquid state, below or above the glass transition temperature, respectively. We characterize the thermal phase transitions by temperature modulated differential scanning calorimetry (TMDSC) and thermogravimetric analysis (TGA). We also determined the crystallinity by TMDSC and compared the result with Fourier transform infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). To understand the protein-water interactions with respect to the protein amino acid sequence, we also modeled the specific reversing heat capacity of the protein-water system, Cp(T), based on the vibrational, rotational and translational motions of protein amino acid residues and water molecules. Advanced thermal analysis methods using TMDSC and TGA show two glass transitions were observed in all samples during heating. The low temperature glass transition, Tg(1), is related to

Block copolymer stabilized nonaqueous biocompatible sub-micron emulsions for topical applications.

Science.gov (United States)

Atanase, Leonard Ionut; Riess, Gérard

2013-05-20

Polyethylene glycol (PEG) 400/Miglyol 812 non-aqueous sub-micron emulsions were developed due to the fact that they are of interest for the design of drug-loaded biocompatible topical formulations. These types of emulsions were favourably stabilized by poly (2-vinylpyridine)-b-poly (butadiene) (P2VP-b-PBut) copolymer with DPBut>DP2VP, each of these sequences being well-adapted to the solubility parameters of PEG 400 and Miglyol 812, respectively. This type of block copolymers, which might limit the Ostwald ripening, appeared to be more efficient stabilizers than low molecular weight non-ionic surfactants. The emulsion characteristics, such as particle size, stability and viscosity at different shear rates were determined as a function of the phase ratio, the copolymer concentration and storage time. It was further shown that Acyclovir, as a model drug of low water solubility, could be incorporated into the PEG 400 dispersed phase, with no significant modification of the initial emulsion characteristics. Copyright © 2013 Elsevier B.V. All rights reserved.

Learning regularization parameters for general-form Tikhonov

International Nuclear Information System (INIS)

Chung, Julianne; Español, Malena I

2017-01-01

Computing regularization parameters for general-form Tikhonov regularization can be an expensive and difficult task, especially if multiple parameters or many solutions need to be computed in real time. In this work, we assume training data is available and describe an efficient learning approach for computing regularization parameters that can be used for a large set of problems. We consider an empirical Bayes risk minimization framework for finding regularization parameters that minimize average errors for the training data. We first extend methods from Chung et al (2011 SIAM J. Sci. Comput. 33 3132–52) to the general-form Tikhonov problem. Then we develop a learning approach for multi-parameter Tikhonov problems, for the case where all involved matrices are simultaneously diagonalizable. For problems where this is not the case, we describe an approach to compute near-optimal regularization parameters by using operator approximations for the original problem. Finally, we propose a new class of regularizing filters, where solutions correspond to multi-parameter Tikhonov solutions, that requires less data than previously proposed optimal error filters, avoids the generalized SVD, and allows flexibility and novelty in the choice of regularization matrices. Numerical results for 1D and 2D examples using different norms on the errors show the effectiveness of our methods. (paper)

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

Science.gov (United States)

Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug

Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

Science.gov (United States)

Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

2017-10-01

A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

Radiation resistance of ethylene-styrene copolymers

International Nuclear Information System (INIS)

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)

pyPaSWAS: Python-based multi-core CPU and GPU sequence alignment.

Science.gov (United States)

Warris, Sven; Timal, N Roshan N; Kempenaar, Marcel; Poortinga, Arne M; van de Geest, Henri; Varbanescu, Ana L; Nap, Jan-Peter

2018-01-01

Our previously published CUDA-only application PaSWAS for Smith-Waterman (SW) sequence alignment of any type of sequence on NVIDIA-based GPUs is platform-specific and therefore adopted less than could be. The OpenCL language is supported more widely and allows use on a variety of hardware platforms. Moreover, there is a need to promote the adoption of parallel computing in bioinformatics by making its use and extension more simple through more and better application of high-level languages commonly used in bioinformatics, such as Python. The novel application pyPaSWAS presents the parallel SW sequence alignment code fully packed in Python. It is a generic SW implementation running on several hardware platforms with multi-core systems and/or GPUs that provides accurate sequence alignments that also can be inspected for alignment details. Additionally, pyPaSWAS support the affine gap penalty. Python libraries are used for automated system configuration, I/O and logging. This way, the Python environment will stimulate further extension and use of pyPaSWAS. pyPaSWAS presents an easy Python-based environment for accurate and retrievable parallel SW sequence alignments on GPUs and multi-core systems. The strategy of integrating Python with high-performance parallel compute languages to create a developer- and user-friendly environment should be considered for other computationally intensive bioinformatics algorithms.

Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

International Nuclear Information System (INIS)

Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

2005-01-01

Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

Short read sequence typing (SRST: multi-locus sequence types from short reads

Directory of Open Access Journals (Sweden)

Inouye Michael

2012-07-01

Full Text Available Abstract Background Multi-locus sequence typing (MLST has become the gold standard for population analyses of bacterial pathogens. This method focuses on the sequences of a small number of loci (usually seven to divide the population and is simple, robust and facilitates comparison of results between laboratories and over time. Over the last decade, researchers and population health specialists have invested substantial effort in building up public MLST databases for nearly 100 different bacterial species, and these databases contain a wealth of important information linked to MLST sequence types such as time and place of isolation, host or niche, serotype and even clinical or drug resistance profiles. Recent advances in sequencing technology mean it is increasingly feasible to perform bacterial population analysis at the whole genome level. This offers massive gains in resolving power and genetic profiling compared to MLST, and will eventually replace MLST for bacterial typing and population analysis. However given the wealth of data currently available in MLST databases, it is crucial to maintain backwards compatibility with MLST schemes so that new genome analyses can be understood in their proper historical context. Results We present a software tool, SRST, for quick and accurate retrieval of sequence types from short read sets, using inputs easily downloaded from public databases. SRST uses read mapping and an allele assignment score incorporating sequence coverage and variability, to determine the most likely allele at each MLST locus. Analysis of over 3,500 loci in more than 500 publicly accessible Illumina read sets showed SRST to be highly accurate at allele assignment. SRST output is compatible with common analysis tools such as eBURST, Clonal Frame or PhyloViz, allowing easy comparison between novel genome data and MLST data. Alignment, fastq and pileup files can also be generated for novel alleles. Conclusions SRST is a novel

Ultraporous films with uniform nanochannels by block copolymer micelles assembly

KAUST Repository

Nunes, Suzana Pereira

2010-10-12

Films with high pore density and regularity that are easy to manufacture by conventional large-scale technology are key components aimed for fabrication of new generations of magnetic arrays for storage media, medical scaffolds, and artificial membranes. However, potential manufacture strategies like the self-assembly of block copolymers, which lead to amazing regular patterns, could be hardly reproduced up to now using commercially feasible methods. Here we report a unique production method of nanoporous films based on the self-assembly of copper(II) ion-polystyrene-b-poly(4-vinylpyridine) complexes and nonsolvent induced phase separation. Extremely high pore densities and uniformity were achieved. Water fluxes of 890 L m-2 h-1 bar-1 were obtained, which are at least 1 order of magnitude higher than those of commercially available membranes with comparable pore size. The pores are also stimuli (pH)-responsive. © 2010 American Chemical Society.

Multi-scale coding of genomic information: From DNA sequence to genome structure and function

International Nuclear Information System (INIS)

Arneodo, Alain; Vaillant, Cedric; Audit, Benjamin; Argoul, Francoise; D'Aubenton-Carafa, Yves; Thermes, Claude

2011-01-01

Understanding how chromatin is spatially and dynamically organized in the nucleus of eukaryotic cells and how this affects genome functions is one of the main challenges of cell biology. Since the different orders of packaging in the hierarchical organization of DNA condition the accessibility of DNA sequence elements to trans-acting factors that control the transcription and replication processes, there is actually a wealth of structural and dynamical information to learn in the primary DNA sequence. In this review, we show that when using concepts, methodologies, numerical and experimental techniques coming from statistical mechanics and nonlinear physics combined with wavelet-based multi-scale signal processing, we are able to decipher the multi-scale sequence encoding of chromatin condensation-decondensation mechanisms that play a fundamental role in regulating many molecular processes involved in nuclear functions.

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

Science.gov (United States)

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.

HPMA-based block copolymers promote differential drug delivery kinetics for hydrophobic and amphiphilic molecules.

Science.gov (United States)

Tomcin, Stephanie; Kelsch, Annette; Staff, Roland H; Landfester, Katharina; Zentel, Rudolf; Mailänder, Volker

2016-04-15

We describe a method how polymeric nanoparticles stabilized with (2-hydroxypropyl)methacrylamide (HPMA)-based block copolymers are used as drug delivery systems for a fast release of hydrophobic and a controlled release of an amphiphilic molecule. The versatile method of the miniemulsion solvent-evaporation technique was used to prepare polystyrene (PS) as well as poly-d/l-lactide (PDLLA) nanoparticles. Covalently bound or physically adsorbed fluorescent dyes labeled the particles' core and their block copolymer corona. Confocal laser scanning microscopy (CLSM) in combination with flow cytometry measurements were applied to demonstrate the burst release of a fluorescent hydrophobic drug model without the necessity of nanoparticle uptake. In addition, CLSM studies and quantitative calculations using the image processing program Volocity® show the intracellular detachment of the amphiphilic block copolymer from the particles' core after uptake. Our findings offer the possibility to combine the advantages of a fast release for hydrophobic and a controlled release for an amphiphilic molecule therefore pointing to the possibility to a 'multi-step and multi-site' targeting by one nanocarrier. We describe thoroughly how different components of a nanocarrier end up in cells. This enables different cargos of a nanocarrier having a consecutive release and delivery of distinct components. Most interestingly we demonstrate individual kinetics of distinct components of such a system: first the release of a fluorescent hydrophobic drug model at contact with the cell membrane without the necessity of nanoparticle uptake. Secondly, the intracellular detachment of the amphiphilic block copolymer from the particles' core after uptake occurs. This offers the possibility to combine the advantages of a fast release for a hydrophobic substance at the time of interaction of the nanoparticle with the cell surface and a controlled release for an amphiphilic molecule later on therefore

Rapid self-assembly of block copolymers to photonic crystals

Science.gov (United States)

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.

Multi-locus sequence typing provides epidemiological insights for diseased sharks infected with fungi belonging to the Fusarium solani species complex.

Science.gov (United States)

Desoubeaux, Guillaume; Debourgogne, Anne; Wiederhold, Nathan P; Zaffino, Marie; Sutton, Deanna; Burns, Rachel E; Frasca, Salvatore; Hyatt, Michael W; Cray, Carolyn

2018-07-01

Fusarium spp. are saprobic moulds that are responsible for severe opportunistic infections in humans and animals. However, we need epidemiological tools to reliably trace the circulation of such fungal strains within medical or veterinary facilities, to recognize environmental contaminations that might lead to infection and to improve our understanding of factors responsible for the onset of outbreaks. In this study, we used molecular genotyping to investigate clustered cases of Fusarium solani species complex (FSSC) infection that occurred in eight Sphyrnidae sharks under managed care at a public aquarium. Genetic relationships between fungal strains were determined by multi-locus sequence typing (MLST) analysis based on DNA sequencing at five loci, followed by comparison with sequences of 50 epidemiologically unrelated FSSC strains. Our genotyping approach revealed that F. keratoplasticum and F. solani haplotype 9x were most commonly isolated. In one case, the infection proved to be with another Hypocrealian rare opportunistic pathogen Metarhizium robertsii. Twice, sharks proved to be infected with FSSC strains with the same MLST sequence type, supporting the hypothesis the hypothesis that common environmental populations of fungi existed for these sharks and would suggest the longtime persistence of the two clonal strains within the environment, perhaps in holding pools and life support systems of the aquarium. This study highlights how molecular tools like MLST can be used to investigate outbreaks of microbiological disease. This work reinforces the need for regular controls of water quality to reduce microbiological contamination due to waterborne microorganisms.

Multi-input and -output logic circuits based on bioelectrocatalysis with horseradish peroxidase and glucose oxidase immobilized in multi-responsive copolymer films on electrodes.

Science.gov (United States)

Yu, Xue; Lian, Wenjing; Zhang, Jiannan; Liu, Hongyun

2016-06-15

Herein, poly(N-isopropylacrylamide-co-N,N'-dimethylaminoethylmethacrylate) copolymer films were polymerized on electrode surface with a simple one-step method, and the enzyme horseradish peroxidase (HRP) was embedded in the films simultaneously, which were designated as P(NiPAAm-co-DMEM)-HRP. The films exhibited a reversible structure change with the external stimuli, such as pH, CO2, temperature and SO4(2-), causing the cyclic voltammetric (CV) response of electroactive K3Fe(CN)6 at the film electrodes to display the corresponding multi-stimuli sensitive ON-OFF behavior. Based on the switchable CV property of the system and the electrochemical reduction of H2O2 catalyzed by HRP in the films and mediated by Fe(CN)6(3-) in solution, a 5-input/3-output logic gate was established. To further increase the complexity of the logic system, another enzyme glucose oxidase (GOD) was added into the films, designated as P(NiPAAm-co-DMEM)-HRP-GOD. In the presence of oxygen, the oxidation of glucose in the solution was catalyzed by GOD in the films, and the produced H2O2 in situ was recognized and electrocatalytically reduced by HRP and mediated by Fe(CN)6(3-). Based on the bienzyme films, a cascaded or concatenated 4-input/3-output logic gate system was proposed. The present work combined the multi-responsive interface with bioelectrocatalysis to construct cascaded logic circuits, which might open a new avenue to develop biocomputing elements with more sophisticated functions and design novel glucose biosensors. Copyright © 2016 Elsevier B.V. All rights reserved.

Lignin poly(lactic acid) copolymers

Energy Technology Data Exchange (ETDEWEB)

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.

Block copolymer membranes for aqueous solution applications

KAUST Repository

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.

Block copolymer membranes for aqueous solution applications

KAUST Repository

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.

Polyether-polyester graft copolymer

Science.gov (United States)

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.

Systematic implementation of implicit regularization for multi-loop Feynman Diagrams

International Nuclear Information System (INIS)

Cherchiglia, Adriano Lana; Sampaio, Marcos; Nemes, Maria Carolina

2011-01-01

Full text: Implicit Regularization (IR) is a candidate to become an invariant framework in momentum space to perform Feynman diagram calculations to arbitrary loop order. The essence of the method is to write the divergences in terms of loop integrals in one internal momentum which do not need to be explicitly evaluated. Moreover it acts in the physical dimension of the theory and gauge invariance is controlled by regularization dependent surface terms which when set to zero define a constrained version of IR (CIR) and deliver gauge invariant amplitudes automatically. Therefore it is in principle applicable to all physical relevant quantum field theories, supersymmetric gauge theories included. A non trivial question is whether we can generalize this program to arbitrary loop order in consonance with locality, unitarity and Lorentz invariance, especially when overlapping divergences occur. In this work we present a systematic implementation of our method that automatically displays the terms to be subtracted by Bogoliubov's recursion formula. Therefore, we achieve a twofold objective: we show that the IR program respects unitarity, locality and Lorentz invariance and we show that our method is consistent since we are able to display the divergent content of a multi-loop amplitude in a well defined set of basic divergent integrals in one internal momentum. We present several examples (from 1-loop to n-loops) using scalar φ 6 3 theory in order to help the reader understand and visualize the essence of the IR program. The choice of a scalar theory does not reduce the generality of the method presented since all other physical theories can be treated within the same strategy after space time and internal algebra are performed. Another result of this contribution is to show that if the surface terms are not set to zero they will contaminate the renormalization group coefficients. Thus, we are forced to adopt CIR which is equivalent to demand momentum routing invariance

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

KAUST Repository

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.

Polyether/Polyester Graft Copolymers

Science.gov (United States)

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.

Multi-objective Analysis for a Sequencing Planning of Mixed-model Assembly Line

Science.gov (United States)

Shimizu, Yoshiaki; Waki, Toshiya; Yoo, Jae Kyu

Diversified customer demands are raising importance of just-in-time and agile manufacturing much more than before. Accordingly, introduction of mixed-model assembly lines becomes popular to realize the small-lot-multi-kinds production. Since it produces various kinds on the same assembly line, a rational management is of special importance. With this point of view, this study focuses on a sequencing problem of mixed-model assembly line including a paint line as its preceding process. By taking into account the paint line together, reducing work-in-process (WIP) inventory between these heterogeneous lines becomes a major concern of the sequencing problem besides improving production efficiency. Finally, we have formulated the sequencing problem as a bi-objective optimization problem to prevent various line stoppages, and to reduce the volume of WIP inventory simultaneously. Then we have proposed a practical method for the multi-objective analysis. For this purpose, we applied the weighting method to derive the Pareto front. Actually, the resulting problem is solved by a meta-heuristic method like SA (Simulated Annealing). Through numerical experiments, we verified the validity of the proposed approach, and discussed the significance of trade-off analysis between the conflicting objectives.

Multi-region and single-cell sequencing reveal variable genomic heterogeneity in rectal cancer.

Science.gov (United States)

Liu, Mingshan; Liu, Yang; Di, Jiabo; Su, Zhe; Yang, Hong; Jiang, Beihai; Wang, Zaozao; Zhuang, Meng; Bai, Fan; Su, Xiangqian

2017-11-23

Colorectal cancer is a heterogeneous group of malignancies with complex molecular subtypes. While colon cancer has been widely investigated, studies on rectal cancer are very limited. Here, we performed multi-region whole-exome sequencing and single-cell whole-genome sequencing to examine the genomic intratumor heterogeneity (ITH) of rectal tumors. We sequenced nine tumor regions and 88 single cells from two rectal cancer patients with tumors of the same molecular classification and characterized their mutation profiles and somatic copy number alterations (SCNAs) at the multi-region and the single-cell levels. A variable extent of genomic heterogeneity was observed between the two patients, and the degree of ITH increased when analyzed on the single-cell level. We found that major SCNAs were early events in cancer development and inherited steadily. Single-cell sequencing revealed mutations and SCNAs which were hidden in bulk sequencing. In summary, we studied the ITH of rectal cancer at regional and single-cell resolution and demonstrated that variable heterogeneity existed in two patients. The mutational scenarios and SCNA profiles of two patients with treatment naïve from the same molecular subtype are quite different. Our results suggest each tumor possesses its own architecture, which may result in different diagnosis, prognosis, and drug responses. Remarkable ITH exists in the two patients we have studied, providing a preliminary impression of ITH in rectal cancer.

PEO-related block copolymer surfactants

DEFF Research Database (Denmark)

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...

SAR Target Recognition via Local Sparse Representation of Multi-Manifold Regularized Low-Rank Approximation

Directory of Open Access Journals (Sweden)

Meiting Yu

2018-02-01

Full Text Available The extraction of a valuable set of features and the design of a discriminative classifier are crucial for target recognition in SAR image. Although various features and classifiers have been proposed over the years, target recognition under extended operating conditions (EOCs is still a challenging problem, e.g., target with configuration variation, different capture orientations, and articulation. To address these problems, this paper presents a new strategy for target recognition. We first propose a low-dimensional representation model via incorporating multi-manifold regularization term into the low-rank matrix factorization framework. Two rules, pairwise similarity and local linearity, are employed for constructing multiple manifold regularization. By alternately optimizing the matrix factorization and manifold selection, the feature representation model can not only acquire the optimal low-rank approximation of original samples, but also capture the intrinsic manifold structure information. Then, to take full advantage of the local structure property of features and further improve the discriminative ability, local sparse representation is proposed for classification. Finally, extensive experiments on moving and stationary target acquisition and recognition (MSTAR database demonstrate the effectiveness of the proposed strategy, including target recognition under EOCs, as well as the capability of small training size.

Combining kernel matrix optimization and regularization to improve particle size distribution retrieval

Science.gov (United States)

Ma, Qian; Xia, Houping; Xu, Qiang; Zhao, Lei

2018-05-01

A new method combining Tikhonov regularization and kernel matrix optimization by multi-wavelength incidence is proposed for retrieving particle size distribution (PSD) in an independent model with improved accuracy and stability. In comparison to individual regularization or multi-wavelength least squares, the proposed method exhibited better anti-noise capability, higher accuracy and stability. While standard regularization typically makes use of the unit matrix, it is not universal for different PSDs, particularly for Junge distributions. Thus, a suitable regularization matrix was chosen by numerical simulation, with the second-order differential matrix found to be appropriate for most PSD types.

The Regularized Iteratively Reweighted MAD Method for Change Detection in Multi- and Hyperspectral Data

DEFF Research Database (Denmark)

Nielsen, Allan Aasbjerg

2007-01-01

This paper describes new extensions to the previously published multivariate alteration detection (MAD) method for change detection in bi-temporal, multi- and hypervariate data such as remote sensing imagery. Much like boosting methods often applied in data mining work, the iteratively reweighted...... to observations that show little change, i.e., for which the sum of squared, standardized MAD variates is small, and small weights are assigned to observations for which the sum is large. Like the original MAD method, the iterative extension is invariant to linear (affine) transformations of the original...... an agricultural region in Kenya, and hyperspectral airborne HyMap data from a small rural area in southeastern Germany are given. The latter case demonstrates the need for regularization....

Regular variation on measure chains

Czech Academy of Sciences Publication Activity Database

Řehák, Pavel; Vitovec, J.

2010-01-01

Roč. 72, č. 1 (2010), s. 439-448 ISSN 0362-546X R&D Projects: GA AV ČR KJB100190701 Institutional research plan: CEZ:AV0Z10190503 Keywords : regularly varying function * regularly varying sequence * measure chain * time scale * embedding theorem * representation theorem * second order dynamic equation * asymptotic properties Subject RIV: BA - General Mathematics Impact factor: 1.279, year: 2010 http://www.sciencedirect.com/science/article/pii/S0362546X09008475

Comparison of multi-echo and single-echo gradient-recalled echo sequences for SPIO-enhanced Liver MRI at 3 T

International Nuclear Information System (INIS)

Choi, J.S.; Kim, M.-J.; Kim, J.H.; Choi, J.-Y.; Chung, Y.E.; Park, M.-S.; Kim, K.W.

2010-01-01

Aim: To assess the utility of a T2*-weighted, multi-echo data imaging combination sequenced on superparamagnetic iron oxide (SPIO)-enhanced liver magnetic resonance imaging (MRI) using a 3 T system. Materials and methods: Fifty patients underwent SPIO-enhanced MRI at 3 T using T2*-weighted, single-echo, gradient-recalled echo (GRE) sequences [fast imaging with steady precession; repetition time (TR)/echo time (TE), 126 ms/9 ms; flip angle, 30 o ] and multi-echo GRE (multi-echo data image combination) sequences (TR/TE, 186 ms/9 ms; flip angle, 30 o ). Three radiologists independently reviewed the images in a random order. The sensitivity and accuracy for the detection of focal hepatic lesions (a total of 76 lesions in 33 patients; 48 solid lesions, 28 non-solid lesions) were compared by analysing the area under the receiver operating characteristic curves. Image artefacts (flow artefacts, susceptibility artefacts, dielectric artefacts, and motion artefacts), lesion conspicuity, and overall image quality were evaluated according to a four-point scale: 1, poor; 2, fair; 3, good; 4, excellent. The signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) of the lesions were compared. Results: Image artefacts were more frequent with single-echo GRE (p < 0.05). The mean scale of image quality assessment for flow, susceptibility, dielectric, and motion artefacts were 2.76, 3.13, 3.42, and 2.89 with singe-echo, respectively, compared with 3.47, 3.43, 3.47, and 3.39, respectively, with multi-echo GRE. There was no significant difference in lesion conspicuity between single-echo (3.15) and multi-echo (3.30) GRE sequences. The overall image quality was significantly (p < 0.05) better with multi-echo (3.37) than with single-echo GRE (2.89). The mean SNR and CNR of the lesions were significantly (p < 0.05) higher on multi-echo (79 ± 23 and 128 ± 59, respectively) images than on single-echo (38 ± 11 and 102 ± 44, respectively) images. Lesion detection accuracy and

Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO_2 substrates

International Nuclear Information System (INIS)

Frascaroli, Jacopo; Seguini, Gabriele; Spiga, Sabina; Perego, Michele; Boarino, Luca

2015-01-01

Block copolymer-based templates can be exploited for the fabrication of ordered arrays of metal nanoparticles (NPs) with a diameter down to a few nanometers. In order to develop this technique on metal oxide substrates, we studied the self-assembly of polymeric templates directly on the HfO_2 surface. Using a random copolymer neutralization layer, we obtained an effective HfO_2 surface neutralization, while the effects of surface cleaning and annealing temperature were carefully examined. Varying the block copolymer molecular weight, we produced regular nanoporous templates with feature size variable between 10 and 30 nm and a density up to 1.5 × 10"1"1 cm"−"2. With the adoption of a pattern transfer process, we produced ordered arrays of Pt and Pt/Ti NPs with diameters of 12, 21 and 29 nm and a constant size dispersion (σ) of 2.5 nm. For the smallest template adopted, the NP diameter is significantly lower than the original template dimension. In this specific configuration, the granularity of the deposited film probably influences the pattern transfer process and very small NPs of 12 nm were achieved without a significant broadening of the size distribution. (paper)

Single Machine Multi-product Capacitated Lotsizing with Sequence-dependent Setups

OpenAIRE

Almada-Lobo , Bernardo; Klabjan , Diego; Carravilla , Maria Antónia; Oliveira , Jose Fernando

2007-01-01

Abstract In production planning in the glass container industry, machine dependent setup times and costs are incurred for switchovers from one product to another. The resulting multi-item capacitated lot sizing problem has sequence-dependent setup times and costs. We present two novel linear mixed integer programming formulations for this problem, incorporating all the necessary features of setup carryovers. The compact formulation has polynomially many constraints, while, on the o...

Block copolymer micelles with a dual-stimuli-responsive core for fast or slow degradation.

Science.gov (United States)

Han, Dehui; Tong, Xia; Zhao, Yue

2012-02-07

We report the design and demonstration of a dual-stimuli-responsive block copolymer (BCP) micelle with increased complexity and control. We have synthesized and studied a new amphiphilic ABA-type triblock copolymer whose hydrophobic middle block contains two types of stimuli-sensitive functionalities regularly and repeatedly positioned in the main chain. Using a two-step click chemistry approach, disulfide and o-nitrobenzyle methyl ester groups are inserted into the main chain, which react to reducing agents and light, respectively. With the end blocks being poly(ethylene oxide), micelles formed by this BCP possess a core that can be disintegrated either rapidly via photocleavage of o-nitrobenzyl methyl esters or slowly through cleavage of disulfide groups by a reducing agent in the micellar solution. This feature makes possible either burst release of an encapsulated hydrophobic species from disintegrated micelles by UV light, or slow release by the action of a reducing agent, or release with combined fast-slow rate profiles using the two stimuli.

Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

NARCIS (Netherlands)

Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

1999-01-01

Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding

Oil recovery with vinyl sulfonic acid-acrylamide copolymers

Energy Technology Data Exchange (ETDEWEB)

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.

Smart systems related to polypeptide sequences

Directory of Open Access Journals (Sweden)

Lourdes Franco

2016-03-01

Full Text Available Increasing interest for the application of polypeptide-based smart systems in the biomedical field has developed due to the advantages given by the peptidic sequence. This is due to characteristics of these systems, which include: biocompatibility, potential control of degradation, capability to provide a rich repertoire of biologically specific interactions, feasibility to self-assemble, possibility to combine different functionalities, and capability to give an environmentally responsive behavior. Recently, applications concerning the development of these systems are receiving greater attention since a targeted and programmable release of drugs (e.g. anti-cancer agents can be achieved. Block copolymers are discussed due to their capability to render differently assembled architectures. Hybrid systems based on silica nanoparticles are also discussed. In both cases, the selected systems must be able to undergo fast changes in properties like solubility, shape, and dissociation or swelling capabilities. This review is structured in different chapters which explain the most recent advances on smart systems depending on the stimuli to which they are sensitive. Amphiphilic block copolymers based on polyanionic or polycationic peptides are, for example, typically employed for obtaining pH-responsive systems. Elastin-like polypeptides are usually used as thermoresponsive polymers, but performance can be increased by using techniques which utilize layer-by-layer electrostatic self-assembly. This approach offers a great potential to create multilayered systems, including nanocapsules, with different functionality. Recent strategies developed to get redox-, magnetic-, ultrasound-, enzyme-, light- and electric-responsive systems are extensively discussed. Finally, some indications concerning the possibilities of multi-responsive systems are discussed.

Hierarchical regular small-world networks

International Nuclear Information System (INIS)

Boettcher, Stefan; Goncalves, Bruno; Guclu, Hasan

2008-01-01

Two new networks are introduced that resemble small-world properties. These networks are recursively constructed but retain a fixed, regular degree. They possess a unique one-dimensional lattice backbone overlaid by a hierarchical sequence of long-distance links, mixing real-space and small-world features. Both networks, one 3-regular and the other 4-regular, lead to distinct behaviors, as revealed by renormalization group studies. The 3-regular network is planar, has a diameter growing as √N with system size N, and leads to super-diffusion with an exact, anomalous exponent d w = 1.306..., but possesses only a trivial fixed point T c = 0 for the Ising ferromagnet. In turn, the 4-regular network is non-planar, has a diameter growing as ∼2 √(log 2 N 2 ) , exhibits 'ballistic' diffusion (d w = 1), and a non-trivial ferromagnetic transition, T c > 0. It suggests that the 3-regular network is still quite 'geometric', while the 4-regular network qualifies as a true small world with mean-field properties. As an engineering application we discuss synchronization of processors on these networks. (fast track communication)

Effects of supported metallocene catalyst active center multiplicity on antioxidant-stabilized ethylene homo- and copolymers

KAUST Repository

Atiqullah, Muhammad

2014-10-09

© 2014 Akadémiai Kiadó, Budapest, Hungary. A silica-supported bis(n-butylcyclopentadienyl) zirconium dichloride [( n BuCp)2ZrCl2] catalyst was synthesized. This was used to prepare an ethylene homopolymer and an ethylene-1-hexene copolymer. The active center multiplicity of this catalyst was modeled by deconvoluting the copolymer molecular mass distribution and chemical composition distribution. Five different active site types were predicted, which matched the successive self-nucleation and annealing temperature peaks. The thermo-oxidative melt stability, with and without Irganox 1010 and Irgafos 168, of the above polyethylenes was investigated using nonisothermal differential scanning calorimetric (DSC) experiments at 150 °C. This is a temperature that ensures complete melting of the samples and avoids the diffusivity of oxygen to interfere into polyethylene crystallinity and its thermo-oxidative melt degradation. The oxidation parameters such as onset oxidation temperature, induction period, protection factor, and S-factor were determined by combining theoretical modeling with the DSC experiments. Subsequently, these findings were discussed considering catalyst active center multiplicity and polymer microstructure, particularly average ethylene sequence length. Several insightful results, which have not been reported earlier in the literature, were obtained. The antioxidant effect, for each polymer, varied as (Irganox + Irgafos) ≈ Irganox > Irgafos > Neat polymer. The as-synthesized homopolymer turned out to be almost twice as stable as the corresponding copolymer. The antioxidant(s) in the copolymer showed higher antioxidant effectiveness (AEX) than those in the homopolymer. Irganox exhibited more AEX than Irgafos. To the best of our knowledge, such findings have not been reported earlier in the literature. However, mixed with Irganox or Irgafos, their melt oxidation stability was comparable. The homopolymer, as per the calculated S-factor, showed Irganox

In-situ crosslinkable and self-assembling elastin-like polypeptide block copolymers for cartilage tissue repair

Science.gov (United States)

Lim, Dong Woo

This work describes the development of genetically engineered elastin-like polypeptide (ELP) block copolymers as in-situ gelling scaffolds for cartilage tissue repair. The central hypothesis underlying this work is that ELP based biopolymers can be exploited as injectable biomaterials by rapid chemical crosslinking. To prove this, gene libraries encoding ELP having different molecular weights and amino acid sequences, and ELP block copolymers composed of various ELP blocks having diverse amino acid composition, length, and phase transition behavior were synthesized by recursive directional ligation, expressed in E. Coli and purified by inverse transition cycling. Mannich-type condensation of hydroxymethylphosphines (HMPs) with primary- and secondary-amines of amino acids was developed as a new crosslinking method of polypeptides. Chemically crosslinked ELP hydrogels were formed rapidly in an aqueous solution by reaction of ELPs containing periodic lysine residues with HMPs. The crosslinking density and mechanical property of the ELP hydrogels were controlled at the sequence level by varying the Lys density in ELPs composed of mono-block as well as by segregation of the Lys residues within specific blocks of tri-block architectures. Fibroblasts embedded in ELP hydrogels survived the crosslinking process and were viable after in vitro culture for at least 3 days. The DNA content of fibroblasts within the tri-block gels was significantly higher than that in the mono-block gels at day 3. These results suggest that the HMP crosslinked ELP block copolymer hydrogels show finely tuned mechanical properties and different microenvironments for cell viability as well as potential as in-situ crosslinkable biopolymers for tissue repair applications with load-bearing environments. As an alternative, rheological behavior of the ELP block copolymers and ELP-grafted hyaluronic acids (HAs) as artificial extracellular matrices (ECMs) showed that they were thermally aggregated into

Quantitative analysis of copolymers : influence of the structure of the monomer on the ionization efficiency in electrospray ionization FTMS

NARCIS (Netherlands)

Koster, S.; Mulder, B.; Duursma, M.C.; Boon, J.J.; Philipsen, H.J.A.; Velde, J.W.; Nielen, M.W.F.; Koster, de C.G.; Heeren, R.M.A.

2002-01-01

The influence of the ionization efficiency on the measured copolymer sequence distribution is presented. Large differences in ionization efficiency were observed for mixtures of homopolyesters containing dipropoxylated bisphenol A/adipic acid and dipropoxylated bisphenol A/isophthalic acid and the

21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

Science.gov (United States)

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...

Sulfomethylated graft copolymers of xanthan gum and polyacrylamide

Energy Technology Data Exchange (ETDEWEB)

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.

Block Copolymers: Synthesis and Applications in Nanotechnology

Science.gov (United States)

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

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

Science.gov (United States)

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.

21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

Science.gov (United States)

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...

21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

Science.gov (United States)

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...

21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

Science.gov (United States)

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...

21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

Science.gov (United States)

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...

Antimicrobial activity of poly(acrylic acid) block copolymers

Energy Technology Data Exchange (ETDEWEB)

Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

2014-05-01

The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

Antimicrobial activity of poly(acrylic acid) block copolymers

International Nuclear Information System (INIS)

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

2014-01-01

The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

Visual Localization across Seasons Using Sequence Matching Based on Multi-Feature Combination.

Science.gov (United States)

Qiao, Yongliang

2017-10-25

Visual localization is widely used in autonomous navigation system and Advanced Driver Assistance Systems (ADAS). However, visual-based localization in seasonal changing situations is one of the most challenging topics in computer vision and the intelligent vehicle community. The difficulty of this task is related to the strong appearance changes that occur in scenes due to weather or season changes. In this paper, a place recognition based visual localization method is proposed, which realizes the localization by identifying previously visited places using the sequence matching method. It operates by matching query image sequences to an image database acquired previously (video acquired during traveling period). In this method, in order to improve matching accuracy, multi-feature is constructed by combining a global GIST descriptor and local binary feature CSLBP (Center-symmetric local binary patterns) to represent image sequence. Then, similarity measurement according to Chi-square distance is used for effective sequences matching. For experimental evaluation, the relationship between image sequence length and sequences matching performance is studied. To show its effectiveness, the proposed method is tested and evaluated in four seasons outdoor environments. The results have shown improved precision-recall performance against the state-of-the-art SeqSLAM algorithm.

Copolymers at the solid - liquid interface

NARCIS (Netherlands)

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

Decentralized formation of random regular graphs for robust multi-agent networks

KAUST Repository

Yazicioglu, A. Yasin; Egerstedt, Magnus; Shamma, Jeff S.

2014-01-01

systems. One family of robust graphs is the random regular graphs. In this paper, we present a locally applicable reconfiguration scheme to build random regular graphs through self-organization. For any connected initial graph, the proposed scheme

Pancreatic Arteriovenous Malformation Involving the Duodenum Embolized with Ethylene-Vinyl Alcohol Copolymer (Onyx)

Energy Technology Data Exchange (ETDEWEB)

Grasso, Rosario Francesco, E-mail: r.grasso@unicampus.it; Cazzato, Roberto Luigi; Luppi, Giacomo; Faiella, Eliodoro; Del Vescovo, Riccardo; Giurazza, Francesco [University ' Campus Bio-Medico of Rome' , Department of Radiology (Italy); Borzomati, Domenico; Coppola, Roberto [University ' Campus Bio-Medico of Rome' , Department of General Surgery (Italy); Beomonte Zobel, Bruno [University ' Campus Bio-Medico of Rome' , Department of Radiology (Italy)

2012-08-15

Arteriovenous malformation (AVM) of the pancreas is a rare condition. Most patients are asymptomatic or alternatively may present with a wide spectrum of symptoms. Traditionally, surgery has been considered the treatment of choice; however, alternative approaches, such as transcatheter embolization (TAE), may be proposed. We report a case of a 48-year-old man with a pancreatic head AVM, presenting with upper abdominal pain and slight anemia. The patient refused surgery and underwent TAE by means of ethylene-vinyl alcohol copolymer (EVOH). At 3 months follow-up, the patient was able to eat regularly, with no residual pain and no signs of anemia.

Synthesis and characterization of waterborne polyurethane acrylate copolymers

International Nuclear Information System (INIS)

Sultan, Misbah; Bhatti, Haq Nawaz; Zuber, Mohammad; Barikani, Mehdi

2013-01-01

Polyurethane acrylate copolymers were synthesized by emulsion polymerization process. To reduce the environmental hazards, organic solvents were replaced by eco-friendly aqueous system. Concentration of polyurethane and acrylate monomer was varied to investigate the effect of chemical composition on performance properties of copolymers. FTIR spectroscopy was used as a key tool to record the chemical synthesis route. The synthesized copolymer emulsions were characterized by evaluating their particle size, viscosity, dry weight content, chemical and water resistance. Thermal decomposition was studied by thermogravimetric analysis. Scanning electron microscope was used to visualize the morphological structure of copolymers. The experimental results indicate better polyurethane acrylate compatibility till the ratio of 30/70. However, these copolymers exhibited synergistic effects between the two polymers and revealed a remarkable improvement in numerous coating properties

The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

NARCIS (Netherlands)

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

Polyketones as alternating copolymers of carbon monoxide

International Nuclear Information System (INIS)

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.

21 CFR 177.2470 - Polyoxymethylene copolymer.

Science.gov (United States)

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...

Nanoparticles based on novel amphiphilic polyaspartamide copolymers

International Nuclear Information System (INIS)

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.

Effect of Sequence Blockiness on the Morphologies of Surface-grafted Elastin-like Polypeptides

Science.gov (United States)

Albert, Julie; Sintavanon, Kornkanok; Mays, Robin; MacEwan, Sarah; Chilkoti, Ashutosh; Genzer, Jan

2014-03-01

The inter- and intra- molecular interactions among monomeric units of copolymers and polypeptides depend strongly on monomer sequence distribution and dictate the phase behavior of these species both in solution and on surfaces. To study the relationship between sequence and phase behavior, we have designed a series of elastin-like polypeptides (ELPs) with controlled monomer sequences that mimic copolymers with various co-monomer sequence distributions and attached them covalently to silicon substrates from buffer solutions at temperatures below and above the bulk ELPs' lower critical solution temperatures (LCSTs). The dependence of ELP grafting density on solution temperature was examined by ellipsometry and the resultant surface morphologies were examined in air and under water with atomic force microscopy. Depositions performed above the LCST resulted in higher grafting densities and greater surface roughness of ELPs relative to depositions carried out below the LCST. In addition, we are using gradient substrates to examine the effect of ELP grafting density on temperature responsiveness.

Morphological transformations of diblock copolymers in binary solvents: A simulation study

Science.gov (United States)

Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

2017-12-01

Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent C S2, the concentration of the polymer C p , and the polymer-solvent interactions ɛ ij ( i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of C p , C S2, and/or ɛ AS2. The copolymer morphological sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing C S2 at a fixed C p . This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure significantly. In particular, when the interaction ɛ BS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar aggregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing C p or with decreasing C S2, but remains almost unchanged with variations in ɛ AS2.

Amphiphilic copolymers for fouling-release coatings

DEFF Research Database (Denmark)

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...

Poly(ferrocenylsilane)-block-Polylactide Block Copolymers

NARCIS (Netherlands)

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

Detection of regularities in variation in geomechanical behavior of rock mass during multi-roadway preparation and mining of an extraction panel

Science.gov (United States)

Tsvetkov, AB; Pavlova, LD; Fryanov, VN

2018-03-01

The results of numerical simulation of the stress–strain state in a rock block and surrounding mass mass under multi-roadway preparation to mining are presented. The numerical solutions obtained by the nonlinear modeling and using the constitutive relations of the theory of elasticity are compared. The regularities of the stress distribution in the vicinity of the pillars located in the zone of the abutment pressure of are found.

Thermodynamics of the multi-stage self-assembly of pH-sensitive gradient copolymers in aqueous solutions

Czech Academy of Sciences Publication Activity Database

Černochová, Zulfiya; Bogomolova, Anna; Borisova, O. V.; Filippov, Sergey K.; Černoch, Peter; Billon, L.; Borisov, O. V.; Štěpánek, Petr

2016-01-01

Roč. 12, č. 32 (2016), s. 6788-6798 ISSN 1744-683X R&D Projects: GA MŠk(CZ) LH14079; GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : gradient copolymers * isothermal titration calorimetry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.889, year: 2016

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

OpenAIRE

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...

Acrylonitrile-methyl Methacrylate Copolymer Films Containing Microencapsulated n-Octadecane

Institute of Scientific and Technical Information of China (English)

LI Jun; HAN Na; ZHANG Xing-xiang

2006-01-01

Acrylonitrile-methyl methacrylate copolymer was synthesized in aqueous solution by Redox. The copolymer was mixed with 10 - 40 wt% of microencapsulated n-octadecane (MicroPCMs) in water. Copolymer films containing MicroPCMs were cast at room temperature in N, N-Dimethylformamide solution. The copolymer of acrylonitrile-methyl methacrylate and the copolymer films containing MicroPCMs were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analyzer (TG), X-ray Diffrac tion (XRD) and Scanning Electron Microscopy (SEM), etc.The microcapsules in the films are evenly distributed in the copolymer matrix. The heat-absorbing temperatures and heat-evolving temperatures of the films are almost the same as that of the MicroPCMs, respectively, and fluctuate in a slight range. In addition, the enthalpy efficiency of MicroPCMs rises with the contents of MicroPCMs increasing.The crystallinity of the film increases with the contents of MicroPCMs increasing.

Functional Nanoporous Polymers from Block Copolymer Precursors

DEFF Research Database (Denmark)

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...

Morphological studies on block copolymer modified PA 6 blends

Energy Technology Data Exchange (ETDEWEB)

Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de [Institut für Kunststofftechnik, University of Stuttgart (Germany)

2014-05-15

Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

Visual Localization across Seasons Using Sequence Matching Based on Multi-Feature Combination

Directory of Open Access Journals (Sweden)

Yongliang Qiao

2017-10-01

Full Text Available Visual localization is widely used in autonomous navigation system and Advanced Driver Assistance Systems (ADAS. However, visual-based localization in seasonal changing situations is one of the most challenging topics in computer vision and the intelligent vehicle community. The difficulty of this task is related to the strong appearance changes that occur in scenes due to weather or season changes. In this paper, a place recognition based visual localization method is proposed, which realizes the localization by identifying previously visited places using the sequence matching method. It operates by matching query image sequences to an image database acquired previously (video acquired during traveling period. In this method, in order to improve matching accuracy, multi-feature is constructed by combining a global GIST descriptor and local binary feature CSLBP (Center-symmetric local binary patterns to represent image sequence. Then, similarity measurement according to Chi-square distance is used for effective sequences matching. For experimental evaluation, the relationship between image sequence length and sequences matching performance is studied. To show its effectiveness, the proposed method is tested and evaluated in four seasons outdoor environments. The results have shown improved precision–recall performance against the state-of-the-art SeqSLAM algorithm.

Photo-Induced Micellization of Block Copolymers

Directory of Open Access Journals (Sweden)

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.

Fast & scalable pattern transfer via block copolymer nanolithography

DEFF Research Database (Denmark)

Li, Tao; Wang, Zhongli; Schulte, Lars

2015-01-01

A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s......A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

Multi-tissue partial volume quantification in multi-contrast MRI using an optimised spectral unmixing approach.

Science.gov (United States)

Collewet, Guylaine; Moussaoui, Saïd; Deligny, Cécile; Lucas, Tiphaine; Idier, Jérôme

2018-06-01

Multi-tissue partial volume estimation in MRI images is investigated with a viewpoint related to spectral unmixing as used in hyperspectral imaging. The main contribution of this paper is twofold. It firstly proposes a theoretical analysis of the statistical optimality conditions of the proportion estimation problem, which in the context of multi-contrast MRI data acquisition allows to appropriately set the imaging sequence parameters. Secondly, an efficient proportion quantification algorithm based on the minimisation of a penalised least-square criterion incorporating a regularity constraint on the spatial distribution of the proportions is proposed. Furthermore, the resulting developments are discussed using empirical simulations. The practical usefulness of the spectral unmixing approach for partial volume quantification in MRI is illustrated through an application to food analysis on the proving of a Danish pastry. Copyright © 2018 Elsevier Inc. All rights reserved.

Morphology and electrical properties of electrochemically synthesized pyrrole–formyl pyrrole copolymer

Energy Technology Data Exchange (ETDEWEB)

Gholami, Mehrdad, E-mail: mehrdad897@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Marvdasht Branch, Islamic Azad University, P.O. Box 465, Marvdasht (Iran, Islamic Republic of); Nia, Pooria Moozarm, E-mail: pooriamn@yahoo.com [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Alias, Yatimah, E-mail: yatimah70@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

2015-12-01

Graphical abstract: - Highlights: • The (Py–co-FPy) copolymer was synthesized electrochemically. • This copolymer has 1.6 times higher surface coverage compared to polypyrrole. • This copolymer showed 2.5 times lower resistance compared to polypyrrole. • The conjugated structure between Py and FPy causes enhancement of conductivity. • This conducting copolymer has a strong potential to be used in various applications. - Abstract: A direct electrochemical copolymerization of pyrrole–formyl pyrrole (Py–co-FPy) was carried out by oxidative copolymerization of formyl pyrrole and pyrrole in LiClO{sub 4} aqueous solution through galvanostatic method. The (Py–co-FPy) copolymer was characterized using Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), energy-filtering transmission electron microscope (EFTEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FESEM images showed that the synthesized copolymer had a hollow whelk-like helixes structure, which justifies the enhancement of charge transportation through the copolymer film. Cyclic voltammetry studies revealed that the electrocatalytic activity of synthesized copolymer has improved and the surface coverage in copolymer enhanced 1.6 times compared to polypyrrole alone. Besides, (Py–co-FPy) copolymer showed 2.5 times lower electrochemical charge transfer resistance (R{sub ct}) value in impedance spectroscopy. Therefore, this copolymer has a strong potential to be used in several applications such as sensor applications.

Meso-scale Modeling of Block Copolymers Self-Assembly in Casting Solutions for Membrane Manufacture

KAUST Repository

Moreno Chaparro, Nicolas

2016-05-01

Isoporous membranes manufactured from diblock copolymer are successfully produced at laboratory scale under controlled conditions. Because of the complex phenomena involved, membrane preparation requires trial and error methodologies to find the optimal conditions, leading to a considerable demand of resources. Experimental insights demonstrate that the self-assembly of the block copolymers in solution has an effect on the final membrane structure. Nevertheless, the complete understanding of these multi-scale phenomena is elusive. Herein we use the coarse-grained method Dissipative Particle Dynamics to study the self-assembly of block copolymers that are used for the preparation of the membranes. To simulate representative time and length scales, we introduce a framework for model reduction of polymer chain representations for dissipative particle dynamics, which preserves the properties governing the phase equilibria. We reduce the number of degrees of freedom by accounting for the correlation between beads in fine-grained models via power laws and the consistent scaling of the simulation parameters. The coarse-graining models are consistent with the experimental evidence, showing a morphological transition of the aggregates as the polymer concentration and solvent affinity change. We show that hexagonal packing of the micelles can occur in solution within different windows of polymer concentration depending on the solvent affinity. However, the shape and size dispersion of the micelles determine the characteristic arrangement. We describe the order of crew-cut micelles using a rigid-sphere approximation and propose different phase parameters that characterize the emergence of monodisperse-spherical micelles in solution. Additionally, we investigate the effect of blending asymmetric diblock copolymers (AB/AC) over the properties of the membranes. We observe that the co-assembly mechanism localizes the AC molecules at the interface of A and B domains, and induces

Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

Science.gov (United States)

Li, Ying; Sun, Min-Na; Zhang, Jin-Jun; Pan, Jun-Xing; Guo, Yu-Qi; Wang, Bao-Feng; Wu, Hai-Shun

2015-12-01

The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional (2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement. We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures. Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20121404110004), the Research Foundation for Excellent Talents of Shanxi Provincial Department of Human Resources and Social Security, China, and the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province, China.

21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-methyl acrylate copolymer resins. 177.1340... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl acrylate copolymer resins may be safely used as articles or components of...

POLYCAPROLACTONE-POLY (ETHYLENE GLYCOL) BLOCK COPOLYMER Ⅲ DRUG RELEASE BEHAVIOR

Institute of Scientific and Technical Information of China (English)

BEI Jianzhong; WANG Zhifeng; WANG Shenguo

1995-01-01

The drug release behavior of degradable polymer - polycaprolactone-poly (ethylene glycol)block copolymer(PCE) in vitro was investigated by using 5-Fluoro-uracil (5-Fu) as a model drug under a condition of pH 7.4 at 37℃. It is found that the release rate of 5-Fu from PCE increased with increasing polyether content of the copolymer. The results show that the increasing polyether content of the copolymer caused increasing hydrophilicity and decreasing crystallinity of the PCE copolymer. Thus, the drug release behavior and the degradable property of the PCE can be controlled by adjusting the composition of the copolymer.

Synthesis and Solution Properties of Zwitterionic Copolymer of Acrylamide with 3-[(2-Acrylamido)dimethylammonio]propanesulfonate

Energy Technology Data Exchange (ETDEWEB)

Xiao, Hui; Hu, Jing; Jin, Shuailin; Li, Rui Hai [Sichuan Univ., Chengdu (China)

2013-09-15

A novel zwitterionic monomer 3-[(2-acrylamido)dimethylammonio]propanesulfonate (DMADAS) was designed and synthesized in this study. Then it was polymerized with acrylamide (AM) by free radical polymerization in 0.5 mol/L NaCl solution with ammonium persulfate ((NH{sub 4}){sub 2}S{sub 2}O{sub 8}) and sodium sulfate (NaHSO{sub 3}) as initiator. The structure and composition of DMADAS and acrylamide-3-[(2-acrylamido)-dimethylammonio]propanesulfonate copolymer (P-AM-DMADAS) were characterized by FT-IR spectroscopy, {sup 1}H NMR and elemental analyses. Isoelectric point (IEP) of P-AM-DMADAS was tested by nanoparticle size and potential analyzer. Solution properties of copolymer were studied by reduced viscosity. Antipolyelectrolyte behavior was observed and was found to be enhanced with increasing DMADAS content in copolymer. The results showed that the viscosity of P-AM-DMADAS is 5.472 dl/g in pure water. Electrolyte was added, which weakened the mutual attraction between sulfonic acid group and quaternary ammonium group. The conformation became loose, which led to the increase of reduced viscosity. The ability of monovalent and divalent cation influencing the viscosity of zwitterionic copolymer obeyed the following sequence: Li{sup +} < Na{sup +} < K{sup +}, Mg{sup 2+} < Ca{sup 2+} < Ba{sup 2+}, and that of anion is in the order: Cl{sup -} < Br{sup -} < I{sup -}, CO{sub 3}{sup 2-} > SO{sub 3}{sup 2-} ≅ SO{sub 4}{sup 2-}.

Estimate of pulse-sequence data acquisition system for multi-dimensional measurement

Energy Technology Data Exchange (ETDEWEB)

Kitamura, Yasunori; Sakae, Takeji; Nohtomi, Akihiro; Matoba, Masaru [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Matsumoto, Yuzuru

1996-07-01

A pulse-sequence data acquisition system has been newly designed and estimated for the measurement of one- or multi-dimensional pulse train coming from radiation detectors. In this system, in order to realize the pulse-sequence data acquisition, the arrival time of each pulse is recorded to a memory of a personal computer (PC). For the multi-dimensional data acquisition with several input channels, each arrival-time data is tagged with a `flag` which indicates the input channel of arriving pulse. Counting losses due to the existence of processing time of the PC are expected to be reduced by using a First-In-First-Out (FIFO) memory unit. In order to verify this system, a computer simulation was performed, Various sets of random pulse trains with different mean pulse rate (1-600 kcps) were generated by using Monte Carlo simulation technique. Those pulse trains were dealt with another code which simulates the newly-designed data acquisition system including a FIFO memory unit; the memory size was assumed to be 0-100 words. And the recorded pulse trains on the PC with the various FIFO memory sizes have been observed. From the result of the simulation, it appears that the system with 3 words FIFO memory unit works successfully up to the pulse rate of 10 kcps without any severe counting losses. (author)

Estimate of pulse-sequence data acquisition system for multi-dimensional measurement

International Nuclear Information System (INIS)

Kitamura, Yasunori; Sakae, Takeji; Nohtomi, Akihiro; Matoba, Masaru; Matsumoto, Yuzuru.

1996-01-01

A pulse-sequence data acquisition system has been newly designed and estimated for the measurement of one- or multi-dimensional pulse train coming from radiation detectors. In this system, in order to realize the pulse-sequence data acquisition, the arrival time of each pulse is recorded to a memory of a personal computer (PC). For the multi-dimensional data acquisition with several input channels, each arrival-time data is tagged with a 'flag' which indicates the input channel of arriving pulse. Counting losses due to the existence of processing time of the PC are expected to be reduced by using a First-In-First-Out (FIFO) memory unit. In order to verify this system, a computer simulation was performed, Various sets of random pulse trains with different mean pulse rate (1-600 kcps) were generated by using Monte Carlo simulation technique. Those pulse trains were dealt with another code which simulates the newly-designed data acquisition system including a FIFO memory unit; the memory size was assumed to be 0-100 words. And the recorded pulse trains on the PC with the various FIFO memory sizes have been observed. From the result of the simulation, it appears that the system with 3 words FIFO memory unit works successfully up to the pulse rate of 10 kcps without any severe counting losses. (author)

Nanostructured Polysulfone-Based Block Copolymer Membranes

KAUST Repository

Xie, Yihui

2016-05-01

The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

Synthesis and Characterization of New ‎Copolymers as Asphalt Additives

Directory of Open Access Journals (Sweden)

Firyal M. ‎ A

2017-12-01

Full Text Available Rheological properties of asphalt S50  were improved by adding different prepared copolymers as additives with high homogeneity of asphalts  samples.  Three types of copolymers were prepared  Poly  (Indene –Co- maleic anhydride(A1 Poly (Acrylonitrile –Co- Maleic anhydride (A2 and Poly (Dipentine –Co-Maleic anhydride (A3, the cross linking of (A3 to (A3d. by using sulfur.              These copolymers  were designed by inserting Maleic anhydride as  rings  containing through backbone of polymer chains to be high potentially to react with water to protect the crack of pavement .And moisture with inhibit bonding of crack of pavement, Many factors should be considered when prepared the additives to enhanced performance to be convenience cost, beneficial thermal safety ,   extended life of the asphalt, preparing conditions which gave high thermal resistance with more stabilities, all these prepared copolymer have been characterized by FTIR and H-NMR spectroscopies .Intrinsic viscosities were calculated. softening point and penetration were observed for all asphalts blends which were  compared with the  asphalt samples, which gave high thermal resistance with more stabilities.                                          The results  showed high properties of these blends when  compared with the original asphalt. The physical properties of a specific polymers are determined by the sequence and chemical structure , When polymers are added to asphalt , the properties of the modified asphalt cement depend on polymer characteristic of asphalt and compatibility of polymer with asphalt. All these prepared copolymers were tested by softening points and penetration for all  asphalt blends which were compared with the asphalt sample. All the Improvements made by adding polymers to asphalt included the Increasing the viscosity of the binder service, the thermal susceptibility of the binder

Quantification of fetal heart rate regularity using symbolic dynamics

Science.gov (United States)

van Leeuwen, P.; Cysarz, D.; Lange, S.; Geue, D.; Groenemeyer, D.

2007-03-01

Fetal heart rate complexity was examined on the basis of RR interval time series obtained in the second and third trimester of pregnancy. In each fetal RR interval time series, short term beat-to-beat heart rate changes were coded in 8bit binary sequences. Redundancies of the 28 different binary patterns were reduced by two different procedures. The complexity of these sequences was quantified using the approximate entropy (ApEn), resulting in discrete ApEn values which were used for classifying the sequences into 17 pattern sets. Also, the sequences were grouped into 20 pattern classes with respect to identity after rotation or inversion of the binary value. There was a specific, nonuniform distribution of the sequences in the pattern sets and this differed from the distribution found in surrogate data. In the course of gestation, the number of sequences increased in seven pattern sets, decreased in four and remained unchanged in six. Sequences that occurred less often over time, both regular and irregular, were characterized by patterns reflecting frequent beat-to-beat reversals in heart rate. They were also predominant in the surrogate data, suggesting that these patterns are associated with stochastic heart beat trains. Sequences that occurred more frequently over time were relatively rare in the surrogate data. Some of these sequences had a high degree of regularity and corresponded to prolonged heart rate accelerations or decelerations which may be associated with directed fetal activity or movement or baroreflex activity. Application of the pattern classes revealed that those sequences with a high degree of irregularity correspond to heart rate patterns resulting from complex physiological activity such as fetal breathing movements. The results suggest that the development of the autonomic nervous system and the emergence of fetal behavioral states lead to increases in not only irregular but also regular heart rate patterns. Using symbolic dynamics to

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

Directory of Open Access Journals (Sweden)

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.

The effect of the multi-pass non-circular drawing sequence on mechanical properties and microstructure evolution of low-carbon steel

International Nuclear Information System (INIS)

Lee, Jung Wan; Baek, Hyun Moo; Hwang, Sun Kwang; Son, Il-Heon; Bae, Chul Min; Im, Yong-Taek

2014-01-01

Highlights: • A multi-pass non-circular drawing sequence is proposed to make high-strength wires. • The sequence was designed and applied for a low-carbon steel wire up to the 10th pass. • Many LAGBs and small grain size of the wire produced by the sequence were obtained. • High plastic deformation was imposed on the wire, resulting in grain refinement. • The sequence made fine-grained wires with improved UTS, ductility and fatigue life. - Abstract: In this study, the multi-pass non-circular drawing sequence was investigated for manufacturing high-strength wires with better ductility in a simple continuous way without adding additional alloys and heat treatment considering the effect of microstructure evolution and die geometry of the sequence on the mechanical properties of low-carbon steel during the process. For this purpose, the non-circular drawing sequence was designed and applied up to the 10th pass at room temperature. Mechanical properties and microstructure evolution of the specimen processed by the sequence were investigated by tension, Vickers micro-hardness, electron backscattering diffraction (EBSD), and fatigue tests compared with those for the conventional wire-drawing process. From the EBSD results, the higher low angle grain boundaries length per unit area and smaller average grain size of the specimen processed by the non-circular drawing sequence were obtained than those of the specimen processed by the wire-drawing process for the 8th pass. These results indicated that more plastic deformation was imposed in the material by the non-circular drawing sequence, resulting in grain refinement of the deformed specimen compared to the wire-drawing process. It is demonstrated that the multi-pass non-circular drawing sequence could be beneficial in producing fine-grained wires with improved ultimate tensile strength, ductility, and fatigue property by simply changing drawing dies geometry of the conventional wire-drawing process

Amphiphilic brushes from metallo-supramolecular block copolymers

NARCIS (Netherlands)

Guillet, P.; Fustin, C.A.; Wouters, D.; Höppener, S.; Schubert, U.S.; Gohy, J.M.W.

2009-01-01

A novel strategy to control the formation of amphiphilic brushes from metallo-supramol. block copolymers is described. The investigated copolymer consists of a polystyrene block linked to a poly(ethylene oxide) one via a charged bis-terpyridine ruthenium(ii) complex (PS-[Ru]-PEO). The initial

Iodinated glycidyl methacrylate copolymer as a radiopaque material for biomedical applications.

Science.gov (United States)

Dawlee, S; Jayabalan, M

2013-07-01

Polymeric biomaterial was synthesized by copolymerizing 50:50 mol% of monomers, glycidyl methacrylate and methyl methacrylate. Iodine atoms were then grafted to the epoxide groups of glycidyl methacrylate units, rendering the copolymer radiopaque. The percentage weight of iodine in the present copolymer was found to be as high as 23%. The iodinated copolymer showed higher glass transition temperature and thermal stability in comparison with unmodified polymer. Radiographic analysis showed that the copolymer possessed excellent radiopacity. The iodinated copolymer was cytocompatible to L929 mouse fibroblast cells. The in vivo toxicological evaluation by intracutaneous reactivity test of the copolymer extracts has revealed that the material was nontoxic. Subcutaneous implantation of iodinated copolymer in rats has shown that the material was well tolerated. Upon explantation and histological examination, no hemorrhage, infection or necrosis was observed. The samples were found to be surrounded by a vascularized capsule consisting of connective tissue cells. The results indicate that the iodinated copolymer is biocompatible and may have suitable applications as implantable materials.

Controlling block copolymer phase behavior using ionic surfactant

Energy Technology Data Exchange (ETDEWEB)

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.

A multi-slice gradient sequence for contrast enhanced MR diagnosis of intracranial tumours

International Nuclear Information System (INIS)

Schoerner, W.; Sander, B.; Kornmesser, W.; Laniado, M.; Nakamura, T.; Felix, R.

1988-01-01

A multi-slice gradient echo sequence (FLASH) was compared with a conventional spin-echo (SE) technique with regard to its value for contrast enhanced MR diagnosis. In 28 patients with cerebral tumours, SE images (SE 400/30; four images/3.4 minutes) and FLASH images (FLASH 315/14; 15 images/1.4 minutes) were obtained before and after gadolinium DTPA. After gadolinium-DTPA results were comparable for both techniques with respect to contrast enhancement, tumor contrast and delineation. Because of the higher efficiency of the FLASH 315/14 technique, this sequence is the method of choice for contrast enhanced cerebral MR imaging. (orig.) [de

78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption

Science.gov (United States)

2013-04-03

...-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY: Environmental Protection Agency (EPA... for residues of styrene-ethylene-propylene block copolymer (CAS Reg. No. 108388-87-0) when used as an...-ethylene-propylene block copolymer on food or feed commodities. DATES: This regulation is effective April 3...

Polyethylene-Based Tadpole Copolymers

KAUST Repository

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.

Nanostructuration of self-assembled poly(styrene-b-isoprene-b-styrene) block copolymer thin films in a highly oriented pyrolytic graphite substrate

Energy Technology Data Exchange (ETDEWEB)

Zalakain, Inaki; Ramos, Jose Angel; Fernandez, Raquel; Etxeberria, Haritz; Mondragon, Inaki, E-mail: inaki.mondragon@ehu.e

2011-01-03

Highly oriented pyrolitic graphite (HOPG) is a useful substrate to visualize epitaxial formation due to its crystallographic structure. The morphology of a poly(styrene-b-isoprene-b-styrene) block copolymer thin film on a HOPG substrate was investigated by atomic force microscopy. Block copolymer domains generated a morphology with triangular regularity. This arrangement was induced by the HOPG substrate structure due to van der Waals attraction between the HOPG {pi}-conjugated system and aromatic ring of polystyrene domains. However, increasing the film thickness, the substrate effect on the surface morphology decreased. As a consequence, film surfaces showed the coexistence of different structures such as highly aligned cylinders and perforated lamellae. When film thickness exceeded a threshold value, the substrate did not have effect in the surface arrangements and the surface showed a similar morphology to that existing in bulk.

Polyamide copolymers having 2,5-furan dicarboxamide units

Science.gov (United States)

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.

WE-FG-207B-03: Multi-Energy CT Reconstruction with Spatial Spectral Nonlocal Means Regularization

Energy Technology Data Exchange (ETDEWEB)

Li, B [University of Texas Southwestern Medical Center, Dallas, TX (United States); Southern Medical University, Guangzhou, Guangdong (China); Shen, C; Ouyang, L; Yang, M; Jiang, S; Jia, X [University of Texas Southwestern Medical Center, Dallas, TX (United States); Zhou, L [Southern Medical University, Guangzhou, Guangdong (China)

2016-06-15

Purpose: Multi-energy computed tomography (MECT) is an emerging application in medical imaging due to its ability of material differentiation and potential for molecular imaging. In MECT, image correlations at different spatial and channels exist. It is desirable to incorporate these correlations in reconstruction to improve image quality. For this purpose, this study proposes a MECT reconstruction technique that employes spatial spectral non-local means (ssNLM) regularization. Methods: We consider a kVp-switching scanning method in which source energy is rapidly switched during data acquisition. For each energy channel, this yields projection data acquired at a number of angles, whereas projection angles among channels are different. We formulate the reconstruction task as an optimziation problem. A least square term enfores data fidelity. A ssNLM term is used as regularization to encourage similarities among image patches at different spatial locations and channels. When comparing image patches at different channels, intensity difference were corrected by a transformation estimated via histogram equalization during the reconstruction process. Results: We tested our method in a simulation study with a NCAT phantom and an experimental study with a Gammex phantom. For comparison purpose, we also performed reconstructions using conjugate-gradient least square (CGLS) method and conventional NLM method that only considers spatial correlation in an image. ssNLM is able to better suppress streak artifacts. The streaks are along different projection directions in images at different channels. ssNLM discourages this dissimilarity and hence removes them. True image structures are preserved in this process. Measurements in regions of interests yield 1.1 to 3.2 and 1.5 to 1.8 times higher contrast to noise ratio than the NLM approach. Improvements over CGLS is even more profound due to lack of regularization in the CGLS method and hence amplified noise. Conclusion: The

Highly-Ordered Magnetic Nanostructures on Self-Assembled α-Al2O3 and Diblock Copolymer Templates

International Nuclear Information System (INIS)

Erb, Denise

2015-08-01

This thesis shows the preparation of nanostructured systems with a high degree of morphological uniformity and regularity employing exclusively selfassembly processes, and documents the investigation of these systems by means of atomic force microscopy (AFM), grazing incidence small angle X-ray scattering (GISAXS), and nuclear resonant scattering of synchrotron radiation (NRS). Whenever possible, the X-ray scattering methods are applied in-situ and simultaneously in order to monitor and correlate the evolution of structural and magnetic properties of the nanostructured systems. The following systems are discussed, where highly-ordered magnetic nanostructures are grown on α-Al 2 O 3 substrates with topographical surface patterning and on diblock copolymer templates with chemical surface patterning: - Nanofaceted surfaces of α-Al 2 O 3 - Magnetic nanostructures on nanofaceted α-Al 2 O 3 substrates - Thin films of microphase separated diblock copolymers - Magnetic nanostructures on diblock copolymer thin film templates The fact that the underlying self-assembly processes can be steered by external factors is utilized to optimize the degree of structural order in the nanostructured systems. The highly-ordered systems are well-suited for investigations with X-ray scattering methods, since due to their uniformity the inherently averaged scattered signal of a sample yields meaningful information on the properties of the contained nanostructures: By means of an in-situ GISAXS experiment at temperatures above 1000 C, details on the facet formation on α-Al 2 O 3 surfaces are determined. A novel method, merging in-situ GISAXS and NRS, shows the evolution of magnetic states in a system with correlated structural and magnetic inhomogeneity with lateral resolution. The temperature-dependence of the shape of Fe nanodots growing on diblock copolymer templates is revealed by in-situ GISAXS during sputter deposition of Fe. Combining in-situ GISAXS and NRS, the magnetization

Complete genome sequence of Acinetobacter baumannii XH386 (ST208, a multi-drug resistant bacteria isolated from pediatric hospital in China

Directory of Open Access Journals (Sweden)

Youhong Fang

2016-03-01

Full Text Available Acinetobacter baumannii is an important bacterium that emerged as a significant nosocomial pathogen worldwide. The rise of A. baumannii was due to its multi-drug resistance (MDR, while it was difficult to treat multi-drug resistant A. baumannii with antibiotics, especially in pediatric patients for the therapeutic options with antibiotics were quite limited in pediatric patients. A. baumannii ST208 was identified as predominant sequence type of carbapenem resistant A. baumannii in the United States and China. As we knew, there was no complete genome sequence reproted for A. baumannii ST208, although several whole genome shotgun sequences had been reported. Here, we sequenced the 4087-kilobase (kb chromosome and 112-kb plasmid of A. baumannii XH386 (ST208, which was isolated from a pediatric hospital in China. The genome of A. baumannii XH386 contained 3968 protein-coding genes and 94 RNA-only encoding genes. Genomic analysis and Minimum inhibitory concentration assay showed that A. baumannii XH386 was multi-drug resistant strain, which showed resistance to most of antibiotics, except for tigecycline. The data may be accessed via the GenBank accession number CP010779 and CP010780. Keywords: Acinetobacter baumannii, Multi-drug resistance, Paediatric

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

Science.gov (United States)

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.

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

Single-variant and multi-variant trend tests for genetic association with next-generation sequencing that are robust to sequencing error.

Science.gov (United States)

Kim, Wonkuk; Londono, Douglas; Zhou, Lisheng; Xing, Jinchuan; Nato, Alejandro Q; Musolf, Anthony; Matise, Tara C; Finch, Stephen J; Gordon, Derek

2012-01-01

As with any new technology, next-generation sequencing (NGS) has potential advantages and potential challenges. One advantage is the identification of multiple causal variants for disease that might otherwise be missed by SNP-chip technology. One potential challenge is misclassification error (as with any emerging technology) and the issue of power loss due to multiple testing. Here, we develop an extension of the linear trend test for association that incorporates differential misclassification error and may be applied to any number of SNPs. We call the statistic the linear trend test allowing for error, applied to NGS, or LTTae,NGS. This statistic allows for differential misclassification. The observed data are phenotypes for unrelated cases and controls, coverage, and the number of putative causal variants for every individual at all SNPs. We simulate data considering multiple factors (disease mode of inheritance, genotype relative risk, causal variant frequency, sequence error rate in cases, sequence error rate in controls, number of loci, and others) and evaluate type I error rate and power for each vector of factor settings. We compare our results with two recently published NGS statistics. Also, we create a fictitious disease model based on downloaded 1000 Genomes data for 5 SNPs and 388 individuals, and apply our statistic to those data. We find that the LTTae,NGS maintains the correct type I error rate in all simulations (differential and non-differential error), while the other statistics show large inflation in type I error for lower coverage. Power for all three methods is approximately the same for all three statistics in the presence of non-differential error. Application of our statistic to the 1000 Genomes data suggests that, for the data downloaded, there is a 1.5% sequence misclassification rate over all SNPs. Finally, application of the multi-variant form of LTTae,NGS shows high power for a number of simulation settings, although it can have

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

OpenAIRE

Hoarfrost, Megan Lane

2012-01-01

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the additio...

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

Science.gov (United States)

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.

Bactericidal and Hemocompatible Coating via the Mixed-Charged Copolymer.

Science.gov (United States)

Fan, Xiao-Li; Hu, Mi; Qin, Zhi-Hui; Wang, Jing; Chen, Xia-Chao; Lei, Wen-Xi; Ye, Wan-Ying; Jin, Qiao; Ren, Ke-Feng; Ji, Jian

2018-03-28

Cationic antibacterial coating based on quaternary ammonium compounds, with an efficient and broad spectrum bactericidal property, has been widely used in various fields. However, the high density of positive charges tends to induce weak hemocompatibility, which hinders the application of the cationic antibacterial coating in blood-contacting devices and implants. It has been reported that a negatively charged surface can reduce blood coagulation, showing improved hemocompatibility. Here, we describe a strategy to combine the cationic and anionic groups by using mixed-charged copolymers. The copolymers of poly (quaternized vinyl pyridine- co- n-butyl methacrylate- co-methacrylate acid) [P(QVP- co- nBMA- co-MAA)] were synthesized through free radical copolymerization. The cationic group of QVP, the anionic group of MAA, and the hydrophobic group of nBMA were designed to provide bactericidal capability, hemocompatibility, and coating stability, respectively. Our findings show that the hydrophilicity of the copolymer coating increased, and its zeta potential decreased from positive charge to negative charge with the increase of the anionic/cationic ratio. Meanwhile, the bactericidal property of the copolymer coating was kept around a similar level compared with the pure quaternary ammonium copolymer coating. Furthermore, the coagulation time, platelet adhesion, and hemolysis tests revealed that the hemocompatibility of the copolymer coating improved with the addition of the anionic group. The mixed-charged copolymer combined both bactericidal property and hemocompatibility and has a promising potential in blood-contacting antibacterial devices and implants.

SYNTHESIS OF STYRENE-METHYL METHACRYLATE BLOCK COPOLYMER BY POLYAZOAMIDE AS INITIATOR

Institute of Scientific and Technical Information of China (English)

WANG Zhongyi; WEI Jeqing

1996-01-01

Polyazoamide(PAA) was used as initiator to prepare block copolymer P(MMA-b-St) by free radical polymerization. The fraction of block copolymer was about 50%. The structure of the block-copolymer was characterized by IR and the results of 1H-NMR and GPC showed that the content of the block and the molecular weight (-Mw) of the prepolymer and block copolymer could be controlled by varying the mol ratio of styrene/PAA and MMA/prepolymer. DSC and TEM results revealed that the block copolymer has two separated glass transition temperatures and phase separation within the domain structure.

Nanoparticle packing within block copolymer micelles prepared by the interfacial instability method.

Science.gov (United States)

Nabar, Gauri M; Winter, Jessica O; Wyslouzil, Barbara E

2018-05-02

The interfacial instability method has emerged as a viable approach for encapsulating high concentrations of nanoparticles (NPs) within morphologically diverse micelles. In this method, transient interfacial instabilities at the surface of an emulsion droplet guide self-assembly of block co-polymers and NP encapsulants. Although used by many groups, there are no systematic investigations exploring the relationship between NP properties and micelle morphology. Here, the effect of quantum dot (QD) and superparamagnetic iron oxide NP (SPION) concentration on the shape, size, and surface deformation of initially spherical poly(styrene-b-ethylene oxide) (PS-b-PEO) micelles was examined. Multi-NP encapsulation and uniform dispersion within micelles was obtained even at low NP concentrations. Increasing NP concentration initially resulted in larger numbers of elongated micelles and cylinders with tightly-controlled diameters smaller than those of spherical micelles. Beyond a critical NP concentration, micelle formation was suppressed; the dominant morphology became densely-loaded NP structures that were coated with polymer and exhibited increased polydispersity. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed that NPs in densely-loaded structures can be well-ordered, with packing volume fractions of up to 24%. These effects were enhanced in magnetic composites, possibly by dipole interactions. Mechanisms governing phase transitions triggered by NP loading in the interfacial instability process were proposed. The current study helps establish and elucidate the active role played by NPs in directing block copolymer assembly in the interfacial instability process, and provides important guiding principles for the use of this approach in generating NP-loaded block copolymer composites.

Microtome Sliced Block Copolymers and Nanoporous Polymers as Masks for Nanolithography

DEFF Research Database (Denmark)

Shvets, Violetta; Schulte, Lars; Ndoni, Sokol

2014-01-01

Introduction. Block copolymers self-assembling properties are commonly used for creation of very fine nanostructures [1]. Goal of our project is to test new methods of the block-copolymer lithography mask preparation: macroscopic pieces of block-copolymers or nanoporous polymers with cross...... PDMS can be chemically etched from the PB matrix by tetrabutylammonium fluoride in tetrahydrofuran and macroscopic nanoporous PB piece is obtained. Both block-copolymer piece and nanoporous polymer piece were sliced with cryomicrotome perpendicular to the axis of cylinder alignment and flakes...... of etching patterns appear only under the certain parts of thick flakes and are not continuous. Although flakes from block copolymer are thinner and more uniform in thickness than flakes from nanoporous polymer, quality of patterns under nanoporous flakes appeared to be better than under block copolymer...

21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

Co-polymer Films for Sensors

Science.gov (United States)

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.

21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

HPMA and HEMA copolymer bead interactions with eukaryotic cells

Directory of Open Access Journals (Sweden)

Cristina D. Vianna-Soares

2004-09-01

Full Text Available Two different hydrophilic acrylate beads were prepared via aqueous suspension polymerization. Beads produced of a hydroxypropyl methacrylate (HPMA and ethyleneglycol methacrylate (EDMA copolymer were obtained using a polyvinyl alcohol suspending medium. Copolymers of 2hydroxyethyl methacrylate (HEMA, methyl methacrylate (MMA and ethyleneglycol methacrylate (EDMA beads were obtained using magnesium hydroxide as the suspending agent. Following characterization by scanning electron microscopy (SEM, nitrogen sorption analysis (NSA and mercury intrusion porosimetry (MIP, the beads were cultured with monkey fibroblasts (COS7 to evaluate their ability to support cell growth, attachment and adhesion. Cell growth behavior onto small HPMA/EDMA copolymer beads and large HEMA/MMA/EDMA copolymer beads is evaluated regarding their hidrophilicity/hidrophobicity and surface roughness.

Functionalization of Block Copolymer Vesicle Surfaces

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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.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

Directory of Open Access Journals (Sweden)

Lee D. Wilson

2011-08-01

Full Text Available Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid have been evaluated. The sorption properties of granular activated carbon (GAC were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g, CDI-X copolymers (< 101 m2/g, and granular activated carbon (GAC ~103 m2/g. The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i surface area of the sorbent; (ii CD content and accessibility; and (iii and the chemical nature of the sorbent material.

Self-assembled Block Copolymer Membranes with Bioinspired Artificial Channels

KAUST Repository

Sutisna, Burhannudin

2018-04-01

Nature is an excellent design that inspires scientists to develop smart systems. In the realm of separation technology, biological membranes have been an ideal model for synthetic membranes due to their ultrahigh permeability, sharp selectivity, and stimuliresponse. In this research, fabrications of bioinspired membranes from block copolymers were studied. Membranes with isoporous morphology were mainly prepared using selfassembly and non-solvent induced phase separation (SNIPS). An effective method that can dramatically shorten the path for designing new isoporous membranes from block copolymers via SNIPS was first proposed by predetermining a trend line computed from the solvent properties, interactions and copolymer block sizes of previously-obtained successful systems. Application of the method to new copolymer systems and fundamental studies on the block copolymer self-assembly were performed. Furthermore, the manufacture of bioinspired membranes was explored using (1) poly(styrene-b-4-hydroxystyrene-b-styrene) (PS-b-PHS-b-PS), (2) poly(styrene-bbutadiene- b-styrene) (PS-b-PB-b-PS) and (3) poly(styrene-b-γ-benzyl-L-glutamate) (PSb- PBLG) copolymers via SNIPS. The structure formation was investigated using smallangle X-ray scattering (SAXS) and time-resolved grazing-Incidence SAXS. The PS-b- PHS-b-PS membranes showed preferential transport for proteins, presumably due to the hydrogen bond interactions within the channels, electrostatic attraction, and suitable pore dimension. Well-defined nanochannels with pore sizes of around 4 nm based on PS-b- PB-b-PS copolymers could serve as an excellent platform to fabricate bioinspired channels due to the modifiable butadiene blocks. Photolytic addition of thioglycolic acid was demonstrated without sacrificing the self-assembled morphology, which led to a five-fold increase in water permeance compared to that of the unmodified. Membranes with a unique feather-like structure and a lamellar morphology for dialysis and

Regularization based on steering parameterized Gaussian filters and a Bhattacharyya distance functional

Science.gov (United States)

Lopes, Emerson P.

2001-08-01

Template regularization embeds the problem of class separability. In the machine vision perspective, this problem is critical when a textural classification procedure is applied to non-stationary pattern mosaic images. These applications often present low accuracy performance due to disturbance of the classifiers produced by exogenous or endogenous signal regularity perturbations. Natural scene imaging, where the images present certain degree of homogeneity in terms of texture element size or shape (primitives) shows a variety of behaviors, especially varying the preferential spatial directionality. The space-time image pattern characterization is only solved if classification procedures are designed considering the most robust tools within a parallel and hardware perspective. The results to be compared in this paper are obtained using a framework based on multi-resolution, frame and hypothesis approach. Two strategies for the bank of Gabor filters applications are considered: adaptive strategy using the KL transform and fix configuration strategy. The regularization under discussion is accomplished in the pyramid building system instance. The filterings are steering Gaussians controlled by free parameters which are adjusted in accordance with a feedback process driven by hints obtained from sequence of frames interaction functionals pos-processed in the training process and including classification of training set samples as examples. Besides these adjustments there is continuous input data sensitive adaptiveness. The experimental result assessments are focused on two basic issues: Bhattacharyya distance as pattern characterization feature and the combination of KL transform as feature selection and adaptive criterion with the regularization of the pattern Bhattacharyya distance functional (BDF) behavior, using the BDF state separability and symmetry as the main indicators of an optimum framework parameter configuration.

Process of irradiating an ethylene-vinyl acetate copolymer to produce low melt index copolymers, and products of said process

International Nuclear Information System (INIS)

Potts, J.E.

1976-01-01

Application of ionizing radiation in a dose between 0.5 and 1.5 megareps to copolymers of ethylene and vinyl acetate lowers the melt index and increases the toughness and flexibility of the copolymers without substantially decreasing solubility or thermoplasticity. The increased toughness and flexibility carries over into blends with wax or polyethylene. (author)

Styrene-spaced copolymers including anthraquinone and β-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions.

Science.gov (United States)

Megiatto, Jackson D; Cazeils, Emmanuel; Ham-Pichavant, Frédérique; Grelier, Stéphane; Gardrat, Christian; Castellan, Alain

2012-05-14

A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida.

Science.gov (United States)

Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang

2011-04-01

Polyhydroxyalkanoate (PHA) synthesis genes phaPCJ(Ac) cloned from Aeromonas caviae were transformed into Pseudomonas putida KTOY06ΔC, a mutant of P. putida KT2442, resulting in the ability of the recombinant P. putida KTOY06ΔC (phaPCJ(A.c)) to produce a short-chain-length and medium-chain-length PHA block copolymer consisting of poly-3-hydroxybutyrate (PHB) as one block and random copolymer of 3-hydroxyvalerate (3HV) and 3-hydroxyheptanoate (3HHp) as another block. The novel block polymer was studied by differential scanning calorimetry (DSC), nuclear magnetic resonance, and rheology measurements. DSC studies showed the polymer to possess two glass transition temperatures (T(g)), one melting temperature (T(m)) and one cool crystallization temperature (T(c)). Rheology studies clearly indicated a polymer chain re-arrangement in the copolymer; these studies confirmed the polymer to be a block copolymer, with over 70 mol% homopolymer (PHB) of 3-hydroxybutyrate (3HB) as one block and around 30 mol% random copolymers of 3HV and 3HHp as the second block. The block copolymer was shown to have the highest tensile strength and Young's modulus compared with a random copolymer with similar ratio and a blend of homopolymers PHB and PHVHHp with similar ratio. Compared with other commercially available PHA including PHB, PHBV, PHBHHx, and P3HB4HB, the short-chain- and medium-chain-length block copolymer PHB-b-PHVHHp showed differences in terms of mechanical properties and should draw more attentions from the PHA research community. © Springer-Verlag 2010

Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

Science.gov (United States)

Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

2018-04-01

We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

Online Manifold Regularization by Dual Ascending Procedure

Directory of Open Access Journals (Sweden)

Boliang Sun

2013-01-01

Full Text Available We propose a novel online manifold regularization framework based on the notion of duality in constrained optimization. The Fenchel conjugate of hinge functions is a key to transfer manifold regularization from offline to online in this paper. Our algorithms are derived by gradient ascent in the dual function. For practical purpose, we propose two buffering strategies and two sparse approximations to reduce the computational complexity. Detailed experiments verify the utility of our approaches. An important conclusion is that our online MR algorithms can handle the settings where the target hypothesis is not fixed but drifts with the sequence of examples. We also recap and draw connections to earlier works. This paper paves a way to the design and analysis of online manifold regularization algorithms.

Surface morphology of PS-PDMS diblock copolymer films

DEFF Research Database (Denmark)

Andersen, T.H.; Tougaard, S.; Larsen, N.B.

2001-01-01

Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which ra...

Reactivity Ratios for Organotin Copolymer Systems

Directory of Open Access Journals (Sweden)

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.

SANS and SAXS study of block copolymer/homopolymer mixtures

International Nuclear Information System (INIS)

Hasegawa, Hirokazu; Tanaka, Hideaki; Hashimoto, Takeji; Han, C.C.

1991-01-01

The lateral and vertical components of the radius of gyration for a single block copolymer chain and those of a single homopolymer chain in the lamellar microdomain space formed by a mixture of diblock copolymers and homopolymers were investigated by means of small-angle neutron scattering (SANS) and the microdomain structures by small-angle X-ray scattering (SAXS). The homopolymers whose molecular weights are much smaller than that of the corresponding chains of the block copolymers were used so that the homopolymers were uniformly solubilized in the corresponding microdomains. The SANS result suggests that the homopolymer chains in the microdomain space as well as the block copolymer chains are more compressed in the direction parallel to the interface and more stretched in the direction perpendicular to the interface than the corresponding unperturbed polymer chains with the same molecular weight. On increasing the volume fraction of the homopolymers the thickness of the lamellar microdomains increases. The block copolymer chains were found to undergo an isochoric affine deformation on addition of the homopolymers or with the change of the thickness of the lamellar microdomains. (orig.)

Slip-spring model of entangled rod-coil block copolymers

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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.

Matlab enhanced multi-threaded tomography optimization sequence (MEMTOS)

International Nuclear Information System (INIS)

Lum, Edward S.; Pope, Chad L.

2016-01-01

Highlights: • Monte Carlo simulation of spent nuclear fuel assembly neutron computed tomography. • Optimized parallel calculations conducted from within the MATLAB environment. • Projection difference technique used to identify anomalies in spent nuclear fuel assemblies. - Abstract: One challenge associated with spent nuclear fuel assemblies is the lack of non-destructive analysis techniques to determine if fuel pins have been removed or replaced or if there are significant defects associated with fuel pins deep within a fuel assembly. Neutron computed tomography is a promising technique for addressing these qualitative issues. Monte Carlo simulation of spent nuclear fuel neutron computed tomography allows inexpensive process investigation and optimization. The main purpose of this work is to provide a fully automated advanced simulation framework for the analysis of spent nuclear fuel inspection using neutron computed tomography. The simulation framework, called Matlab Enhanced Multi-Threaded Tomography Optimization Sequence (MEMTOS) not only automates the simulation process, but also generates superior tomography image results. MEMTOS is written in the MATLAB scripting language and addresses file management, parallel Monte Carlo execution, results extraction, and tomography image generation. This paper describes the mathematical basis for neutron computed tomography, the Monte Carlo technique used to simulate neutron computed tomography, and the overall tomography simulation optimization algorithm. Sequence results presented include overall simulation speed enhancement, tomography and image results obtained for Experimental Breeder Reactor II spent fuel assemblies and light water reactor fuel assemblies. Optimization using a projection difference technique are also described.

Robust visual tracking via structured multi-task sparse learning

KAUST Repository

Zhang, Tianzhu

2012-11-09

In this paper, we formulate object tracking in a particle filter framework as a structured multi-task sparse learning problem, which we denote as Structured Multi-Task Tracking (S-MTT). Since we model particles as linear combinations of dictionary templates that are updated dynamically, learning the representation of each particle is considered a single task in Multi-Task Tracking (MTT). By employing popular sparsity-inducing lp,q mixed norms (specifically p∈2,∞ and q=1), we regularize the representation problem to enforce joint sparsity and learn the particle representations together. As compared to previous methods that handle particles independently, our results demonstrate that mining the interdependencies between particles improves tracking performance and overall computational complexity. Interestingly, we show that the popular L1 tracker (Mei and Ling, IEEE Trans Pattern Anal Mach Intel 33(11):2259-2272, 2011) is a special case of our MTT formulation (denoted as the L11 tracker) when p=q=1. Under the MTT framework, some of the tasks (particle representations) are often more closely related and more likely to share common relevant covariates than other tasks. Therefore, we extend the MTT framework to take into account pairwise structural correlations between particles (e.g. spatial smoothness of representation) and denote the novel framework as S-MTT. The problem of learning the regularized sparse representation in MTT and S-MTT can be solved efficiently using an Accelerated Proximal Gradient (APG) method that yields a sequence of closed form updates. As such, S-MTT and MTT are computationally attractive. We test our proposed approach on challenging sequences involving heavy occlusion, drastic illumination changes, and large pose variations. Experimental results show that S-MTT is much better than MTT, and both methods consistently outperform state-of-the-art trackers. © 2012 Springer Science+Business Media New York.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

Science.gov (United States)

Wilson, Lee D; Mohamed, Mohamed H; Berhaut, Christopher L

2011-08-29

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Diblock Copolymer/Layered Silicate Nanocomposite Thin Film Stability

Science.gov (United States)

Limary, Ratchana; Green, Peter

2000-03-01

The stability of thin film symmetric diblock copolymers blended with layered silicate nanocomposites were examined using a combination of optical microscopy, atomic force microscopy (AFM), and X-ray diffraction (XRD). Two cases were examined PS-b-PMMA (polystyrene-b-polymethylacrylate) blended with montmorillonite stoichiometrically loaded with alkyl ammonium ions, OLS(S), and PS-b-PMMA blended with montmorillonite loaded with excess alkyl ammonium ions, OLS(E). XRD spectra show an increase in the gallery spacing of the OLSs, indicating that the copolymer chains have intercalated the layered silicates. AFM images reveal a distinct difference between the two nanocomposite thin films: regions in the vicinity of OLS(S) aggregates were depleted of material, while in the vicinity of OLS(E) aggregates, dewetting of the substrate occurred. We show that the stability of the copolymer/OLS nanocomposite films is determined by the enthalpic driving force associated with intercalation of the copolymer chains into the galleries of the modified OLS layers and by the substrate/organic modifier interactions.

Influence of Chirality in Ordered Block Copolymer Phases

Science.gov (United States)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Block copolymer-nanoparticle hybrid self-assembly

KAUST Repository

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.

UNFOLDED REGULAR AND SEMI-REGULAR POLYHEDRA

Directory of Open Access Journals (Sweden)

IONIŢĂ Elena

2015-06-01

Full Text Available This paper proposes a presentation unfolding regular and semi-regular polyhedra. Regular polyhedra are convex polyhedra whose faces are regular and equal polygons, with the same number of sides, and whose polyhedral angles are also regular and equal. Semi-regular polyhedra are convex polyhedra with regular polygon faces, several types and equal solid angles of the same type. A net of a polyhedron is a collection of edges in the plane which are the unfolded edges of the solid. Modeling and unfolding Platonic and Arhimediene polyhedra will be using 3dsMAX program. This paper is intended as an example of descriptive geometry applications.

Position transitions of polymer-grafted nanoparticles in diblock-copolymer nanocomposites

Directory of Open Access Journals (Sweden)

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.

Melt-processable, radiation cross-linkable E--CTFE copolymer compositions

International Nuclear Information System (INIS)

Robertson, A.B.; Schaffhauser, R.J.

1976-01-01

Melt-processable, radiation cross-linkable ethylene/chlorotrifluoroethylene copolymer compositions are provided which contain about 0.1 to 5 percent by weight of the copolymer of a radiation cross-linking promoter, about 0.01 to 5 percent by weight of an anti-oxidant and about 0.1 to 30 precent by weight of an acid scavenger. Such compositions do not give off odors when irradiated to cross-link the copolymer and do not develop bubbles after irradiation. 15 claims, no drawings

Design strategy of pH-sensitive triblock copolymer micelles for efficient cellular uptake by computer simulations

Science.gov (United States)

Xia, Qiang-sheng; Ding, Hong-ming; Ma, Yu-qiang

2018-03-01

Efficient delivery of nanoparticles into specific cell interiors is of great importance in biomedicine. Recently, the pH-responsive micelle has emerged as one potential nanocarrier to realize such purpose since there exist obvious pH differences between normal tissues and tumors. Herein, by using dissipative particle dynamics simulation, we investigate the interaction of the pH-sensitive triblock copolymer micelles composed of ligand (L), hydrophobic block (C) and polyelectrolyte block (P) with cell membrane. It is found that the structure rearrangement of the micelle can facilitate its penetration into the lower leaflet of the bilayer. However, when the ligand-receptor specific interaction is weak, the micelles may just fuse with the upper leaflet of the bilayer. Moreover, the ionization degree of polyelectrolyte block and the length of hydrophobic block also play a vital role in the penetration efficiency. Further, when the sequence of the L, P, C beads in the copolymers is changed, the translocation pathways of the micelles may change from direct penetration to Janus engulfment. The present study reveals the relationship between the molecular structure of the copolymer and the uptake of the pH-sensitive micelles, which may give some significant insights into the experimental design of responsive micellar nanocarriers for highly efficient cellular delivery.

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

Science.gov (United States)

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.

Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites

Science.gov (United States)

Bowman, Michelle Kathleen

Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a

Responsive Copolymers for Enhanced Petroleum Recovery

Energy Technology Data Exchange (ETDEWEB)

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.

Phase behavior of model ABC triblock copolymers

Science.gov (United States)

Chatterjee, Joon

The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that

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

Science.gov (United States)

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.

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

KAUST Repository

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

Melt-processable hydrophobic acrylonitrile-based copolymer systems with adjustable elastic properties designed for biomedical applications.

Science.gov (United States)

Cui, J; Trescher, K; Kratz, K; Jung, F; Hiebl, B; Lendlein, A

2010-01-01

Acrylonitrile-based polymer systems (PAN) are comprehensively explored as versatile biomaterials having various potential biomedical applications, such as membranes for extra corporal devices or matrixes for guided skin reconstruction. The surface properties (e.g. hydrophilicity or charges) of such materials can be tailored over a wide range by variation of molecular parameters such as different co-monomers or their sequence structure. Some of these materials show interesting biofunctionalities such as capability for selective cell cultivation. So far, the majority of AN-based copolymers, which were investigated in physiological environments, were processed from the solution (e.g. membranes), as these materials are thermo-sensitive and might degrade when heated. In this work we aimed at the synthesis of hydrophobic, melt-processable AN-based copolymers with adjustable elastic properties for preparation of model scaffolds with controlled pore geometry and size. For this purpose a series of copolymers from acrylonitrile and n-butyl acrylate (nBA) was synthesized via free radical copolymerisation technique. The content of nBA in the copolymer varied from 45 wt% to 70 wt%, which was confirmed by 1H-NMR spectroscopy. The glass transition temperatures (Tg) of the P(AN-co-nBA) copolymers determined by differential scanning calorimetry (DSC) decreased from 58 degrees C to 20 degrees C with increasing nBA-content, which was in excellent agreement with the prediction of the Gordon-Taylor equation based on the Tgs of the homopolymers. The Young's modulus obtained in tensile tests was found to decrease significantly with rising nBA-content from 1062 MPa to 1.2 MPa. All copolymers could be successfully processed from the melt with processing temperatures ranging from 50 degrees C to 170 degrees C, whereby thermally induced decomposition was only observed at temperatures higher than 320 degrees C in thermal gravimetric analysis (TGA). Finally, the melt processed P

Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

KAUST Repository

Moreno Chaparro, Nicolas; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor; Calo, Victor M.

2015-01-01

We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

KAUST Repository

Moreno Chaparro, Nicolas

2015-10-27

We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

Physical properties of metallocenes propene-higher α-olefins copolymers

International Nuclear Information System (INIS)

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)

ADDRESS SEQUENCES FOR MULTI RUN RAM TESTING

Directory of Open Access Journals (Sweden)

V. N. Yarmolik

2014-01-01

Full Text Available A universal approach for generation of address sequences with specified properties is proposed and analyzed. A modified version of the Antonov and Saleev algorithm for Sobol sequences genera-tion is chosen as a mathematical description of the proposed method. Within the framework of the proposed universal approach, the Sobol sequences form a subset of the address sequences. Other sub-sets are also formed, which are Gray sequences, anti-Gray sequences, counter sequences and sequenc-es with specified properties.

Directed self-assembly of poly(styrene)-block-poly(acrylic acid) copolymers for sub-20nm pitch patterning

Science.gov (United States)

Cheng, Jing; Lawson, Richard A.; Yeh, Wei-Ming; Jarnagin, Nathan D.; Peters, Andrew; Tolbert, Laren M.; Henderson, Clifford L.

2012-03-01

Directed self-assembly (DSA) of block copolymers is a promising technology for extending the patterning capability of current lithographic exposure tools. For example, production of sub-40 nm pitch features using 193nm exposure technologies is conceivably possible using DSA methods without relying on time consuming, challenging, and expensive multiple patterning schemes. Significant recent work has focused on demonstration of the ability to produce large areas of regular grating structures with low numbers of defects using self-assembly of poly(styrene)-b-poly(methyl methacrylate) copolymers (PS-b-PMMA). While these recent results are promising and have shown the ability to print pitches approaching 20 nm using DSA, the ability to advance to even smaller pitches will be dependent upon the ability to develop new block copolymers with higher χ values and the associated alignment and block removal processes required to achieve successful DSA with these new materials. This paper reports on work focused on identifying higher χ block copolymers and their associated DSA processes for sub-20 nm pitch patterning. In this work, DSA using polystyrene-b-polyacid materials has been explored. Specifically, it is shown that poly(styrene)-b-poly(acrylic acid) copolymers (PS-b-PAA) is one promising material for achieving substantially smaller pitch patterns than those possible with PS-b-PMMA while still utilizing simple hydrocarbon polymers. In fact, it is anticipated that much of the learning that has been done with the PS-b-PMMA system, such as development of highly selective plasma etch block removal procedures, can be directly leveraged or transferred to the PS-b-PAA system. Acetone vapor annealing of PS-b-PAA (Mw=16,000 g/mol with 50:50 mole ratio of PS:PAA) and its self-assembly into a lamellar morphology is demonstrated to generate a pattern pitch size (L0) of 21 nm. The χ value for PS-b-PAA was estimated from fingerprint pattern pitch data to be approximately 0.18 which

Incorporation of fluconazole in copolymer PMMA-g-PEG derivatives

International Nuclear Information System (INIS)

Silveira, B.M.; Santos, V.M.R. dos; Novack, K.M.; Lopes, S.A.

2014-01-01

The graft copolymer PMMA-g-PEG went through chemical transformations in its chain through acetylation, halogenation, methylation and esterification followed by hydrolysis reactions. Subsequently, the copolymer PMMA-g-PEG derivatives passed through the process of emulsification and incorporation of the drug fluconazole. Derivatives copolymers were characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) after incorporation in order to evaluate their effectiveness. The efficiency of incorporation was observed and it was also verified that the complexity of polymer chain influence in the incorporated fluconazole content. (author)

Model-Checking of Linear-Time Properties in Multi-Valued Systems

OpenAIRE

Li, Yongming; Droste, Manfred; Lei, Lihui

2012-01-01

In this paper, we study model-checking of linear-time properties in multi-valued systems. Safety property, invariant property, liveness property, persistence and dual-persistence properties in multi-valued logic systems are introduced. Some algorithms related to the above multi-valued linear-time properties are discussed. The verification of multi-valued regular safety properties and multi-valued $\\omega$-regular properties using lattice-valued automata are thoroughly studied. Since the law o...

Polyethylene-Based Tadpole Copolymers

KAUST Repository

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

Morphologies of precise polyethylene-based acid copolymers and ionomers

Science.gov (United States)

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

Robust visual tracking via multi-task sparse learning

KAUST Repository

Zhang, Tianzhu

2012-06-01

In this paper, we formulate object tracking in a particle filter framework as a multi-task sparse learning problem, which we denote as Multi-Task Tracking (MTT). Since we model particles as linear combinations of dictionary templates that are updated dynamically, learning the representation of each particle is considered a single task in MTT. By employing popular sparsity-inducing p, q mixed norms (p D; 1), we regularize the representation problem to enforce joint sparsity and learn the particle representations together. As compared to previous methods that handle particles independently, our results demonstrate that mining the interdependencies between particles improves tracking performance and overall computational complexity. Interestingly, we show that the popular L 1 tracker [15] is a special case of our MTT formulation (denoted as the L 11 tracker) when p q 1. The learning problem can be efficiently solved using an Accelerated Proximal Gradient (APG) method that yields a sequence of closed form updates. As such, MTT is computationally attractive. We test our proposed approach on challenging sequences involving heavy occlusion, drastic illumination changes, and large pose variations. Experimental results show that MTT methods consistently outperform state-of-the-art trackers. © 2012 IEEE.

Block coordination copolymers

Science.gov (United States)

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.

Human visual system automatically encodes sequential regularities of discrete events.

Science.gov (United States)

Kimura, Motohiro; Schröger, Erich; Czigler, István; Ohira, Hideki

2010-06-01

For our adaptive behavior in a dynamically changing environment, an essential task of the brain is to automatically encode sequential regularities inherent in the environment into a memory representation. Recent studies in neuroscience have suggested that sequential regularities embedded in discrete sensory events are automatically encoded into a memory representation at the level of the sensory system. This notion is largely supported by evidence from investigations using auditory mismatch negativity (auditory MMN), an event-related brain potential (ERP) correlate of an automatic memory-mismatch process in the auditory sensory system. However, it is still largely unclear whether or not this notion can be generalized to other sensory modalities. The purpose of the present study was to investigate the contribution of the visual sensory system to the automatic encoding of sequential regularities using visual mismatch negativity (visual MMN), an ERP correlate of an automatic memory-mismatch process in the visual sensory system. To this end, we conducted a sequential analysis of visual MMN in an oddball sequence consisting of infrequent deviant and frequent standard stimuli, and tested whether the underlying memory representation of visual MMN generation contains only a sensory memory trace of standard stimuli (trace-mismatch hypothesis) or whether it also contains sequential regularities extracted from the repetitive standard sequence (regularity-violation hypothesis). The results showed that visual MMN was elicited by first deviant (deviant stimuli following at least one standard stimulus), second deviant (deviant stimuli immediately following first deviant), and first standard (standard stimuli immediately following first deviant), but not by second standard (standard stimuli immediately following first standard). These results are consistent with the regularity-violation hypothesis, suggesting that the visual sensory system automatically encodes sequential

Limited-angle multi-energy CT using joint clustering prior and sparsity regularization

Science.gov (United States)

Zhang, Huayu; Xing, Yuxiang

2016-03-01

In this article, we present an easy-to-implement Multi-energy CT scanning strategy and a corresponding reconstruction method, which facilitate spectral CT imaging by improving the data efficiency the number-of-energy- channel fold without introducing visible limited-angle artifacts caused by reducing projection views. Leveraging the structure coherence at different energies, we first pre-reconstruct a prior structure information image using projection data from all energy channels. Then, we perform a k-means clustering on the prior image to generate a sparse dictionary representation for the image, which severs as a structure information constraint. We com- bine this constraint with conventional compressed sensing method and proposed a new model which we referred as Joint Clustering Prior and Sparsity Regularization (CPSR). CPSR is a convex problem and we solve it by Alternating Direction Method of Multipliers (ADMM). We verify our CPSR reconstruction method with a numerical simulation experiment. A dental phantom with complicate structures of teeth and soft tissues is used. X-ray beams from three spectra of different peak energies (120kVp, 90kVp, 60kVp) irradiate the phantom to form tri-energy projections. Projection data covering only 75◦ from each energy spectrum are collected for reconstruction. Independent reconstruction for each energy will cause severe limited-angle artifacts even with the help of compressed sensing approaches. Our CPSR provides us with images free of the limited-angle artifact. All edge details are well preserved in our experimental study.

About morphology in ethylene-propylene(-diene) copolymers-based latexes

NARCIS (Netherlands)

Tillier, D.L.; Meuldijk, J.; Hoehne, G.W.H.; Frederik, P.M.; Regev, O.; Koning, C.E.

2005-01-01

Coatings and engineering plastics often require high impact strength. This property can be achieved with tougheners. For the present paper, core-shell impact modifiers were synthesized using ethylene–propylene copolymers (EPM), ethylene–propylene-diene copolymers (EPDM) or a mixture of both types

Adsorption of charged diblock copolymers : effect on colloidal stability

NARCIS (Netherlands)

Israels, R.

1994-01-01

In this thesis we present Scheutjens-Fleer (SF) calculations on the adsorption of diblock copolymers. More specifically, we restrict ourselves to adsorption at uncharged surfaces, while the specific type of block copolymers we consider have one uncharged adsorbing "anchor" block and one

Monte Carlo simulations of the phase separation of a copolymer blend in a thin film

KAUST Repository

Wang, Zhexiao

2014-12-11

Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.

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

Directory of Open Access Journals (Sweden)

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.

Responsive copolymers for enhanced petroleum recovery. Second annual report

Energy Technology Data Exchange (ETDEWEB)

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.

Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers

Energy Technology Data Exchange (ETDEWEB)

Li, Xiaohui; Zhao, Yunhui [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China); Li, Hui [School of Chemistry and Chemical Engineering, Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, University of Jinan, Jinan 250022 (China); Yuan, Xiaoyan, E-mail: xyuan28@yahoo.com [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China)

2014-10-15

Highlights: • PMTFPS–b-polyacrylate copolymers in five different compositions were synthesized. • Enrichment of PMTFPS amounts at the surface made high F/Si value. • Icing delay time was related to the surface roughness. • Ice shear strength was decreased by the synergistic effect of silicone and fluorine. - Abstract: Five polymethyltrifluoropropylsiloxane (PMTFPS)–polyacrylate block copolymers (PMTFPS–b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10–50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at −15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS–b-polyacrylate copolymer can be used as icephobic coating materials potentially.

Realization of an integrated VDF/TrFE copolymer-on-silicon pyroelectric sensor

NARCIS (Netherlands)

Setiadi, D.; Setiadi, D.; Regtien, Paulus P.L.; Sarro, P.M.

1995-01-01

An integrated pyroelectric sensor based on a vinylidene fluoride trifluoroethylene (VDF/TrFE) copolymer is presented. A silicon substrate that contains FET readout electronics is coated with the VDF/TrFE copolymer film using a spin-coating technique. On-chip poling of the copolymer has been applied

Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer

National Research Council Canada - National Science Library

Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

2006-01-01

...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

Radiation crosslinked block copolymer blends with improved impact resistance

International Nuclear Information System (INIS)

Saunders, F.L.; Pelletier, R.R.

1976-01-01

Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

Block copolymer battery separator

Science.gov (United States)

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.

Contour Propagation With Riemannian Elasticity Regularization

DEFF Research Database (Denmark)

Bjerre, Troels; Hansen, Mads Fogtmann; Sapru, W.

2011-01-01

Purpose/Objective(s): Adaptive techniques allow for correction of spatial changes during the time course of the fractionated radiotherapy. Spatial changes include tumor shrinkage and weight loss, causing tissue deformation and residual positional errors even after translational and rotational image...... the planning CT onto the rescans and correcting to reflect actual anatomical changes. For deformable registration, a free-form, multi-level, B-spline deformation model with Riemannian elasticity, penalizing non-rigid local deformations, and volumetric changes, was used. Regularization parameters was defined...... on the original delineation and tissue deformation in the time course between scans form a better starting point than rigid propagation. There was no significant difference of locally and globally defined regularization. The method used in the present study suggests that deformed contours need to be reviewed...

Highly conductive side chain block copolymer anion exchange membranes.

Science.gov (United States)

Wang, Lizhu; Hickner, Michael A

2016-06-28

Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

Industrial applications of multi-functional, multi-phase reactors

NARCIS (Netherlands)

Harmsen, G.J.; Chewter, L.A.

1999-01-01

To reveal trends in the design and operation of multi-functional, multi-phase reactors, this paper describes, in historical sequence, three industrial applications of multi-functional, multi-phase reactors developed and operated by Shell Chemicals during the last five decades. For each case, we

Cultural Transmission and Evolution of Melodic Structures in Multi-generational Signaling Games

DEFF Research Database (Denmark)

Lumaca, Massimo; Baggio, G.

2017-01-01

, and basic and compound emotions as meanings, were transmitted from senders to receivers along diffusion chains in which the receiver in each game became the sender in the next game. During transmission, structural regularities accumulated in the signaling systems, following principles of proximity, symmetry...... and cognitive constraints similarly affect the evolution of musical systems? We conducted an experiment on the cultural evolution of artificial melodic systems, using multi-generational signaling games as a laboratory model of cultural transmission. Signaling systems, using five-tone sequences as signals...

Hybrid Silicon-Based Organic/Inorganic Block Copolymers with Sol-Gel Active Moieties: Synthetic Advances, Self-Assembly and Applications in Biomedicine and Materials Science.

Science.gov (United States)

Czarnecki, Sebastian; Bertin, Annabelle

2018-03-07

Hybrid silicon-based organic/inorganic (multi)block copolymers are promising polymeric precursors to create robust nano-objects and nanomaterials due to their sol-gel active moieties via self-assembly in solution or in bulk. Such nano-objects and nanomaterials have great potential in biomedicine as nanocarriers or scaffolds for bone regeneration as well as in materials science as Pickering emulsifiers, photonic crystals or coatings/films with antibiofouling, antibacterial or water- and oil-repellent properties. Thus, this Review outlines recent synthetic efforts in the preparation of these hybrid inorganic/organic block copolymers, gives an overview of their self-assembled structures and finally presents recent examples of their use in the biomedical field and material science. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Directory of Open Access Journals (Sweden)

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.

Oriented Structure of Pentablock Copolymers Induced by Solution Extrusion

Science.gov (United States)

Harada, Tamotsu; Bates, Frank S.; Lodge, Timothy P.

2002-03-01

Highly oriented structure of a poly(styrene-co-butadiene) pentablock copolymer (Mw; 104,700 g/mol, weight percentage of polybutadiene blocks; 29 wt of concentrated solutions. The pentablock copolymer was dissolved into mixtures of toluene and heptane, and the polymer concentration ranged from 40 wt extrusion, the pentablock copolymer was solidified either by coagulation in methanol or by evaporation of the solvent. Interestingly, a highly oriented lamellar structure was confirmed through the small angle X-ray scattering over a specific range of heptane composition, which is a good solvent for polybutadiene, although the hexagonal cylinder morphology was identified for the melt sample. The transition from the oriented lamellar to highly oriented cylinder structure was observed by annealing the samples at temperatures above the glass transition temperature of polystyrene. Moreover, a transition from parallel to perpendicular orientation in the lamellar state was observed with an increase of the extrusion shear rate. A comparison between pentablock and triblock copolymers will be also discussed.

Resonant soft x-ray GISAXS on block copolymer films

Science.gov (United States)

Wang, Cheng; Araki, T.; Watts, B.; Ade, H.; Hexemer, A.; Park, S.; Russell, T. P.; Schlotter, W. F.; Stein, G. E.; Tang, C.; Kramer, E. J.

2008-03-01

Ordered block copolymer thin films may have important applications in modern device fabrication. Current characterization methods such as conventional GISAXS have fixed electron density contrast that can be overwhelmed by surface scattering. However, soft x-rays have longer wavelength, energy dependent contrast and tunable penetration, making resonant GISAXS a very promising tool for probing nanostructured polymer thin films. Our preliminary investigation was performed using PS-b-P2VP block copolymer films on beam-line 5-2 SSRL, and beam-line 6.3.2 at ALS, LBNL. The contrast/sensitivity of the scattering pattern varies significantly with photon energy close to the C K-edge (˜290 eV). Also, higher order peaks are readily observed, indicating hexagonal packing structure in the sample. Comparing to the hard x-ray GISAXS data of the same system, it is clear that resonant GISAXS has richer data and better resolution. Beyond the results on the A-B diblock copolymers, results on ABC block copolymers are especially interesting.

Modification of ethylene-norbornene copolymer by Gamma irradiation

Directory of Open Access Journals (Sweden)

Kačarević-Popović Zorica M.

2006-01-01

Full Text Available The possibility of modifying polyethylene and many other polymers with high energy radiation has led to many useful applications. Due to their new combination of properties and the shortage of experimental data, the radiolysis of a new class of materials, cyclo-olefin copolymers (COC, polymerised from norbornene and ethylene using metallocene catalysts, is of great interest to the study of radiation chemistry and the physics of polymeric systems. Ethylenenorbornene copolymer, pristine and containing an antioxidant were subjected to gamma irradiation in the presence of air and in water. The irradiated copolymer was studied using IR and UV-vis spectrophotometric analysis. The radiation-induced changes in the molecular structure were correlated to changes in the glass transition temperature measured by the DSC method.

ABC triblock copolymer vesicles with mesh-like morphology.

Science.gov (United States)

Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

2011-01-25

Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

Science.gov (United States)

Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

2011-12-01

The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

Double Sequences and Iterated Limits in Regular Space

Directory of Open Access Journals (Sweden)

Coghetto Roland

2016-09-01

Full Text Available First, we define in Mizar [5], the Cartesian product of two filters bases and the Cartesian product of two filters. After comparing the product of two Fréchet filters on ℕ (F1 with the Fréchet filter on ℕ × ℕ (F2, we compare limF₁ and limF₂ for all double sequences in a non empty topological space.

Anomalous Behaviors of Block Copolymers at the Interface of an Immiscible Polymer Blend

Science.gov (United States)

Ryu, Ji Ho; Lee, Won Bo

We investigate the effects of structure and stiffness of block copolymers on the interface of an immiscible polymer blend using coarse-grained molecular dynamics (CGMD) simulation. The diblock and grafted copolymers, which are described by Kremer and Grest bead spring model, are used to compare the compatibilization efficiency, that is, reduction of the interfacial tension. It is found that, overall, the grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, it is noted that an increase in the stiffness of one block of diblock copolymer causes inhomogeneous interfacial coverage due to bundle formation among the stiff blocks and orientational constraint on bundled structures near the interface, which makes copolymers poor compatibilizers. The dependence of anomalous orientational constraint on the chain length of homopolymers is also investigated. Theoretical and Computational Soft Matters Lab.

Responsive copolymers for enhanced petroleum recovery. Annual report

Energy Technology Data Exchange (ETDEWEB)

McCormick, C.; Hester, R.

1994-08-01

A coordinated research program involving synthesis, characterization, and rheology has been undertaken to develop advanced polymer system which should be significantly more efficient than polymers presently used for mobility control and conformance. Unlike the relatively inefficient, traditional EOR polymers, these advanced polymer systems possess microstructural features responsive to temperature, electrolyte concentration, and shear conditions. Contents of this report include the following chapters. (1) First annual report responsive copolymers for enhanced oil recovery. (2) Copolymers of acrylamide and sodium 3-acrylamido-3-methylbutanoate. (3) Terpolymers of NaAMB, Am, and n-decylacrylamide. (4) Synthesis and characterization of electrolyte responsive terpolymers of acrylamide, N-(4-butyl)phenylacrylamide, and sodium acrylate, sodium-2-acrylamido-2-methylpropanesulphonate or sodium-3-acrylamido-3-methylbutanoate. (5) Synthesis and solution properties of associative acrylamido copolymers with pyrensulfonamide fluorescence labels. (6) Photophysical studies of the solution behavior of associative pyrenesulfonamide-labeled polyacrylamides. (7) Ampholytic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate with [2-(acrylamido)-2-methypropyl]trimethylammonium chloride. (8) Ampholytic terpolymers of acrylamide with sodium 2-acrylamido-2-methylpropanesulphoante and 2-acrylamido-2-methylpropanetrimethyl-ammonium chloride and (9) Polymer solution extensional behavior in porous media.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

Science.gov (United States)

Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

2016-01-27

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

Preservation of beech and spruce wood by allyl alcohol-based copolymers

International Nuclear Information System (INIS)

Solpan, Dilek; Gueven, Olgun

1999-01-01

Allyl alcohol (AA), acrylonitrile (AN), methyl methacrylate (MMA), monomers and monomer mixtures AA+AN, AA+MMA were used to conserve and consolidate Beech and Spruce. After impregnation, copolymerisation and polymerisation were accomplished by gamma irradiation. The fine structure of wood+polymer(copolymer) composites was investigated by Scanning Electron Microscopy (SEM). It was observed that copolymer obtained from AA+MMA monomer mixture showed the optimum compatibility. The compressional strength and Brinell Hardness Numbers determined for untreated and treated wood samples indicated that the mechanical strength of wood+copolymer composites was increased. It was found that the mechanical strength of the wood samples containing the AA+MMA copolymer was higher than the others. In the presence of P(AA/MMA), at highest conversion, the compressive strength perpendicular to the fibres in Beech and Spruce increased approximately 100 times. The water uptake capacity of wood+copolymer composites was observed to decrease by more than 50% relative to the original samples, and biodegradation did not take place

Strategies in protein sequencing and characterization: Multi-enzyme digestion coupled with alternate CID/ETD tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Nardiello, Donatella; Palermo, Carmen, E-mail: carmen.palermo@unifg.it; Natale, Anna; Quinto, Maurizio; Centonze, Diego

2015-01-07

Highlights: • Multi-enzyme digestion for protein sequencing and characterization by CID/ETD. • Simultaneous use of trypsin/chymotrypsin for the maximization of sequence. • Identification of PTMs, sequence variants and species-specific residues. • Increase of accuracy in sequence assignments by orthogonal fragmentation techniques. - Abstract: A strategy based on a simultaneous multi-enzyme digestion coupled with electron transfer dissociation (ETD) and collision-induced dissociation (CID) was developed for protein sequencing and characterization, as a valid alternative platform in ion-trap based proteomics. The effect of different proteolytic procedures using chymotrypsin, trypsin, a combination of both, and Lys-C, was carefully evaluated in terms of number of identified peptides, protein coverage, and score distribution. A systematic comparison between CID and ETD is shown for the analysis of peptides originating from the in-solution digestion of standard caseins. The best results were achieved with a trypsin/chymotrypsin mix combined with CID and ETD operating in alternating mode. A post-database search validation of MS/MS dataset was performed, then, the matched peptides were cross checked by the evaluation of ion scores, rank, number of experimental product ions, and their relative abundances in the MS/MS spectrum. By integrated CID/ETD experiments, high quality-spectra have been obtained, thus allowing a confirmation of spectral information and an increase of accuracy in peptide sequence assignments. Overlapping peptides, produced throughout the proteins, reduce the ambiguity in mapping modifications between natural variants and animal species, and allow the characterization of post translational modifications. The advantages of using the enzymatic mix trypsin/chymotrypsin were confirmed by the nanoLC and CID/ETD tandem mass spectrometry of goat milk proteins, previously separated by two-dimensional gel electrophoresis.

Multi-template synthesis of hierarchically porous carbon spheres with potential application in supercapacitors

NARCIS (Netherlands)

Zhou, Weizheng; Lin, Zhixing; Tong, Gangsheng; Stoyanov, Simeon D.; Yan, Deyue; Mai, Yiyong; Zhu, Xinyuan

2016-01-01

A new and simple multi-template approach towards hierarchical porous carbon (HPC) materials was reported. HPC spheres were prepared by using hierarchical silica capsules (HSCs) as the hard template and triblock copolymer Pluronic P123 as the soft template. Three types of pores were tunably

Molecular architecture of electroactive and biodegradable copolymers composed of polylactide and carboxyl-capped aniline trimer.

Science.gov (United States)

Guo, Baolin; Finne-Wistrand, Anna; Albertsson, Ann-Christine

2010-04-12

Two-, four-, and six-armed branched copolymers with electroactive and biodegradable properties were synthesized by coupling reactions between poly(l-lactides) (PLLAs) with different architecture and carboxyl-capped aniline trimer (CCAT). The aniline oligomer CCAT was prepared from amino-capped aniline trimer and succinic anhydride. FT-IR, NMR, and SEC analyses confirmed the structure of the branched copolymers. UV-vis spectra and cyclic voltammetry of CCAT and copolymer solution showed good electroactive properties, similar to those of polyaniline. The water contact angle of the PLLAs was the highest, followed by the undoped copolymer and the doped copolymers. The values of doped four-armed copolymers were 54-63 degrees . Thermal properties of the polymers were studied by DSC and TGA. The copolymers had better thermal stability than the pure PLLAs, and the T(g) between 48-58 degrees C and T(m) between 146-177 degrees C of the copolymers were lower than those of the pure PLLA counterparts. This kind of electroactive and biodegradable copolymer has a great potential for applications in cardiovascular or neuronal tissue engineering.

New thiol-responsive mono-cleavable block copolymer micelles labeled with single disulfides.

Science.gov (United States)

Sourkohi, Behnoush Khorsand; Schmidt, Rolf; Oh, Jung Kwon

2011-10-18

Thiol-responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono-cleavable block copolymers, ss-ABP(2)) were synthesized by atom transfer radical polymerization in the presence of a disulfide-labeled difunctional Br-initiator. These brush-like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and (1)H NMR results confirmed the synthesis of well-defined mono-cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self-assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL(-1). In response to reductive reactions, disulfides in thiol-responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller-sized assembled structures in water. Moreover, in a biomedical perspective, the mono-cleavable block copolymer micelles are not cytotoxic and thus biocompatible. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrophilic block copolymer-directed growth of lanthanum hydroxide nano-particles

Energy Technology Data Exchange (ETDEWEB)

Bouyer, F.; Sanson, N.; Gerardin, C. [Laboratoire de Materiaux Catalytiques et Catalyse en Chimie Organique, UMR 5618 CNRS-ENSCM-UM1, FR 1878, Institut Gerhardt, 34 - Montpellier (France); Destarac, M. [Centre de Recherches Rhodia Aubervilliers, 93 - Aubervilliers (France)

2006-03-15

Stable hairy lanthanum hydroxide nano-particles were synthesized in water by performing hydrolysis and condensation reactions of lanthanum cations in the presence of double hydrophilic poly-acrylic acid-b-polyacrylamide block copolymers (PAA-b-PAM). In the first step, the addition of asymmetric PAA-b-PAM copolymers (M{sub w,PAA} {<=} M{sub w,PAM}) to lanthanum salt solutions, both at pH = 5.5, induces the formation of monodispersed micellar aggregates, which are predominantly isotropic. The core of the hybrid aggregates is constituted of a lanthanum polyacrylate complex whose formation is due to bidentate coordination bonding between La{sup 3+} and acrylate groups, as shown by ATR-FTIR experiments and pH measurements. The size of the micellar aggregates depends on the molecular weight of the copolymer but is independent of the copolymer to metal ratio in solution. In the second step, the hydrolysis of lanthanum ions is induced by addition of a strong base such as sodium hydroxide. Either flocculated suspensions or stable anisotropic or spherical nano-particles of lanthanum hydrolysis products were obtained depending on the metal complexation ratio [acrylate]/[La]. The variation of that parameter also enables the control of the size of the core-corona nano-particles obtained by lanthanum hydroxylation. The asymmetry degree of the copolymer was shown to influence both the size and the shape of the particles. Elongated particles with a high aspect ratio, up to 10, were obtained with very asymmetric copolymers (M{sub w,PAM}/M{sub w,PAA}{>=}10) while shorter rice grain-like particles were obtained with a less asymmetric copolymer. The asymmetry degree also influences the value of the critical metal complexation degree required to obtain stable colloidal suspensions of polymer-stabilized lanthanum hydroxide. (authors)

Self-oscillating AB diblock copolymer developed by post modification strategy

Energy Technology Data Exchange (ETDEWEB)

Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota; Yoshida, Ryo, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Shibayama, Mitsuhiro [Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwano-ha, Kashiwa, Chiba 277-8581 (Japan)

2015-06-15

We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle at reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.

Temperature-Responsive Biocompatible Copolymers Incorporating Hyperbranched Polyglycerols for Adjustable Functionality

Directory of Open Access Journals (Sweden)

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.

Multiblock copolymers synthesized in aqueous dispersions using multifunctional RAFT agents

NARCIS (Netherlands)

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

Rapid Ordering in "Wet Brush" Block Copolymer/Homopolymer Ternary Blends.

Science.gov (United States)

Doerk, Gregory S; Yager, Kevin G

2017-12-26

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the "wet brush" regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved within minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. These results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order-disorder transition through low molecular weight homopolymer blending.

Multi-qubit compensation sequences

International Nuclear Information System (INIS)

Tomita, Y; Merrill, J T; Brown, K R

2010-01-01

The Hamiltonian control of n qubits requires precision control of both the strength and timing of interactions. Compensation pulses relax the precision requirements by reducing unknown but systematic errors. Using composite pulse techniques designed for single qubits, we show that systematic errors for n-qubit systems can be corrected to arbitrary accuracy given either two non-commuting control Hamiltonians with identical systematic errors or one error-free control Hamiltonian. We also examine composite pulses in the context of quantum computers controlled by two-qubit interactions. For quantum computers based on the XY interaction, single-qubit composite pulse sequences naturally correct systematic errors. For quantum computers based on the Heisenberg or exchange interaction, the composite pulse sequences reduce the logical single-qubit gate errors but increase the errors for logical two-qubit gates.

Oxidation effect on templating of metal oxide nanoparticles within block copolymers

International Nuclear Information System (INIS)

Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

2009-01-01

Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

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

Directory of Open Access Journals (Sweden)

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.

PredPPCrys: accurate prediction of sequence cloning, protein production, purification and crystallization propensity from protein sequences using multi-step heterogeneous feature fusion and selection.

Directory of Open Access Journals (Sweden)

Huilin Wang

Full Text Available X-ray crystallography is the primary approach to solve the three-dimensional structure of a protein. However, a major bottleneck of this method is the failure of multi-step experimental procedures to yield diffraction-quality crystals, including sequence cloning, protein material production, purification, crystallization and ultimately, structural determination. Accordingly, prediction of the propensity of a protein to successfully undergo these experimental procedures based on the protein sequence may help narrow down laborious experimental efforts and facilitate target selection. A number of bioinformatics methods based on protein sequence information have been developed for this purpose. However, our knowledge on the important determinants of propensity for a protein sequence to produce high diffraction-quality crystals remains largely incomplete. In practice, most of the existing methods display poorer performance when evaluated on larger and updated datasets. To address this problem, we constructed an up-to-date dataset as the benchmark, and subsequently developed a new approach termed 'PredPPCrys' using the support vector machine (SVM. Using a comprehensive set of multifaceted sequence-derived features in combination with a novel multi-step feature selection strategy, we identified and characterized the relative importance and contribution of each feature type to the prediction performance of five individual experimental steps required for successful crystallization. The resulting optimal candidate features were used as inputs to build the first-level SVM predictor (PredPPCrys I. Next, prediction outputs of PredPPCrys I were used as the input to build second-level SVM classifiers (PredPPCrys II, which led to significantly enhanced prediction performance. Benchmarking experiments indicated that our PredPPCrys method outperforms most existing procedures on both up-to-date and previous datasets. In addition, the predicted crystallization

Multi-objective optimization of linear multi-state multiple sliding window system

International Nuclear Information System (INIS)

Konak, Abdullah; Kulturel-Konak, Sadan; Levitin, Gregory

2012-01-01

This paper considers the optimal element sequencing in a linear multi-state multiple sliding window system that consists of n linearly ordered multi-state elements. Each multi-state element can have different states: from complete failure up to perfect functioning. A performance rate is associated with each state. The failure of type i in the system occurs if for any i (1≤i≤I) the cumulative performance of any r i consecutive elements is lower than w i . The element sequence strongly affects the probability of any type of system failure. The sequence that minimizes the probability of certain type of failure can provide high probability of other types of failures. Therefore the optimization problem for the multiple sliding window system is essentially multi-objective. The paper formulates and solves the multi-objective optimization problem for the multiple sliding window systems. A multi-objective Genetic Algorithm is used as the optimization engine. Illustrative examples are presented.

Variational analysis of regular mappings theory and applications

CERN Document Server

Ioffe, Alexander D

2017-01-01

This monograph offers the first systematic account of (metric) regularity theory in variational analysis. It presents new developments alongside classical results and demonstrates the power of the theory through applications to various problems in analysis and optimization theory. The origins of metric regularity theory can be traced back to a series of fundamental ideas and results of nonlinear functional analysis and global analysis centered around problems of existence and stability of solutions of nonlinear equations. In variational analysis, regularity theory goes far beyond the classical setting and is also concerned with non-differentiable and multi-valued operators. The present volume explores all basic aspects of the theory, from the most general problems for mappings between metric spaces to those connected with fairly concrete and important classes of operators acting in Banach and finite dimensional spaces. Written by a leading expert in the field, the book covers new and powerful techniques, whic...

Image degradation characteristics and restoration based on regularization for diffractive imaging

Science.gov (United States)

Zhi, Xiyang; Jiang, Shikai; Zhang, Wei; Wang, Dawei; Li, Yun

2017-11-01

The diffractive membrane optical imaging system is an important development trend of ultra large aperture and lightweight space camera. However, related investigations on physics-based diffractive imaging degradation characteristics and corresponding image restoration methods are less studied. In this paper, the model of image quality degradation for the diffraction imaging system is first deduced mathematically based on diffraction theory and then the degradation characteristics are analyzed. On this basis, a novel regularization model of image restoration that contains multiple prior constraints is established. After that, the solving approach of the equation with the multi-norm coexistence and multi-regularization parameters (prior's parameters) is presented. Subsequently, the space-variant PSF image restoration method for large aperture diffractive imaging system is proposed combined with block idea of isoplanatic region. Experimentally, the proposed algorithm demonstrates its capacity to achieve multi-objective improvement including MTF enhancing, dispersion correcting, noise and artifact suppressing as well as image's detail preserving, and produce satisfactory visual quality. This can provide scientific basis for applications and possesses potential application prospects on future space applications of diffractive membrane imaging technology.

Spanning k-ended trees of 3-regular connected graphs

Directory of Open Access Journals (Sweden)

Hamed Ghasemian Zoeram

2017-10-01

Full Text Available A vertex of degree one is called an end-vertex and the set of end-vertices of G is denoted by End(G. For a positive integer k, a tree T be called k-ended tree if $|End(T| \\leq k$. In this paper, we obtain sufficient conditions for spanning k-trees of 3-regular connected graphs. We give a construction sequence of graphs satisfying the condition. At the end, we present a conjecture about spanning k-ended trees of 3-regular connected graphs.

Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

OpenAIRE

Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

2015-01-01

We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affiniti...

Distributions of chain ends and junction points in ordered block copolymers

International Nuclear Information System (INIS)

Mayes, A.M.; Johnson, R.D.; Russell, T.P.; Smith, S.D.; Satija, S.K.; Majkrzak, C.F.

1993-01-01

Chain configurations in ordered symmetric poly(styrene-b-methyl methacrylate) diblock copolymers were examined by neutron reflectively. In a thin-film geometry the copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers were synthesized with small fractions of deuterated segments at either the chain ends or centers. This selective labeling permitted characterization of the spatial distribution of chain ends and junction points normal to the plane of the film. From the reflectivity analysis, the junction points are found to be confined to the PS/PMMA interfacial regions. The chain ends, however, are well distributed through their respective domains, exhibiting only a weak maximum in concentration at the center of the domains

Protein resistance of dextran and dextran-PEG copolymer films

Science.gov (United States)

Kozak, Darby; Chen, Annie; Bax, Jacinda; Trau, Matt

2011-01-01

The protein resistance of dextran and dextran-poly(ethylene glycol) (PEG) copolymer films was examined on an organosilica particle-based assay support. Comb-branched dextran-PEG copolymer films were synthesized in a two step process using the organosilica particle as a solid synthetic support. Particles modified with increasing amounts (0.1-1.2 mg m−2) of three molecular weights (10 000, 66 900, 400 000 g mol−1) of dextran were found to form relatively poor protein-resistant films compared to dextran-PEG copolymers and previously studied PEG films. The efficacy of the antifouling polymer films was found to be dependent on the grafted amount and its composition, with PEG layers being the most efficient, followed by dextran-PEG copolymers, and dextran alone being the least efficient. Immunoglobulin gamma (IgG) adsorption decreased from ~ 5 to 0.5 mg m−2 with increasing amounts of grafted dextran, but bovine serum albumin (BSA) adsorption increased above monolayer coverage (to ~2 mg m−2) indicating ternary adsorption of the smaller protein within the dextran layer. PMID:21614699

Features of radiation chemical processes in ethylene-styrene copolymers

International Nuclear Information System (INIS)

Leshchenko, S.S.; Mal'tseva, A.P.; Iskakov, L.I.; Karpov, V.L.

1976-01-01

A study was made of statistical copolymers of ethylene with styrene to determine their structure and properties and radio-chemical transformations. The styrene content of the copolymers ranged from 1 to 85 mole%. The investigation covered non-irradiated copolymers and those irradiated with doses of 1-1000Mrad at room temperature and at liquid nitrogen temperature. It is shown that styrene units present in the CES inhibited all radio-chemical processes compared with PE irradiated under similar conditions. It is suggested that the radiation resistance of CES with styrene contents up to 10 mole % increases in the course of irradiation as a result of the formation of structures with a high degree of conjugation which are more capable of scattering absorbed energy than in the case of phenyl rings by themselves. The most promising of the CES examined is the one with a styrene content of 5 mole %. The mechanical properties of this copolymer are similar to those of PE, and its radiation resistance rises under service conditions in the presence of ionizing radiation

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

Institute of Scientific and Technical Information of China (English)

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.

Segmentation of myocardial perfusion MR sequences with multi-band Active Appearance Models driven by spatial and temporal features

NARCIS (Netherlands)

Baka, N.; Milles, J.; Hendriks, E.A.; Suinesiaputra, A.; Jerosh Herold, M.; Reiber, J.H.C.; Lelieveldt, B.P.F.

2008-01-01

This work investigates knowledge driven segmentation of cardiac MR perfusion sequences. We build upon previous work on multi-band AAMs to integrate into the segmentation both spatial priors about myocardial shape as well as temporal priors about characteristic perfusion patterns. Different temporal

Regularized rare variant enrichment analysis for case-control exome sequencing data.

Science.gov (United States)

Larson, Nicholas B; Schaid, Daniel J

2014-02-01

Rare variants have recently garnered an immense amount of attention in genetic association analysis. However, unlike methods traditionally used for single marker analysis in GWAS, rare variant analysis often requires some method of aggregation, since single marker approaches are poorly powered for typical sequencing study sample sizes. Advancements in sequencing technologies have rendered next-generation sequencing platforms a realistic alternative to traditional genotyping arrays. Exome sequencing in particular not only provides base-level resolution of genetic coding regions, but also a natural paradigm for aggregation via genes and exons. Here, we propose the use of penalized regression in combination with variant aggregation measures to identify rare variant enrichment in exome sequencing data. In contrast to marginal gene-level testing, we simultaneously evaluate the effects of rare variants in multiple genes, focusing on gene-based least absolute shrinkage and selection operator (LASSO) and exon-based sparse group LASSO models. By using gene membership as a grouping variable, the sparse group LASSO can be used as a gene-centric analysis of rare variants while also providing a penalized approach toward identifying specific regions of interest. We apply extensive simulations to evaluate the performance of these approaches with respect to specificity and sensitivity, comparing these results to multiple competing marginal testing methods. Finally, we discuss our findings and outline future research. © 2013 WILEY PERIODICALS, INC.

nanocomposites of PA6/ABS blends compatibilized with styrene-maleic anhydride copolymer

International Nuclear Information System (INIS)

Oliveira, Amanda D. de; Pessan, Luiz A.

2009-01-01

To achieve a balance between stiffness and toughness, ternary nanocomposites based on blends of polyamide 6 (PA6) and acrylonitrile-butadiene-styrene (ABS) were prepared by the melt intercalation using the organoclay Cloisite R 30B (OMMT) and the styrene-maleic anhydride copolymer (SMA) as compatibilizer. Four blending sequences were used to prepare studied systems and their mechanical properties studied through the Young's modulus and notched Izod impact. It was observed that the materials prepared by all blending sequences studied showed an increase in the Young's modulus compared to the neat PA6. However, a decrease in the toughness was observed for the systems with the addition of the organoclay. The DRX results showed an intercalated structure for the some systems that used ABS in their compositions. HDT measurements of the nanocomposites showed an increase in this property compared to the neat PA6. The use of nanoclay lead to a reinforcement of the polymeric matrix. (author)

Carboxylic Terminated Thermo-Responsive Copolymer Hydrogel and Improvement in Peptide Release Profile

Directory of Open Access Journals (Sweden)

Zi-Kun Rao

2018-02-01

Full Text Available To improve the release profile of peptide drugs, thermos-responsive triblock copolymer poly (ε-caprolactone-co-p-dioxanone-b-poly (ethylene glycol-b-poly (ε-caprolactone-co-p-dioxanone (PECP was prepared and end capped by succinic anhydride to give its carboxylic terminated derivative. Both PCEP block copolymer and its end group modified derivative showed temperature-dependent reversible sol-gel transition in water. The carboxylic end group could significantly decrease the sol-gel transition temperature by nearly 10 °C and strengthen the gel due to enhanced intermolecular force among triblock copolymer chains. Furthermore, compared with the original PECP triblock copolymer, HOOC–PECP–COOH copolymer displayed a retarded and sustained release profile for leuprorelin acetate over one month while effectively avoiding the initial burst. The controlled release was believed to be related to the formation of conjugated copolymer-peptide pair by ionic interaction and enhanced solubility of drug molecules into the hydrophobic domains of the hydrogel. Therefore, carboxyl terminated HOOC–PECP–COOH hydrogel was a promising and well-exhibited sustained release carrier for peptide drugs with the advantage of being able to develop injectable formulation by simple mixing.

Block copolymer/homopolymer dual-layer hollow fiber membranes

KAUST Repository

Hilke, Roland

2014-12-01

We manufactured the first time block copolymer dual-layer hollow fiber membranes and dual layer flat sheet membranes manufactured by double solution casting and phase inversion in water. The support porous layer was based on polystyrene and the selective layer with isopores was formed by micelle assembly of polystyrene-. b-poly-4-vinyl pyridine. The dual layers had an excellent interfacial adhesion and pore interconnectivity. The dual membranes showed pH response behavior like single layer block copolymer membranes with a low flux for pH values less than 3, a fast increase between pH4 and pH6 and a constant high flux level for pH values above 7. The dry/wet spinning process was optimized to produce dual layer hollow fiber membranes with polystyrene internal support layer and a shell block copolymer selective layer.

Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer (Postprint)

National Research Council Canada - National Science Library

Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man

2006-01-01

...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors

KAUST Repository

Kanimozhi, Catherine K.

2012-10-10

In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to ∼1100 nm) and field-effect electron mobility values of >1 cm 2 V -1 s -1. The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics. © 2012 American Chemical Society.

Study of the mechanical behavior of thermo reversible gels of PS-b-poly(ethylene/butylene)-b-PS triblock copolymers in a selective solvent for the middle block of the copolymer

International Nuclear Information System (INIS)

Hernaez, E.; Inchausti, I.; Quintana, J. R.; Katime, I.

2001-01-01

The thermo reversible gelation of three triblock copolymers polystyrene-b-poly(ethylene/butylene)-b-polystyrene, with different molar mass and a similar chemical composition, in n-octane was studied. The solvent is selective for the middle poly(ethylene/butylene) block of the copolymers. the influence of the molar mass of the three copolymers on the gelation and on the mechanical properties of the gels was analysed. The sol-gel transition temperatures. T g el have been determined and they increase with the copolymer concentration and the copolymer molar mass. On the other land, the mechanical properties of the different gels were examined through oscillatory shear and compressive stress relaxation measurements. The concentration dependence of the elastic storage modules, G' for the three copolymer studied fit a sole straight line in a double-logarithmic scale and its slope (2.22) is close to that expected for systems in good solvents (2.25). As the temperature is near to the sol-gel transition temperate, the elastic modulus are smaller and the relaxation rates are higher. (Author) 12 refs

Ordering phenomena in ABA triblock copolymer gels

DEFF Research Database (Denmark)

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...

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

International Nuclear Information System (INIS)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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.

Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers.

Science.gov (United States)

Mok, M M; Kim, J; Marrou, S R; Torkelson, J M

2010-03-01

Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T (g)) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T (g) breadths were observed to increase from approximately 17( degrees ) C in styrene-rich cases to almost 30( degrees ) C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4x10(-4) K-1 in PS to 3.5x10(-4) K-1 in PnBMA. The first characterization of block copolymer T (g) 's and T (g) breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T (g) 's expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T (g) breadths of 69- 71( degrees ) C , factors of 4-5 larger than the T (g) breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T (g) breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected

Infrared and ultraviolet spectroscopic studies of low-temperature radiolysis of ethylene - styrene copolymers

International Nuclear Information System (INIS)

Mal'tseva, A.P.; Golikov, V.P.; Leshchenko, S.S.; Karpov, V.L.

1977-01-01

Certain features of low-temperature radiolysis of statistic ethylene-styrene copolymers have been studied by infrared and ultraviolet spectroscopy. It is shown that the nature of the accumulation and decay of trans-vinylene, vinyl and vinylidene double bonds in an ethylene-styrene copolymer is essentially influenced by both the dose absorbed and copolymer composition. A suggestion is made that the ethylene-styrene copolymer is formed when structures are irradiated containing double bonds conjugated with the phenyl rings of styrene groups - which more effectively dissipate the absorbed energy than solitary phenyl rings

PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

2008-01-01

The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface

International Nuclear Information System (INIS)

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.

A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface.

Science.gov (United States)

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.

Two-Dimensional Liquid Chromatography Analysis of Polystyrene/Polybutadiene Block Copolymers.

Science.gov (United States)

Lee, Sanghoon; Choi, Heejae; Chang, Taihyun; Staal, Bastiaan

2018-05-15

A detailed characterization of a commercial polystyrene/polybutadiene block copolymer material (Styrolux) was carried out using two-dimensional liquid chromatography (2D-LC). The Styrolux is prepared by statistical linking reaction of two different polystyrene- block-polybutadienyl anion precursors with a multivalent linking agent. Therefore, it is a mixture of a number of branched block copolymers different in molecular weight, composition, and chain architecture. While individual LC analysis, including size exclusion chromatography, interaction chromatography, or liquid chromatography at critical condition, is not good enough to resolve all the polymer species, 2D-LC separations coupling two chromatography methods were able to resolve all polymer species present in the sample; at least 13 block copolymer species and a homopolystyrene blended. Four different 2D-LC analyses combining a different pair of two LC methods provide their characteristic separation results. The separation characteristics of the 2D-LC separations are compared to elucidate the elution characteristics of the block copolymer species.

Synthesis of graft copolymers onto starch and its semiconducting properties

Directory of Open Access Journals (Sweden)

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

Fast assembly of ordered block copolymer nanostructures through microwave annealing.

Science.gov (United States)

Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

2010-11-23

Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy.

Molecular weight and its distribution of tetrafluoroethylene and propylene copolymer

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Okamoto, Jiro; Yamaguchi, Koichi.

1978-04-01

In comparison of molecular structure of tetrafluoroethylene and propylene copolymer produced by radiation and chemical initiators respectively, both were fractionated by elution method and fine structure was examined. For the fractionated sample by radiation, the relation between molecular weight anti Mn and intrinsic viscosity ( eta] is ( eta] = 3.97 x 10 -4 anti Mnsup(0.630) The result is not in agreement with that of the unfractionated sample by radiation, and similar to those of samples by chemical initiators. There is no difference, however, in the elution method of GPC between both these copolymers; the elution behavior agrees with that of standard polystyrene. Long chain branching thus exists little in the copolymer of tetrafluoroethylene and propylene. To reveal the relations between reaction conditions and molecular weight and its distribution of the copolymer produced by flow apparatus, the molecular weight distribution was measured by GPC. The method of analysis could evaluate molecular weight distribution changing constantly. (auth.)

Making a difference? A comparison between multi-sensory and regular storytelling for persons with profound intellectual and multiple disabilities.

Science.gov (United States)

Ten Brug, A; Van der Putten, A A J; Penne, A; Maes, B; Vlaskamp, C

2016-11-01

Multi-sensory storytelling (MSST) was developed to include persons with profound intellectual and multiple disabilities in storytelling culture. In order to increase the listeners' attention, MSST stories are individualised and use multiple sensory stimuli to support the verbal text. In order to determine the value of MSST, this study compared listeners' attention under two conditions: (1) being read MSST books and (2) being read regular stories. A non-randomised control study was executed in which the intervention group read MSST books (n = 45) and a comparison group (n = 31) read regular books. Books were read 10 times during a 5-week period. The 1st, 5th and 10th storytelling sessions were recorded on video in both groups, and the percentage of attention directed to the book and/or stimuli and to the storyteller was scored by a trained and independent rater. Two repeated measure analyses (with the storytelling condition as a between-subject factor and the three measurements as factor) were performed to determine the difference between the groups in terms of attention directed to the book/stimuli (first analysis) and storyteller (second analysis). A further analysis established whether the level of attention changed between the reading sessions and whether there was an interaction effect between the repetition of the book and the storytelling condition. The attention directed to the book and/or the stimuli was significantly higher in the MSST group than in the comparison group. No significant difference between the two groups was found in the attention directed to the storyteller. For MSST stories, most attention was observed during the fifth reading session, while for regular stories, the fifth session gained least attentiveness from the listener. The persons with profound intellectual and multiple disabilities paid more attention to the book and/or stimuli in the MSST condition compared with the regular story telling group. Being more attentive towards

Top-down attention affects sequential regularity representation in the human visual system.

Science.gov (United States)

Kimura, Motohiro; Widmann, Andreas; Schröger, Erich

2010-08-01

Recent neuroscience studies using visual mismatch negativity (visual MMN), an event-related brain potential (ERP) index of memory-mismatch processes in the visual sensory system, have shown that although sequential regularities embedded in successive visual stimuli can be automatically represented in the visual sensory system, an existence of sequential regularity itself does not guarantee that the sequential regularity will be automatically represented. In the present study, we investigated the effects of top-down attention on sequential regularity representation in the visual sensory system. Our results showed that a sequential regularity (SSSSD) embedded in a modified oddball sequence where infrequent deviant (D) and frequent standard stimuli (S) differing in luminance were regularly presented (SSSSDSSSSDSSSSD...) was represented in the visual sensory system only when participants attended the sequential regularity in luminance, but not when participants ignored the stimuli or simply attended the dimension of luminance per se. This suggests that top-down attention affects sequential regularity representation in the visual sensory system and that top-down attention is a prerequisite for particular sequential regularities to be represented. Copyright 2010 Elsevier B.V. All rights reserved.

Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

KAUST Repository

Peinemann, Klaus-Viktor; Karunakaran, Madhavan

2015-01-01

Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

KAUST Repository

Peinemann, Klaus-Viktor

2015-04-16

Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

Energy Technology Data Exchange (ETDEWEB)

Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo, E-mail: zghu@htu.cn

2014-10-01

Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10{sup −4} mg/mL and 3.9 × 10{sup −5} mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability.

Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

International Nuclear Information System (INIS)

Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

2014-01-01

Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by 1 H nuclear magnetic resonance ( 1 H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10 −4 mg/mL and 3.9 × 10 −5 mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability

Synthesis of biodegradable and electroactive multiblock polylactide and aniline pentamer copolymer for tissue engineering applications.

Science.gov (United States)

Huang, Lihong; Zhuang, Xiuli; Hu, Jun; Lang, Le; Zhang, Peibiao; Wang, Yu; Chen, Xuesi; Wei, Yen; Jing, Xiabin

2008-03-01

To obtain one biodegradable and electroactive polymer as the scaffold for tissue engineering, the multiblock copolymer PLAAP was designed and synthesized with the condensation polymerization of hydroxyl-capped poly( l-lactide) (PLA) and carboxyl-capped aniline pentamer (AP). The PLAAP copolymer exhibited excellent electroactivity, solubility, and biodegradability. At the same time, as one scaffold material, PLAAP copolymer possesses certain mechanical properties with the tensile strength of 3 MPa, tensile Young 's modulus of 32 MPa, and breaking elongation rate of 95%. We systematically studied the compatibility of PLAAP copolymer in vitro and proved that the electroactive PLAAP copolymer was innocuous, biocompatible, and helpful for the adhesion and proliferation of rat C6 cells. Moreover, the PLAAP copolymer stimulated by electrical signals was demonstrated as accelerating the differentiation of rat neuronal pheochromocytoma PC-12 cells. This biodegradable and electroactive PLAAP copolymer thus possessed the properties in favor of the long-time application in vivo as nerve repair scaffold materials in tissue engineering.

Novel Pentablock Copolymers as Thermosensitive Self-Assembling Micelles for Ocular Drug Delivery

Directory of Open Access Journals (Sweden)

Mitra Alami-Milani

2017-04-01

Full Text Available Many studies have focused on how drugs are formulated in the sol state at room temperature leading to the formation of in situ gel at eye temperature to provide a controlled drug release. Stimuli-responsive block copolymer hydrogels possess several advantages including uncomplicated drug formulation and ease of application, no organic solvent, protective environment for drugs, site-specificity, prolonged and localized drug delivery, lower systemic toxicity, and capability to deliver both hydrophobic and hydrophilic drugs. Self-assembling block copolymers (such as diblock, triblock, and pentablock copolymers with large solubility variation between hydrophilic and hydrophobic segments are capable of making temperature-dependent micellar assembles, and with further increase in the temperature, of jellifying due to micellar aggregation. In general, molecular weight, hydrophobicity, and block arrangement have a significant effect on polymer crystallinity, micelle size, and in vitro drug release profile. The limitations of creature triblock copolymers as initial burst release can be largely avoided using micelles made of pentablock copolymers. Moreover, formulations based on pentablock copolymers can sustain drug release for a longer time. The present study aims to provide a concise overview of the initial and recent progresses in the design of hydrogel-based ocular drug delivery systems.

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

Directory of Open Access Journals (Sweden)

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.

A novel family of sequence-specific endoribonucleases associated with the clustered regularly interspaced short palindromic repeats.

Science.gov (United States)

Beloglazova, Natalia; Brown, Greg; Zimmerman, Matthew D; Proudfoot, Michael; Makarova, Kira S; Kudritska, Marina; Kochinyan, Samvel; Wang, Shuren; Chruszcz, Maksymilian; Minor, Wladek; Koonin, Eugene V; Edwards, Aled M; Savchenko, Alexei; Yakunin, Alexander F

2008-07-18

Clustered regularly interspaced short palindromic repeats (CRISPRs) together with the associated CAS proteins protect microbial cells from invasion by foreign genetic elements using presently unknown molecular mechanisms. All CRISPR systems contain proteins of the CAS2 family, suggesting that these uncharacterized proteins play a central role in this process. Here we show that the CAS2 proteins represent a novel family of endoribonucleases. Six purified CAS2 proteins from diverse organisms cleaved single-stranded RNAs preferentially within U-rich regions. A representative CAS2 enzyme, SSO1404 from Sulfolobus solfataricus, cleaved the phosphodiester linkage on the 3'-side and generated 5'-phosphate- and 3'-hydroxyl-terminated oligonucleotides. The crystal structure of SSO1404 was solved at 1.6A resolution revealing the first ribonuclease with a ferredoxin-like fold. Mutagenesis of SSO1404 identified six residues (Tyr-9, Asp-10, Arg-17, Arg-19, Arg-31, and Phe-37) that are important for enzymatic activity and suggested that Asp-10 might be the principal catalytic residue. Thus, CAS2 proteins are sequence-specific endoribonucleases, and we propose that their role in the CRISPR-mediated anti-phage defense might involve degradation of phage or cellular mRNAs.

21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer.

Science.gov (United States)

2010-04-01

... methacrylate copolymer identified in this section may be safely used as an article or component of articles... monomer content of the finished copolymer articles is not more than 11 parts per million as determined by... available from the Center for Food Safety and Applied Nutrition (HFS-200), Food and Drug Administration...

Investigation of some copolymers based on acrylic salts as circulation loss control agents

Directory of Open Access Journals (Sweden)

Ahmed Mohamed Alsabagh

2013-12-01

The prepared copolymers were investigated as loss circulation control materials by measuring different filtration parameters such as; spurt loss, fluid loss and permeability plugging tester value according to the American Petroleum Institute (API standard. From the obtained data, it was found that the 0.6% from the poly[PA-co-AM](0.4:0.6 exhibited the best results of the filtration parameters among the other copolymers. At the same time all the studied copolymers enhanced the rheological properties of the drilling mud. These results were discussed on the light of the swelling capacity of the copolymers.

Diverse Regular Employees and Non-regular Employment (Japanese)

OpenAIRE

MORISHIMA Motohiro

2011-01-01

Currently there are high expectations for the introduction of policies related to diverse regular employees. These policies are a response to the problem of disparities between regular and non-regular employees (part-time, temporary, contract and other non-regular employees) and will make it more likely that workers can balance work and their private lives while companies benefit from the advantages of regular employment. In this paper, I look at two issues that underlie this discussion. The ...

Synthesis, characterization and antimicrobial activity of important heterocyclic acrylic copolymers

Directory of Open Access Journals (Sweden)

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.

Highly fluorinated comb-shaped copolymer as proton exchange membranes (PEMs): Fuel cell performance

Energy Technology Data Exchange (ETDEWEB)

Kim, Dae Sik; Guiver, Michael D.; Ding, Jianfu [Institute for Chemical Process and Environmental Technology, National Research Council, 1200 Montreal Road, Ottawa, Ontario K1A 0R6 (Canada); Kim, Yu.Seung; Pivovar, Bryan S. [Materials Physics and Applications, Sensors and Electrochemical Devices Group, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

2008-07-15

The fuel cell performance (DMFC and H{sub 2}/air) of highly fluorinated comb-shaped copolymer is reported. The initial performance of membrane electrode assemblies (MEAs) fabricated from comb-shaped copolymer containing a side-chain weight fraction of 22% are compared with those derived from Nafion and sulfonated polysulfone (BPSH-35) under DMFC conditions. The low water uptake of comb copolymer enabled an increase in proton exchange site concentrations in the hydrated polymer, which is a desirable membrane property for DMFC application. The comb-shaped copolymer architecture induces phase separated morphology between the hydrophobic fluoroaromatic backbone and the polysulfonic acid side chains. The initial performance of the MEAs using BPSH-35 and Comb 22 copolymer were comparable and higher than that of the Nafion MEA at all methanol concentrations. For example, the power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 0.5 M methanol was 145 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 136 mW cm{sup -2}. The power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 2.0 M methanol was 144.5 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 143 mW cm{sup -2}. (author)

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

KAUST Repository

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.

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

KAUST Repository

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.

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

Science.gov (United States)

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).

Ionic Liquids As Self-Assembly Guide for the Formation of Nanostructured Block Copolymer Membranes

KAUST Repository

Madhavan, Poornima

2015-04-30

Nanostructured block copolymer membranes were manufactured by water induced phase inversion, using ionic liquids (ILs) as cosolvents. The effect of ionic liquids on the morphology was investigated, by using polystyrene-b-poly(4-vinyl pyridine) (PS-b-PV4P) diblock as membrane copolymer matrix and imidazolium and pyridinium based ILs. The effect of IL concentration and chemical composition was evident with particular interaction with P4VP blocks. The order of block copolymer/ILs solutions previous to the membrane casting was confirmed by cryo scanning electron microscopy and the morphologies of the manufactured nanostructured membranes were characterized by transmission and scanning electron microscopy. Non-protic ionic liquids facilitate the formation of hexagonal nanoporous block copolymer structure, while protic ILs led to a lamella-structured membrane. The rheology of the IL/block copolymer solutions was investigated, evaluating the storage and loss moduli. Most membranes prepared with ionic liquid had higher water flux than pure block copolymer membranes without additives.

Nanoporous Crosslinked Polyisoprene from Polyisoprene-Polydimethylsiloxane Block Copolymer

DEFF Research Database (Denmark)

Hansen, Michael Steffen; Vigild, Martin Etchells; Berg, Rolf Henrik

2004-01-01

The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride or tetrabut......The polyisoprene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) diblock copolymer with 0.68 volume fraction of PI was tightly crosslinked with dicumylperoxide. The PDMS part of the obtained glassy material was subsequently quantitatively etched with anhydrous hydrogen fluoride...

Morphology evolution of PS-b-PDMS block copolymer and its hierarchical directed self-assembly on block copolymer templates

DEFF Research Database (Denmark)

Rasappa, Sozaraj; Schulte, Lars; Borah, Dipu

2018-01-01

Cylinder-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS, 27.2k-b-11.7k, SD39) block copolymer having a total molecular weight of 39 kg mol−1 was exploited to achieve in-plane morphologies of lines, dots and antidots. Brush-free self-assembly of the SD39 on silicon substrates was invest...... substrates provides a simplified method for surface nanopatterning, templated growth of nanomaterials and nanofabrication....... the pattern into the underlying substrate. Directed self-assembly and hierarchical directed self-assembly on block copolymer templates for confinement of dots was successfully demonstrated. The strategy for achieving multiple morphologies using one BCP by mere choice of the annealing solvents on unmodified...

Chimeric mitochondrial peptides from contiguous regular and swinger RNA.

Science.gov (United States)

Seligmann, Hervé

2016-01-01

Previous mass spectrometry analyses described human mitochondrial peptides entirely translated from swinger RNAs, RNAs where polymerization systematically exchanged nucleotides. Exchanges follow one among 23 bijective transformation rules, nine symmetric exchanges (X ↔ Y, e.g. A ↔ C) and fourteen asymmetric exchanges (X → Y → Z → X, e.g. A → C → G → A), multiplying by 24 DNA's protein coding potential. Abrupt switches from regular to swinger polymerization produce chimeric RNAs. Here, human mitochondrial proteomic analyses assuming abrupt switches between regular and swinger transcriptions, detect chimeric peptides, encoded by part regular, part swinger RNA. Contiguous regular- and swinger-encoded residues within single peptides are stronger evidence for translation of swinger RNA than previously detected, entirely swinger-encoded peptides: regular parts are positive controls matched with contiguous swinger parts, increasing confidence in results. Chimeric peptides are 200 × rarer than swinger peptides (3/100,000 versus 6/1000). Among 186 peptides with > 8 residues for each regular and swinger parts, regular parts of eleven chimeric peptides correspond to six among the thirteen recognized, mitochondrial protein-coding genes. Chimeric peptides matching partly regular proteins are rarer and less expressed than chimeric peptides matching non-coding sequences, suggesting targeted degradation of misfolded proteins. Present results strengthen hypotheses that the short mitogenome encodes far more proteins than hitherto assumed. Entirely swinger-encoded proteins could exist.

Supramolecular Cross-Links in Poly(alkyl methacrylate) Copolymers and Their Impact on the Mechanical and Reversible Adhesive Properties.

Science.gov (United States)

Heinzmann, Christian; Salz, Ulrich; Moszner, Norbert; Fiore, Gina L; Weder, Christoph

2015-06-24

Hydrogen-bonded, side-chain-functionalized supramolecular poly(alkyl methacrylate)s were investigated as light- and temperature-responsive reversible adhesives that are useful for bonding and debonding on demand applications. Here, 2-hydroxyethyl methacrylate (HEMA) was functionalized with 2-ureido-4[1H]pyrimidinone (UPy) via a hexamethylenediisocyanate (HMDI) linker, to create a monomer (UPy-HMDI-HEMA) that serves to form supramolecular cross-links by way of forming quadruple hydrogen bonded dimers. UPy-HMDI-HEMA was copolymerized with either hexyl methacrylate or butyl methacrylate to create copolymers comprising 2.5, 5, or 10 mol % of the cross-linker. The mechanical properties of all (co)polymers were investigated with stress-strain experiments and dynamic mechanical analysis. Furthermore, the adhesive properties were studied at temperatures between 20 and 60 °C by testing single lap joints formed with stainless steel substrates. It was found that increasing the concentration of the UPy-HMDI-HEMA cross-linker leads to improved mechanical and adhesive properties at elevated temperatures. Concurrently, the reversibility of the bond formation remained unaffected, where rebonded samples displayed the same adhesive strength as regularly bonded samples. Debonding on demand abilities were also tested exemplarily for one copolymer, which for light-induced debonding experiments was blended with a UV-absorber that served as light-heat converter. Single lap joints were subjected to a constant force and heated or irradiated with UV light until debonding occurred. The necessary debonding temperature was comparable for direct heating and UV irradiation and varied between 28 and 82 °C, depending on the applied force. The latter also influenced the debonding time, which under the chosen conditions ranged from 30 s to 12 min.

Taxonomic evaluation of putative Streptomyces scabiei strains held in the ARS (NRRL) Culture Collection using multi-locus sequence analysis

Science.gov (United States)

Multi-locus sequence analysis has been demonstrated to be a useful tool for identification of Streptomyces species and was previously applied to phylogenetically differentiate the type strains of species pathogenic on potatoes (Solanum tuberosum L.). The ARS Culture Collection (NRRL) contains 43 str...

Overview on the Preparation and Characterization of some Itaconic Acid Chelating Copolymers

International Nuclear Information System (INIS)

Abd El-Ghaffar, M.A.; Youssef, E.A.; El-Halawany, N.R.

2005-01-01

Itaconic acid (IA) was copolymerised by an emulsion process with butyl acrylate (BuA), butyl methacrylate (BuMA) and styrene (St) using potassium persulphate/sodium meta bisulphite as a redox initiation system and sodium dodecyl benzene sulfonate as an emulsifier. The rate of copolymerization was found to decrease with increasing (IA) content . The prepared copolymers were characterized by spectrophotometric analysis (IR and lINMR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) . The monomer reactivity ratios (r1and r2) for the prepared copolymers were determined and discussed . The copolymers having the best properties were incorporated in latex paint formulations. The Ac.. conductivity of the binary itaconic copolymers have been investigated and studied at room temperature and showed semiconducting properties

Tuning of Block Copolymer Membrane Morphology through Water Induced Phase Inversion Technique

KAUST Repository

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

Application of Bottlebrush Block Copolymers as Photonic Crystals.

Science.gov (United States)

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.

Adsorption of Poly(ethylene oxide)-Poly(lactide) Copolymers. Effects of Composition and Degradation.

Science.gov (United States)

Muller, Dries; Carlsson, Fredrik; Malmsten, Martin

2001-04-01

The effect of chemical degradation of two diblock copolymers of poly(ethylene oxide) (E) and poly(lactide) (L), E(39)L(5) and E(39)L(20), on their adsorption at silica and methylated silica was investigated with in situ ellipsometry. Steric stablization of polystyrene dispersions was investigated in relation to degradation. Hydrolysis of the poly(lactide) block of the copolymers was followed at different temperatures and pH by using HPLC to measure the occurrence of lactic acid in solution. The block copolymers were quite stable in pH-unadjusted solution at low temperature, whereas degradation was facilitated by increasing temperature or lowering of the pH. Lower degradation rates of E(39)L(20) where observed at low temperature in comparison with those of E(39)L(5), whereas the degradation rates of the copolymers were quantitatively similar at high temperature. The adsorption of the copolymers at methylated silica substrates decreased with increasing degree of degradation due to the reduction in the ability of hydrophobic block to anchor the copolymer layer at the surface. At silica the adsorption initially increased with increasing degradation, particularly for E(39)L(20) due to deposition of aggregates onto the surface. After extensive degradation the adsorption of the copolymers at both silica and methylated silica resembled that of the corresponding poly(ethylene oxide) homopolymer. Overall, it was found that the eventual reduction in adsorption occurred at a lower degree of degradation for E(39)L(5) than for E(39)L(20). Mean-field calculations showed a reduced anchoring for the block copolymers with decreasing poly(lactide) block length at hydrophobic surfaces. In accordance with this finding, it was observed that polystyrene dispersions were stabilized by E(39)L(20) or E(39)L(5) in a way that depended on both the lactide block length and the degree of degradation. Upon degradation of the hydrophobic block, stabilization of the polystyrene dispersions was

21 CFR 177.1315 - Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-1, 4-cyclohexylene dimethylene... Ethylene-1, 4-cyclohexylene dimethylene terephthalate copolymers. Ethylene-1, 4-cyclohexylene dimethylene... purposes of this section, ethylene-1,4-cyclohexylene dimethylene terephthalate copolymers (1,4-benzene...

Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

DEFF Research Database (Denmark)

Jankova, Katja; Hvilsted, Søren

2005-01-01

Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

Controlled specific placement of nanoparticles into microdomains of block copolymer thin films

Energy Technology Data Exchange (ETDEWEB)

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.

Controlled specific placement of nanoparticles into microdomains of block copolymer thin films

International Nuclear Information System (INIS)

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

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

DEFF Research Database (Denmark)

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...

Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups

Science.gov (United States)

Moszner, Norbert; Lukáč, Ivan

2012-01-01

Summary (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed. PMID:22509202

Temporally Regular Musical Primes Facilitate Subsequent Syntax Processing in Children with Specific Language Impairment.

Science.gov (United States)

Bedoin, Nathalie; Brisseau, Lucie; Molinier, Pauline; Roch, Didier; Tillmann, Barbara

2016-01-01

Children with developmental language disorders have been shown to be also impaired in rhythm and meter perception. Temporal processing and its link to language processing can be understood within the dynamic attending theory. An external stimulus can stimulate internal oscillators, which orient attention over time and drive speech signal segmentation to provide benefits for syntax processing, which is impaired in various patient populations. For children with Specific Language Impairment (SLI) and dyslexia, previous research has shown the influence of an external rhythmic stimulation on subsequent language processing by comparing the influence of a temporally regular musical prime to that of a temporally irregular prime. Here we tested whether the observed rhythmic stimulation effect is indeed due to a benefit provided by the regular musical prime (rather than a cost subsequent to the temporally irregular prime). Sixteen children with SLI and 16 age-matched controls listened to either a regular musical prime sequence or an environmental sound scene (without temporal regularities in event occurrence; i.e., referred to as "baseline condition") followed by grammatically correct and incorrect sentences. They were required to perform grammaticality judgments for each auditorily presented sentence. Results revealed that performance for the grammaticality judgments was better after the regular prime sequences than after the baseline sequences. Our findings are interpreted in the theoretical framework of the dynamic attending theory (Jones, 1976) and the temporal sampling (oscillatory) framework for developmental language disorders (Goswami, 2011). Furthermore, they encourage the use of rhythmic structures (even in non-verbal materials) to boost linguistic structure processing and outline perspectives for rehabilitation.

Thermal and radiochemical degradation of some PAN copolymers

Energy Technology Data Exchange (ETDEWEB)

Jipa, S. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Zaharescu, T. [' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania)], E-mail: traian_zaharescu@yahoo.com; Setnescu, R. [INCDIE, ICPE CA, 313 Splaiul Unirii, P.O. Box 149, Bucharest 030138 (Romania); ' Valachia' University of Targoviste, 18-22 Unirii Av., Targoviste 130082 (Romania); Dragan, E.S.; Dinu, M.V. [' Petru Poni' Institute of Macromolecular Chemistry, Iasi 700487 (Romania)

2008-12-01

Polyacrylonitrile (PAN) and some copolymers of acrylonitrile with divinylbenzene (AN-DVB) were investigated by the characterization of their thermal and radiation stabilities. The contribution of DVB to the thermal stability of PAN by the modification in the amount of unsaturated hydrocarbon between 6 and 20% was revealed by the evaluation of oxidation induction periods and required activation energies. The exposure of these materials to the action of {gamma}-radiation points out the higher stability of copolymers (AN-DVB) in comparison to the relative stability of PAN.

21 CFR 175.365 - Vinylidene chloride copolymer coatings for polycarbonate film.

Science.gov (United States)

2010-04-01

... polycarbonate film. 175.365 Section 175.365 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... chloride copolymer coatings for polycarbonate film. Vinylidene chloride copolymer coatings identified in this section and applied on polycarbonate film may be safely used as food-contact surfaces, in...

Study of the Pyrrol/Diphenylamine Copolymer by FT-IR spectroscopy and conductivity

Directory of Open Access Journals (Sweden)

Carlos Alberto Perez

2004-01-01

Full Text Available The main goal of this study was to analyze the physical properties of the copolymer formed by the electrochemical deposition of the polydiphenylamine (PDPA on polypyrrole (Ppy and Ppy on PDPA, in different conditions, through the characterization of the materials formed by the resonant Raman, FT-IR and conductivity techniques. The interactions among the species which are present in the new copolymer structure and the changes in electronic conductivity, were verified. The copolymer was also synthesized electrochemically in the presence of iodide species and the material was characterized by FT-IR spectroscopy and conductivity. The role of the dopant was studied in the process of charge transfer between the copolymer-dopant, acting in the stabilization of the species in the polymer backbone and the increase of the electronic conductivity.

Electrosyntheses and characterizations of a new soluble conducting copolymer of 5-cyanoindole and 3,4-ethylenedioxythiophene

International Nuclear Information System (INIS)

Nie Guangming; Qu Liangyan; Xu Jingkun; Zhang Shusheng

2008-01-01

The copolymerization of 5-cyanoindole (CNIn) and 3,4-ethylenedioxythiophene (EDOT) was successfully performed electrochemically in acetonitrile containing tetrabutylammonium tetrafluoroborate by direct oxidation of monomer mixtures. The electrochemical properties of the copolymers were studied by cyclic voltammetry. The influence of applied polymerization potential on the synthesis of copolymer was investigated. This novel copolymer owns the advantages of poly(5-cyanoindole) (PCNIn) and poly(3,4-ethylenedioxythiophene) (PEDOT), i.e., good redox activity, good thermal stability and high conductivity. The copolymer was soluble in dimethyl sulfoxide. The fluorescence spectra indicate that the copolymer is a good blue-light emitter. The structure and morphology of the copolymers were investigated by UV-vis, infrared spectroscopy, 1 H NMR spectra and scanning electron microscopy (SEM), respectively

Photodegradable neutral-cationic brush block copolymers for nonviral gene delivery.

Science.gov (United States)

Hu, Xianglong; Li, Yang; Liu, Tao; Zhang, Guoying; Liu, Shiyong

2014-08-01

We report on the fabrication of a photodegradable gene-delivery vector based on PEO-b-P(GMA-g-PDMAEMA) neutral-cationic brush block copolymers that possess cationic poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) brushes for DNA compaction, poly(ethylene oxide) (PEO) as a hydrophilic block, and poly(glycidyl methacrylate) (PGMA) as the backbone. The PEO-b-P(GMA-g-PDMAEMA) copolymers were synthesized through the combination of reversible addition-fragmentation transfer (RAFT) polymerization and postmodification. A photocleavable PEO-based macroRAFT agent was first synthesized; next, the PEO-b-PGMA block copolymer was prepared by RAFT polymerization of GMA; this was followed by a click reaction to introduce the RAFT initiators on the side chains of the PGMA block; then, RAFT polymerization of DMAEMA afforded the PEO-b-P(GMA-g-PDMAEMA) copolymer. The obtained neutral-cationic brush block copolymer could effectively complex plasmid DNA (pDNA) into nanoparticles at an N/P ratio (i.e., the number of nitrogen residues per DNA phosphate) of 4. Upon UV irradiation, pDNA could be released owing to cleavage of the pDNA-binding cationic PDMAEMA side chains as well as the nitrobenzyl ester linkages at the diblock junction point. In addition, in vitro gene transfection results demonstrated that the polyplexes could be effectively internalized by cells with good transfection efficiency, and the UV irradiation protocol could considerably enhance the efficiency of gene transfection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of block copolymer membranes using segregation strength trend lines

KAUST Repository

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.

Relaxation processes in a lower disorder order transition diblock copolymer

International Nuclear Information System (INIS)

Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

2015-01-01

The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T ODT , the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system

Low molecular weight block copolymers as plasticizers for polystyrene

DEFF Research Database (Denmark)

Hansen, Kristoffer Karsten; Nielsen, Charlotte Juel; Hvilsted, Søren

2005-01-01

/mol and minimum polystyrene content of 50 w/w%, which by us is predicted as the limits for solubility of polystyrene-b-alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight...... of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene-b-alkyl is found to be an efficient plasticizer also...... for polystyrene-b-polyisoprene-b-polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene-b-alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene-b-polybutadiene-b-polystyrene and polystyrene-bpoly(propylene glycol...

Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

Science.gov (United States)

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

Modeling of emulsion copolymer microstructure

NARCIS (Netherlands)

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

REGULAR PATTERN MINING (WITH JITTER ON WEIGHTED-DIRECTED DYNAMIC GRAPHS

Directory of Open Access Journals (Sweden)

A. GUPTA

2017-02-01

Full Text Available Real world graphs are mostly dynamic in nature, exhibiting time-varying behaviour in structure of the graph, weight on the edges and direction of the edges. Mining regular patterns in the occurrence of edge parameters gives an insight into the consumer trends over time in ecommerce co-purchasing networks. But such patterns need not necessarily be precise as in the case when some product goes out of stock or a group of customers becomes unavailable for a short period of time. Ignoring them may lead to loss of useful information and thus taking jitter into account becomes vital. To the best of our knowledge, no work has been yet reported to extract regular patterns considering a jitter of length greater than unity. In this article, we propose a novel method to find quasi regular patterns on weight and direction sequences of such graphs. The method involves analysing the dynamic network considering the inconsistencies in the occurrence of edges. It utilizes the relation between the occurrence sequence and the corresponding weight and direction sequences to speed up this process. Further, these patterns are used to determine the most central nodes (such as the most profit yielding products. To accomplish this we introduce the concept of dynamic closeness centrality and dynamic betweenness centrality. Experiments on Enron e-mail dataset and a synthetic dynamic network show that the presented approach is efficient, so it can be used to find patterns in large scale networks consisting of many timestamps.

Light scattering from block copolymer melts near the order-disorder transition

Czech Academy of Sciences Publication Activity Database

Štěpánek, Petr; Lodge, T. P.; Bates, F. S.

1994-01-01

Roč. 2, - (1994), s. 110 ISSN 0009-2347. [Symposium Block Copolymer Dynamics, Chain Dynamics of Block Copolymers: Dynamics near the Ordering Transition. San Diego, 13.03.1994-18.03.1994] R&D Projects: GA AV ČR IA45023 Impact factor: 0.331, year: 1994

Design of block-copolymer-based micelles for active and passive targeting

NARCIS (Netherlands)

Lebouille, Jérôme G J L; Leermakers, Frans A M; Cohen Stuart, Martien A.; Tuinier, Remco

2016-01-01

A self-consistent field study is presented on the design of active and passive targeting block-copolymeric micelles. These micelles form in water by self-assembly of triblock copolymers with a hydrophilic middle block and two hydrophobic outer blocks. A minority amount of diblock copolymers with the

Design of block-copolymer-based micelles for active and passive targeting

NARCIS (Netherlands)

Lebouille, Jérôme G.J.L.; Leermakers, Frans A.M.; Cohen Stuart, Martien A.; Tuinier, Remco

2016-01-01

A self-consistent field study is presented on the design of active and passive targeting block-copolymeric micelles. These micelles form in water by self-assembly of triblock copolymers with a hydrophilic middle block and two hydrophobic outer blocks. A minority amount of diblock copolymers with

Development and evaluation of a multi-locus sequence typing scheme for Mycoplasma synoviae.

Science.gov (United States)

Dijkman, R; Feberwee, A; Landman, W J M

2016-08-01

Reproducible molecular Mycoplasma synoviae typing techniques with sufficient discriminatory power may help to expand knowledge on its epidemiology and contribute to the improvement of control and eradication programmes of this mycoplasma species. The present study describes the development and validation of a novel multi-locus sequence typing (MLST) scheme for M. synoviae. Thirteen M. synoviae isolates originating from different poultry categories, farms and lesions, were subjected to whole genome sequencing. Their sequences were compared to that of M. synoviae reference strain MS53. A high number of single nucleotide polymorphisms (SNPs) indicating considerable genetic diversity were identified. SNPs were present in over 40 putative target genes for MLST of which five target genes were selected (nanA, uvrA, lepA, ruvB and ugpA) for the MLST scheme. This scheme was evaluated analysing 209 M. synoviae samples from different countries, categories of poultry, farms and lesions. Eleven clonal clusters and 76 different sequence types (STs) were obtained. Clustering occurred following geographical origin, supporting the hypothesis of regional population evolution. M. synoviae samples obtained from epidemiologically linked outbreaks often harboured the same ST. In contrast, multiple M. synoviae lineages were found in samples originating from swollen joints or oviducts from hens that produce eggs with eggshell apex abnormalities indicating that further research is needed to identify the genetic factors of M. synoviae that may explain its variations in tissue tropism and disease inducing potential. Furthermore, MLST proved to have a higher discriminatory power compared to variable lipoprotein and haemagglutinin A typing, which generated 50 different genotypes on the same database.

Optimal Golomb Ruler Sequences Generation for Optical WDM Systems: A Novel Parallel Hybrid Multi-objective Bat Algorithm

Science.gov (United States)

Bansal, Shonak; Singh, Arun Kumar; Gupta, Neena

2017-02-01

In real-life, multi-objective engineering design problems are very tough and time consuming optimization problems due to their high degree of nonlinearities, complexities and inhomogeneity. Nature-inspired based multi-objective optimization algorithms are now becoming popular for solving multi-objective engineering design problems. This paper proposes original multi-objective Bat algorithm (MOBA) and its extended form, namely, novel parallel hybrid multi-objective Bat algorithm (PHMOBA) to generate shortest length Golomb ruler called optimal Golomb ruler (OGR) sequences at a reasonable computation time. The OGRs found their application in optical wavelength division multiplexing (WDM) systems as channel-allocation algorithm to reduce the four-wave mixing (FWM) crosstalk. The performances of both the proposed algorithms to generate OGRs as optical WDM channel-allocation is compared with other existing classical computing and nature-inspired algorithms, including extended quadratic congruence (EQC), search algorithm (SA), genetic algorithms (GAs), biogeography based optimization (BBO) and big bang-big crunch (BB-BC) optimization algorithms. Simulations conclude that the proposed parallel hybrid multi-objective Bat algorithm works efficiently as compared to original multi-objective Bat algorithm and other existing algorithms to generate OGRs for optical WDM systems. The algorithm PHMOBA to generate OGRs, has higher convergence and success rate than original MOBA. The efficiency improvement of proposed PHMOBA to generate OGRs up to 20-marks, in terms of ruler length and total optical channel bandwidth (TBW) is 100 %, whereas for original MOBA is 85 %. Finally the implications for further research are also discussed.

Thin Films of Novel Linear-Dendritic Diblock Copolymers

Science.gov (United States)

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.

Polymers and block copolymers of fluorostyrenes by ATRP

DEFF Research Database (Denmark)

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....

Barite formation in the presence of a commercial copolymer

Science.gov (United States)

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

Characteristics of immobilized aminoacylase from Aspergillus oryzae on macroporous copolymers.

Science.gov (United States)

He, B L; Jiang, P; Qiu, Y B

1990-01-01

Aminoacylase from Aspergillus oryzae was adsorbed on functionallized macroporous copolymers where the enzyme showed excellent catalyzing activity and operation stability. Various factors which effect the activity of the immobilized aminoacylase such as temperature, pH and ionic strength were investigated. The continuous operation of the enzyme immobilized on macroporous copolymers was compared with that of the enzyme immobilized on DEAE-Sephadex.

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

Directory of Open Access Journals (Sweden)

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.

Polarizability of DNA Block Copolymer Nanoparticles Observed by Electrostatic Force Microscopy

NARCIS (Netherlands)

Sowwan, Mukhles; Faroun, Maryam; Mentovich, Elad; Ibrahim, Imad; Haboush, Shayma; Alemdaroglu, Fikri Emrah; Kwak, Minseok; Richter, Shachar; Herrmann, Andreas

2010-01-01

In this study, DNA block copolymer (DBC) micelles with a polystyrene (PS) core and a single-stranded (ss) DNA shell were doped with ferrocene (Fc) molecules. Tapping mode atomic force microscopy (AFM) was used to study the morphology of the doped and undoped block copolymer aggregates. We show that

Cellulose-based graft copolymers prepared by simplified electrochemically mediated ATRP

Directory of Open Access Journals (Sweden)

P. Chmielarz

2017-02-01

Full Text Available Brush-shaped block copolymer with a dual hydrophilic poly(acrylic acid-block-poly(oligo(ethylene glycol acrylate (PAA-b-POEGA arms was synthesized for the first time via a simplified electrochemically mediated ATRP (seATRP under both constant potential electrolysis and constant current electrolysis conditions, utilizing only 30 ppm of catalyst complex. The polymerization conditions were optimized to provide fast reactions while employing low catalyst concentrations and preparation of cellulose-based brush-like copolymers with narrow molecular weight distributions. The results from proton nuclear magnetic resonance (1H NMR spectral studies support the formation of cellulose-based graft (copolymers. It is expected that these new polymer brushes may find application as pH- and thermo-sensitive drug delivery systems.

Polydimethylsiloxane-polymethacrylate block copolymers tethering quaternary ammonium salt groups for antimicrobial coating

Energy Technology Data Exchange (ETDEWEB)

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.

Responsive linear-dendritic block copolymers.

Science.gov (United States)

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.

SYNTHESIS OF AMPHIPHILIC COMB-SHAPED COPOLYMERS USED FOR SURFACE MODIFICATION OF PVDF MEMBRANES

Institute of Scientific and Technical Information of China (English)

徐又一

2009-01-01

The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4- hydroxyphenyl) maleimide)(SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate(PEGMA) side groups was achieved by atom transfer radical polymerization(ATRP).The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).From thermogravimetric analysis (TGA),the decomposition temperature of SHMI-g-PEGMA is low...

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

Energy Technology Data Exchange (ETDEWEB)

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.

Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

International Nuclear Information System (INIS)

Müller, Marcus; Li, Weihua; Rey, Juan Carlos Orozco; Welling, Ulrich

2015-01-01

Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies (”chemoepitaxy”). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer. (paper)

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

Science.gov (United States)

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.

Applying thermosettable zwitterionic copolymers as general fouling-resistant and thermal-tolerant biomaterial interfaces.

Science.gov (United States)

Chou, Ying-Nien; Chang, Yung; Wen, Ten-Chin

2015-05-20

We introduced a thermosettable zwitterionic copolymer to design a high temperature tolerance biomaterial as a general antifouling polymer interface. The original synthetic fouling-resistant copolymer, poly(vinylpyrrolidone)-co-poly(sulfobetaine methacrylate) (poly(VP-co-SBMA)), is both thermal-tolerant and fouling-resistant, and the antifouling stability of copolymer coated interfaces can be effectively controlled by regulating the VP/SBMA composition ratio. We studied poly(VP-co-SBMA) copolymer gels and networks with a focus on their general resistance to protein, cell, and bacterial bioadhesion, as influenced by the thermosetting process. Interestingly, we found that the shape of the poly(VP-co-SBMA) copolymer material can be set at a high annealing temperature of 200 °C while maintaining good antifouling properties. However, while the zwitterionic PSBMA polymer gels were bioinert as expected, control of the fouling resistance of the PSBMA polymer networks was lost in the high temperature annealing process. A poly(VP-co-SBMA) copolymer network composed of PSBMA segments at 32 mol % showed reduced fibrinogen adsorption, tissue cell adhesion, and bacterial attachment, but a relatively higher PSBMA content of 61 mol % was required to optimize resistance to platelet adhesion and erythrocyte attachment to confer hemocompatibility to human blood. We suggest that poly(VP-co-SBMA) copolymers capable of retaining stable fouling resistance after high temperature shaping have a potential application as thermosettable materials in a bioinert interface for medical devices, such as the thermosettable coating on a stainless steel blood-compatible metal stent investigated in this study.

Thin Film Assembly of Spider Silk-like Block Copolymers

Science.gov (United States)

2011-01-01

Shipley, N. H.; Lewis, R. V. Int. J. Biol.Macromol. 1999, 24, 271. (c) Thiel, B. L.; Guess, K. B.; Viney, C. Biopolymers 1997, 41, 703. (13) Silk ...Film Assembly of Spider Silk -like Block Copolymers Sreevidhya T. Krishnaji,†,‡ Wenwen Huang,§ Olena Rabotyagova,†,‡ Eugenia Kharlampieva, ) Ikjun Choi...Received November 26, 2010 We report the self-assembly of monolayers of spider silk -like block copolymers. Langmuir isotherms were obtained for a series of

Novel block, graft and random copolymers for biomedical applications

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Jankova Atanasova, Katja; Tanaka, Masaru

Despite the simple structure, poly(2-methoxyethyl acrylate) (PMEA) shows excellent blood compatibility [1]. Both the freezing-bound water (intermediate water: preventing the biocomponents from directly contacting the polymer surface) and non-freezing water on the polymer surface play important...... copolymers with MMA [4] utilizing ATRP. Here we present other block, graft and random copolymers of MEA intended for biomedical applications. These macromolecular architectures have been constructed by employing controlled radical polymerization methods such as RAFT and ATRP....

In-situ Polymerization of Polyaniline/Polypyrrole Copolymer using Different Techniques

Science.gov (United States)

Hammad, A. S.; Noby, H.; Elkady, M. F.; El-Shazly, A. H.

2018-01-01

The morphology and surface area of the poly(aniline-co-pyrrole) copolymer (PANPY) are important properties which improve the efficiency of the copolymer in various applications. In this investigation, different techniques were employed to produce PANPY in different morphologies. Aniline and pyrrole were used as monomers, and ammonium peroxydisulfate (APS) was used as an oxidizer with uniform molar ratio. Rapid mixing, drop-wise mixing, and supercritical carbon dioxide (ScCO2) polymerization techniques were appointed. The chemical structure, crystallinity, porosity, and morphology of the composite were distinguished by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) analysis, and transmission electron microscopy (TEM) respectively. The characterization tests indicated that the polyaniline/polypyrrole copolymer was successfully prepared with different morphologies. Based on the obtained TEM, hollow nanospheres were formed using rapid mixing technique with acetic acid that have a diameter of 75 nm and thickness 26 nm approximately. Also, according to the XRD, the produced structures have a semi- crystalline structure. The synthesized copolymer with ScCO2-assisted polymerization technique showed improved surface area (38.1 m2/g) with HCl as dopant.

Water stale and structure analysis of Konjac irradiation copolymer

International Nuclear Information System (INIS)

Geng Shengrong; Xia Hezhou; Chen Xueling; Ye Lixiu; Hua Yuejin

2011-01-01

To study the absorption performance of Konjac-AA copolymer prepared by using irradiation, the water absorption capacity, sorbent speed and water keeping ability were determined, DSC and TEM analysis were used to investigate the water content and structure characters. The results showed that the largest water absorption speed was 16 g · -1 · min -1 at room temperature, and the largest water absorption was 400 times within 60 minutes. The water absorption was affected by granularity, temperature, ion content and ion type, especially the ion type. The water keeping ability was affected by temperature and time, which was up to 35% of absorbed water when the fully water absorbed copolymer was kept under room temperature for 15 d. The free and bounder water content which could be assimilated by the plants was 99.617%. The water stale copolymer has a three-dimensional spiral structure. (authors)

40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of a...

Influence of the content of hard segments on the properties of novel urethane-siloxane copolymers based on a poly(ε-caprolactone-b-poly(dimethylsiloxane-b-poly(ε- caprolactone triblock copolymer

Directory of Open Access Journals (Sweden)

Antić Vesna V.

2011-01-01

Full Text Available A series of novel thermoplastic urethane-siloxane copolymers (TPUSs based on a α,ω-dihydroxy-[poly(ε-caprolactone-bpoly( dimethylsiloxane-b-poly(ε-caprolactone] (α,ω-dihydroxy-PCLPDMS- PCL triblock copolymer, 4,4?-methylenediphenyl diisocyanate (MDI and 1,4-butanediol (BD was synthesized. The effects of the content (9-63 wt. % of hard urethane segments and their degree of polymerization on the properties of the segmented TPUSs were investigated. The structure, composition and hard segment degree of polymerization of the hard segments were examined using 1H- and quantitative 13C-NMR spectroscopy. The degree of crystallinity of the synthesized copolymers was determined using wide-angle X-ray scattering (WAXS. The surface properties were evaluated by measuring the water contact angle and water absorption. In the series of the TPUSs, the average degree of polymerization of the hard segments was varied from 1.2 to 14.4 MDI-BD units. It was found that average values from 3.8 to 14.4 MDI-BD units were effective segment lengths for crystallization of hard segments, which resulted in an increase in the degree of microphase separation of the copolymers. Spherulite-like superstructures were observed in copolymer films by scanning electron microscopy (SEM, which are believed to arise from the crystallization of the hard segments and/or PCL segments, depending on the content of the hard segments. The surface of the copolymers became more hydrophobic with increasing weight fraction of PDMS. The synthesized copolymers based on a PCL-PDMS-PCL segment showed good thermal stability, which increased with increasing content of soft PDMS segments, as was confirmed by the value of the starting temperature of thermal degradation.

Sequence Algebra, Sequence Decision Diagrams and Dynamic Fault Trees

International Nuclear Information System (INIS)

Rauzy, Antoine B.

2011-01-01

A large attention has been focused on the Dynamic Fault Trees in the past few years. By adding new gates to static (regular) Fault Trees, Dynamic Fault Trees aim to take into account dependencies among events. Merle et al. proposed recently an algebraic framework to give a formal interpretation to these gates. In this article, we extend Merle et al.'s work by adopting a slightly different perspective. We introduce Sequence Algebras that can be seen as Algebras of Basic Events, representing failures of non-repairable components. We show how to interpret Dynamic Fault Trees within this framework. Finally, we propose a new data structure to encode sets of sequences of Basic Events: Sequence Decision Diagrams. Sequence Decision Diagrams are very much inspired from Minato's Zero-Suppressed Binary Decision Diagrams. We show that all operations of Sequence Algebras can be performed on this data structure.

Influence of copolymer architectures on adhesion and compatibilization of polymers at interfaces

Science.gov (United States)

Guo, Lantao

Adhesion and compatibilization of immiscible homopolymers by a variety of copolymer architectures were studied. The work is arranged into 5 chapters: In Chapter 1, an introduction to recent studies on improvement of adhesion and compatibilization of polymer blends using copolymers was made including the advantages and shortcomings of interfacial reinforcement by a diblock copolymer architecture. Emphasis is on the novel ways to improve adhesion at polymer interfaces by a variety of copolymer architectures, including physical entanglement and chemical modification and chemical bonding. In Chapter 2, a series of Polystyrene-Poly(methyl methacrylate) (PS-PMMA) graft copolymers were introduced to modify the PS and PMMA homopolymer interface and was found to increase the interfacial fracture toughness to a large extent, depending on the detailed architectural variables such as the graft number per chain, the lengths of the backbone and the grafts, and the total molecular weights of the graft copolymers. It was also found that there was an optimal number of grafts per chain which can be interpreted based on the graft length and inter-branch length of the backbone of the copolymer. Effect of in-situ grafting via a chemical reaction between Polystyrene-Poly(vinyl phenol) (PS-PSOH) and oxazoline containing Styrene-Acrylonitril (SAN) was also discussed compared with the physical grafting of a graft copolymer of different structural parameters. In Chapter 3, hydrogen bonding was utilized to toughen the interface between PS and PAA poly(acrylic acid)) or PMMA using a random copolymer architecture of Polystyrene-Poly(vinyl pyridine) (PS-PVP). It was shown that random copolymer architecture is not only economically feasible due to its low cost of producing but also very effective on adhesion because it not only overcomes the issue of micelle formation which is an unavoidable situation in the diblock and graft cases but the enhancement of adhesion is much higher utilizing a H

Copolymers of fluorinated polydienes and sulfonated polystyrene

Science.gov (United States)

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.

Synthesis and Characterization of Novel Magnetite Nanoparticle Block Copolymer Complexes

OpenAIRE

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...

Coordinate-invariant regularization

International Nuclear Information System (INIS)

Halpern, M.B.

1987-01-01

A general phase-space framework for coordinate-invariant regularization is given. The development is geometric, with all regularization contained in regularized DeWitt Superstructures on field deformations. Parallel development of invariant coordinate-space regularization is obtained by regularized functional integration of the momenta. As representative examples of the general formulation, the regularized general non-linear sigma model and regularized quantum gravity are discussed. copyright 1987 Academic Press, Inc

The effect of copolymers on the interfaces in incompatible homopolymers blend: Molecular dynamics study

Science.gov (United States)

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.

Microphase separation behavior on the surfaces of PEG-MDI-PDMS multiblock copolymer coatings

International Nuclear Information System (INIS)

Fang Hongxia; Zhou Shuxue; Wu Limin

2006-01-01

A series of poly(ethylene glycol)(PEG)-4,4'-diphenylmethanediisocyanate(MDI)-poly(dimethylsiloxane) (PDMS) multiblock copolymers were synthesized by employing two-step growth polymerization technique. Atomic force microscopy (AFM) observed nanoscopically well-organized phase-separated surfaces consisting of hydrophilic domain from PEG and MDI segments and hydrophobic domain from PDMS segments even with 50 wt.% PDMS in the copolymer, and the multiblock copolymer coatings presented a surface free energy of as low as 6-8 mN m -1

Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing

Energy Technology Data Exchange (ETDEWEB)

Cong, Zhinan; Zhang, Liangshun, E-mail: zhangls@ecust.edu.cn, E-mail: jlin@ecust.edu.cn; Wang, Liquan; Lin, Jiaping, E-mail: zhangls@ecust.edu.cn, E-mail: jlin@ecust.edu.cn [Shanghai Key Laboratory of Advanced Polymeric Materials, State Key Laboratory of Bioreactor Engineering, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2016-03-21

A theoretical method based on dynamic version of self-consistent field theory is extended to investigate directed self-assembly behaviors of block copolymers subjected to zone annealing. The ordering mechanisms and orientation modulation of microphase-separated nanostructures of block copolymers are discussed in terms of sweep velocity, wall preference, and Flory-Huggins interaction parameter. The simulated results demonstrate that the long-range ordered nanopatterns are achieved by lowering the sweep velocity of zone annealing due to the incorporation of templated ordering of block copolymers. The surface enrichment by one of the two polymer species induces the orientation modulation of defect-free nanostructures through finely tuning the composition of block copolymers and the preference of walls. Additionally, the Flory-Huggins interaction parameters of block copolymers in the distinct regions are main factors to design the zone annealing process for creating the highly ordered nanostructures with single orientation.

Evaluation of TSE- and T1-3D-GRE-sequences for focal cartilage lesions in vitro in comparison to ultrahigh resolution multi-slice CT

International Nuclear Information System (INIS)

Stork, A.; Schulze, D.; Koops, A.; Kemper, J.; Adam, G.

2002-01-01

Purpose: Evaluation of TSE- and T 1 -3D-GRE-sequences for focal cartilage lesions in vitro in comparison to ultrahigh resolution multi-slice CT. Materials and methods: Forty artificial cartilage lesions in ten bovine patellae were immersed in a solution of iodinated contrast medium and assessed with ultrahigh resolution multi-slice CT. Fat-suppressed TSE images with intermediate- and T 2 -weighting at a slice thickness of 2, 3 and 4 mm as well as fat-suppressed T 1 -weighted 3D-FLASH images with an effective slice thickness of 1, 2 and 3 mm were acquired at 1.5 T. After adding Gd-DTPA to the saline solution containing the patellae, the T 1 -weighted 3D-FLASH imaging was repeated. Results: All cartilage lesions were visualised and graded with ultrahigh resolution multi-slice CT. The TSE images had a higher sensitivity and a higher inter- and intraobserver kappa compared to the FLASH-sequences (TSE: 70-95%; 0.82-0.83; 0.85-0.9; FLASH: 57.5-85%; 0.53-0.72; 0.73-0.82, respectively). An increase in slice thickness decreased the sensitivity, whereby deep lesions were even reliably depicted on TSE images at a slice thickness of 3 and 4 mm. Adding Gd-DTPA to the saline solution increased the sensitivity by 10% with no detectable advantage over the T 2 -weighted TSE images. Conclusion: TSE sequences and application of Gd-DTPA seemed to be superior to T 1 -weighted 3D-FLASH sequences without Gd-DTPA in the detection of focal cartilage lesions. The ultrahigh resolution multi-slice CT can serve as in vitro reference standard for focal cartilage lesions. (orig.) [de

Process for producing a novel copolymer. [electron beams

Energy Technology Data Exchange (ETDEWEB)

Oiwa, M; Matsumoto, A; Tojima, M; Matsumoto, K; Sasaki, H

1970-11-27

Diaryl oxalate present in a polymer not only decomposes at lower temperatures, but also provides for stronger free radicals initiating polymerization than diaryl oxalate present in a monomer. A copolymer of vinyl monomers is produced by providing a diaryl oxalate polymer or a diaryl oxalate monomer-co-vinyl monomer, decomposing them to release the diaryl oxalate units by heating or irradiating with radiation thereby copolymerizing the vinyl monomer with the polymer radicals by utilizing the diaryl oxalate unit. For example, a single diaryl oxalate polymer or a copolymer containing the diaryl oxalate polymer as a constituent of the copolymer are irradiated or heated with a vinyl monomer, i.e. methyl methacrylate, acrylnitrile, vinyl acetate, styrene etc., to form a copolymer without difficulty. In one of the examples, 500 g of diaryl oxalate monomer, 1,200 ml of benzene and 0.2 mol/l of benzoil peroxide as an initiator were mixed and polymerized in nitrogen gas at 70/sup 0/C for 8 hrs. From this polymerized solution, a polymer was deposited in methanol. The produced polymer had an iodin value of 77.7 with a yield of 35%. The gel content of the produced polymer was 98.9% for 10 Mrad. This polymer was dissolved in methyl methacrylate, thereafter filled in a mold and irradiated with electron beams of 2 MeV in nitrogen gas to harden it. The advantage of this process is that the polymerization is effected with low energy radiations at room temperature without requiring any catalyst.

Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

International Nuclear Information System (INIS)

Zhou, Xiao-Ming

2012-01-01

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, 1 HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T m ), crystallization temperature (T c ), and crystallinity (X c ) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers. - Graphical abstract: The composition of polyester copolymer was determined from the 1 H NMR spectra using the relative intensities of the proton peaks. As a sample, the 1 H NMR spectrum of polyester copolymer with 10 mol% of PEG is shown in Fig. 2: CO-(CH 2 ) 2 -CO; O-CH 2 - and C-(CH 2 ) 2 -C from the SA and BD unit at δ2.59; δ 4.08 and δ1.67; O-(CH 2 CH 2 ) n -O from the PEG unit at δ 3.61. The molar composition of polyester copolymer was measured as the area ratio of δ3.61/(δ4.08 + δ1.67) peak. The PEG unit is incorporated into the copolymers in an amount of about 9.12mol% less than that of the feed proportion. These results showed that the composition of the copolymers is in good agreement with that expected from the feed proportion. Highlights: ► The introduction of PEG unit changed the flexibility of PBS main chain. ► PEG unit did not alter the crystal form of PBS in copolymers. ► PEG unit hindered the formation of ring-banded spherulite morphology in copolymers. ► The copolyesters had good in vitro degradation performance. ► The composition ratio of PEG unit can adjust the in vitro degradation performance.

Copolymers of various architectures containing ethylene and 5-norbornen-2-yl derivatives

Science.gov (United States)

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

Incorporating multi-leaf collimator leaf sequencing into iterative IMRT optimization

International Nuclear Information System (INIS)

Siebers, Jeffrey V.; Lauterbach, Marc; Keall, Paul J.; Mohan, Radhe

2002-01-01

Intensity modulated radiation therapy (IMRT) treatment planning typically considers beam optimization and beam delivery as separate tasks. Following optimization, a multi-leaf collimator (MLC) or other beam delivery device is used to generate fluence patterns for patient treatment delivery. Due to limitations and characteristics of the MLC, the deliverable intensity distributions often differ from those produced by the optimizer, leading to differences between the delivered and the optimized doses. Objective function parameters are then adjusted empirically, and the plan is reoptimized to achieve a desired deliverable dose distribution. The resulting plan, though usually acceptable, may not be the best achievable. A method has been developed to incorporate the MLC restrictions into the optimization process. Our in-house IMRT system has been modified to include the calculation of the deliverable intensity into the optimizer. In this process, prior to dose calculation, the MLC leaf sequencer is used to convert intensities to dynamic MLC sequences, from which the deliverable intensities are then determined. All other optimization steps remain the same. To evaluate the effectiveness of deliverable-based optimization, 17 patient cases have been studied. Compared with standard optimization plus conversion to deliverable beams, deliverable-based optimization results show improved isodose coverage and a reduced dose to critical structures. Deliverable-based optimization results are close to the original nondeliverable optimization results, suggesting that IMRT can overcome the MLC limitations by adjusting individual beamlets. The use of deliverable-based optimization may reduce the need for empirical adjustment of objective function parameters and reoptimization of a plan to achieve desired results

Self-Assembling Diblock Copolymers of Poly[N-(2-hydroxypropyl)methacrylamide] and a β-Sheet Peptide

Science.gov (United States)

Radu, Larisa Cristina; Yang, Jiyuan

2015-01-01

The self-assembly of hybrid diblock copolymers composed of poly(HPMA) and β-sheet peptide P11 (CH3CO-QQRFQWQFEQQ-NH2) blocks was investigated. Copolymers were synthesized via thiol-maleimide coupling reaction, by conjugation of semitelechelic poly(HPMA)-SH with maleimide-modified β-sheet peptide. As expected, CD and CR binding studies showed that the peptide block imposed its β-sheet structural arrangement on the structure of diblock copolymers. TEM and AFM proved that peptide and these copolymers had the ability to self-assemble into fibrils. PMID:18855948

Colorectal Cancer Genetic Heterogeneity Delineated by Multi-Region Sequencing.

Directory of Open Access Journals (Sweden)

You-Wang Lu

Full Text Available Intratumor heterogeneity (ITH leads to an underestimation of the mutational landscape portrayed by a single needle biopsy and consequently affects treatment precision. The extent of colorectal cancer (CRC genetic ITH is not well understood in Chinese patients. Thus, we conducted deep sequencing by using the OncoGxOne™ Plus panel, targeting 333 cancer-specific genes in multi-region biopsies of primary and liver metastatic tumors from three Chinese CRC patients. We determined that the extent of ITH varied among the three cases. On average, 65% of all the mutations detected were common within individual tumors. KMT2C aberrations and the NCOR1 mutation were the only ubiquitous events. Subsequent phylogenetic analysis showed that the tumors evolved in a branched manner. Comparison of the primary and metastatic tumors revealed that PPP2R1A (E370X, SETD2 (I1608V, SMAD4 (G382T, and AR splicing site mutations may be specific to liver metastatic cancer. These mutations might contribute to the initiation and progression of distant metastasis. Collectively, our analysis identified a substantial level of genetic ITH in CRC, which should be considered for personalized therapeutic strategies.

Gas-permeation properties of poly(ethylene oxide) poly(butylene terephthalate block copolymers

NARCIS (Netherlands)

Metz, S.J.; Mulder, M.H.V.; Wessling, Matthias

2004-01-01

This paper reports the gas-permeation properties of poly(ethylene oxide) (PEO) poly(butylene terephthalate) (PBT) segmented multiblock copolymers. These block copolymers allow a precise structural modification by the amount of PBT and the PEO segment length, enabling a systematic study of the

Controlled release of potassium chloride from radiation-polymerized copolymer matrices

International Nuclear Information System (INIS)

Yoshida, Masaru; Kumakura, Minoru; Kaetsu, Isao

1979-01-01

Release behavior of potassium chloride (KCl) from the flat circular copolymer composites, obtained by radiation-induced polymerization at low temperatures, was studied. The release rate agreed with the first-order kinetics based on the Noyes-Whitney equation in relation to the swelling of the composites. Release profiles of KCl from copolymer composites was affected by monomer composition between hydroxyethyl acrylate (HEA) and polyfunctional glass-forming monomers such as 2-hydroxyethyl methacrylate (HEMA), diethylene glycol dimethacrylate (DGDA), and trimethylolpropane trimethacrylate (TMPT) owing to change of swelling property of copolymers. The release rate decreased at HEA-poor composition in any system. In the case of hydrophobic comonomer system such as glycidyl methacrylate (GMA) and DGDA, release profile of KCl showed a minimum at 50% GMA-50% DGDA monomer composition. (author)

Pressure and temperature effects in homopolymer blends and diblock copolymers

DEFF Research Database (Denmark)

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...

High-frequency ultrasound-responsive block copolymer micelle.

Science.gov (United States)

Wang, Jie; Pelletier, Maxime; Zhang, Hongji; Xia, Hesheng; Zhao, Yue

2009-11-17

Micelles of a diblock copolymer composed of poly(ethylene oxide) and poly(2-tetrahydropyranyl methacrylate) (PEO-b-PTHPMA) in aqueous solution could be disrupted by high-frequency ultrasound (1.1 MHz). It was found that, upon exposure to a high-intensity focused ultrasound (HIFU) beam at room temperature, the pH value of the micellar solution decreased over irradiation time. The infrared spectroscopic analysis of solid block copolymer samples collected from the ultrasound irradiated micellar solution revealed the formation of carboxylic acid dimers and hydroxyl groups. These characterization results suggest that the high-frequency HIFU beam could induce the hydrolysis reaction of THPMA at room temperature resulting in the cleavage of THP groups. The disruption of PEO-b-PTHPMA micelles by ultrasound was investigated by using dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. On the basis of the pH change, it was found that the disruption process was determined by a number of factors such as the ultrasound power, the micellar solution volume and the location of the focal spot of the ultrasound beam. This study shows the potential to develop ultrasound-sensitive block copolymer micelles by having labile chemical bonds in the polymer structure, and to use the high-frequency HIFU to trigger a chemical reaction for the disruption of micelles.

(Electro)Mechanical Properties of Olefinic Block Copolymers

Science.gov (United States)

Spontak, Richard

2014-03-01

Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

Nonlinear optical measurements of conducting copolymers of aniline under CW laser excitation

Science.gov (United States)

Pramodini, S.; Poornesh, P.

2015-08-01

Synthesis and measurements of third-order optical nonlinearity and optical limiting of conducting copolymers of aniline are presented. Single beam z-scan technique was employed for the nonlinear optical studies. Continuous wave He-Ne laser operating at 633 nm was used as the source of excitation. Copolymer samples exhibited reverse saturable absorption (RSA) process. The nonlinear refraction studies depict that the copolymers exhibit self-defocusing property. The estimated values of βeff, n2 and χ(3) were found to be of the order of 10-2 cm/W, 10-5 esu and 10-7 esu respectively. Self-diffraction rings were observed due to refractive index change when exposed to the laser beam. A good optical limiting and clamping of power of ∼0.9 mW and ∼0.05 mW was observed. Therefore, copolymers of aniline emerge as a potential candidate for photonic device applications.

Ionization of amphiphilic acidic block copolymers.

Science.gov (United States)

Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

2012-06-28

The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

Phase Separation and Elastic Properties of Poly(Trimethylene Terephthalate-block-poly(Ethylene Oxide Copolymers

Directory of Open Access Journals (Sweden)

Elżbieta Piesowicz

2016-06-01

Full Text Available A series of poly(trimethylene terephthalate-block-poly(ethylene oxide (PTT-b-PEOT copolymers with different compositions of rigid PTT and flexible PEOT segments were synthesized via condensation in the melt. The influence of the block length and the block ratio on the micro-separated phase structure and elastic properties of the synthesized multiblock copolymers was studied. The PEOT segments in these copolymers were kept constant at 1130, 2130 or 3130 g/mol, whereas the PTT content varied from 30 up to 50 wt %. The phase separation was assessed using differential scanning calorimetry (DSC and dynamic mechanical thermal analysis (DMTA. The crystal structure of the synthesised block copolymers and their microstructure on the manometer scale was evaluated by using WAXS and SAXS analysis. Depending on the PTT/PEOT ratio, but also on the rigid and flexible segment length in PTT-b-PEO copolymers, four different domains were observed i.e.,: a crystalline PTT phase, a crystalline PEO phase (which exists for the whole series based on three types of PEOT segments, an amorphous PTT phase (only at 50 wt % content of PTT rigid segments and an amorphous PEO phase. Moreover, the elastic deformability and reversibility of PTT-b-PEOT block copolymers were studied during a cyclic tensile test. Determined values of permanent set resultant from maximum attained stain (100% and 200% for copolymers were used to evaluate their elastic properties.

Molecular designing of novel ternary copolymers of donor-acceptor polymers using genetic algorithm

International Nuclear Information System (INIS)

Arora, Vinita; Bakhshi, A.K.

2010-01-01

Graphical abstract: Alternate arrangement of donor acceptor moieties in the carbon backbone chain of an organic conjugated polymer is capable of inducing charge transfer and affects the electronic properties of the copolymer. Genetic algorithm along with simple NFC (negative factor counting) and IIM (inverse iteration method) has been used to optimize the properties of novel ternary copolymers based on polypyrrole PPy, polythiophene PTh and polyfuran PFu (as donor moieties) and containing >C=O and >C=CF 2 bridging units as acceptor moieties. - Abstract: An efficient designing route to novel ternary copolymers consisting of polypyrrole (PPy), polythiophene (PTh) and polyfuran (PFu) is developed with the help of genetic algorithm. Using the band structure results obtained from ab initio crystal orbital (CO) calculations, the electronic structures and conduction properties of real ternary copolymers based on donor acceptor type polymers are investigated. The electron rich heterocyclic rings in the backbone chain of the copolymer are joined together by electron withdrawing groups Y, carbonyl group (>C=O) and difluoromethylene group (>C=CF 2 ) in an attempt to design the conducting polymer with lowest band gap. A comparative study of various electronic properties is presented. The effects of substitution on the behaviour and properties of the copolymers as well as on the density of states (DOS) are discussed. Band gap decreases as a result of substitution on the polymer backbone chain due to decrease in ionization potential and increase in electron affinity values. This is expected to enhance the intrinsic conductivity of the resulting copolymer. Use of alternate donor acceptor moieties within the repeat units should maximize the extended π conjugation.

Molecular designing of novel ternary copolymers of donor-acceptor polymers using genetic algorithm

Energy Technology Data Exchange (ETDEWEB)

Arora, Vinita [Department of Chemistry, University of Delhi, Delhi 110 007 (India); Bakhshi, A.K., E-mail: akbakhshi2000@yahoo.com [Department of Chemistry, University of Delhi, Delhi 110 007 (India)

2010-08-03

Graphical abstract: Alternate arrangement of donor acceptor moieties in the carbon backbone chain of an organic conjugated polymer is capable of inducing charge transfer and affects the electronic properties of the copolymer. Genetic algorithm along with simple NFC (negative factor counting) and IIM (inverse iteration method) has been used to optimize the properties of novel ternary copolymers based on polypyrrole PPy, polythiophene PTh and polyfuran PFu (as donor moieties) and containing >C=O and >C=CF{sub 2} bridging units as acceptor moieties. - Abstract: An efficient designing route to novel ternary copolymers consisting of polypyrrole (PPy), polythiophene (PTh) and polyfuran (PFu) is developed with the help of genetic algorithm. Using the band structure results obtained from ab initio crystal orbital (CO) calculations, the electronic structures and conduction properties of real ternary copolymers based on donor acceptor type polymers are investigated. The electron rich heterocyclic rings in the backbone chain of the copolymer are joined together by electron withdrawing groups Y, carbonyl group (>C=O) and difluoromethylene group (>C=CF{sub 2}) in an attempt to design the conducting polymer with lowest band gap. A comparative study of various electronic properties is presented. The effects of substitution on the behaviour and properties of the copolymers as well as on the density of states (DOS) are discussed. Band gap decreases as a result of substitution on the polymer backbone chain due to decrease in ionization potential and increase in electron affinity values. This is expected to enhance the intrinsic conductivity of the resulting copolymer. Use of alternate donor acceptor moieties within the repeat units should maximize the extended {pi} conjugation.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

Science.gov (United States)

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Thermoresponsive behavior of chitosan-g-N-isopropylacrylamide copolymer solutions.

Science.gov (United States)

Recillas, Maricarmen; Silva, Luisa L; Peniche, Carlos; Goycoolea, Francisco M; Rinaudo, Marguerite; Argüelles-Monal, Waldo M

2009-06-08

Chitosan-g-N-isopropylacrylamide (NIPAm) water-soluble copolymers were synthesized and characterized by FTIR and (1)H NMR spectroscopies combined with conductometric and potentiometric titrations. Their thermoresponsive, fully reversible, behavior in aqueous solutions was characterized by means of microcalorimetry and rheology. During heating of copolymer solutions there is a well-known endothermic effect, which coincides with a marked increase in G' and a moderate decrement in G'' due to the formation of a hydrophobic network at the expense of the net amount of sol fraction. It was also found that a straight dependence between the values of G' above the LCST and the enthalpies associated with the transition reflecting that the connectivity in the gel network is governed by the net number of formed enthalpic-hydrophobic driven-junctions. Both the LCST and the enthalpy change vary with the ionic strength of copolymer solutions, but no dependence was found with the neutralization of the polyelectrolyte chain.

Electrorheological Properties of Suspensions Prepared from Polystyrene- Block- Polyisoprene Copolymer

OpenAIRE

YAVUZ, Mustafa

2014-01-01

Considerable scientific and industrial interest is currently being focused on a class of materials known as electrorheological (ER) fluids, which display remarkable rheological behaviour, being able to convert rapidly and repeatedly from a liquid to solid when an electric field (E) is applied or removed. In this article, the synthesis, characterization, partial hydrolysis and ER properties of polystyrene- block}-polyisoprene copolymer (COP) were investigated. The block copolymer was ...

Study of the molecular mobility of methyl-methacrylate and methacrylic acid copolymers by solid state NMR

International Nuclear Information System (INIS)

Tavares, Maria Ines B.; Mansur, Claudia R.E.; Monteiro, Elisabeth E.C.

1997-01-01

Several methyl-methacrylate/methacrylic acid copolymers were prepared in the presence of concentrated nitric acid. The obtained copolymers were characterized by molecular weigh determination and hydrolization degree. The molecular mobility of these copolymers was studied by solid state nuclear magnetic resonance. Results are presented

Imaging appearance of dextranomer/hyaluronic acid copolymer implant injections for treatment of velopharyngeal insufficiency.

Science.gov (United States)

Brinjikji, W; Cofer, S A; Lane, J I

2015-06-01

Dextranomer/hyaluronic acid copolymer implants are used in treating velopharyngeal insufficiency. These posterior nasopharyngeal implants can be mistaken for pathologic conditions such as retropharyngeal abscess on imaging. We studied the imaging appearance of dextranomer/hyaluronic acid copolymer implants in patients treated for velopharyngeal insufficiency. A consecutive series of patients with velopharyngeal insufficiency treated with dextranomer/hyaluronic acid copolymer were included in this study. Data on patient characteristics and volume of dextranomer/hyaluronic acid copolymer injected were obtained. Postoperative imaging characteristics on plain radiography, CT, and MR imaging were assessed. The imaging appearance of postoperative complications was determined. Sixteen patients were included in this study. Seven patients underwent postoperative plain radiographs, 5 patients underwent CT, and 9 patients underwent MR imaging. Plain radiographs demonstrated soft-tissue swelling in the retropharyngeal space, which resolved at 1 month. On CT, dextranomer/hyaluronic acid copolymer implants appeared as bilateral nasopharyngeal soft-tissue masses isoattenuated to hypoattenuated relative to muscle in 80% (4/5) of patients. On MR imaging, dextranomer/hyaluronic acid copolymer implants appeared as bilateral nasopharyngeal soft-tissue masses that were isointense to muscle on T1 (8/9, 88.9%) and hyperintense to muscle on T2 (8/9, 88.9%) and demonstrated no restricted diffusion (4/4, 100.0%) or peripheral enhancement (7/7, 100.0%). The normal postoperative findings of posterior nasopharyngeal dextranomer/hyaluronic acid copolymer injection on MR imaging is characterized by the presence of bilateral nasopharyngeal soft-tissue masses that are isointense to muscle on T1 and hyperintense on T2, with no restricted diffusion or peripheral enhancement. Velopharyngeal dextranomer/hyaluronic acid copolymer implants are iso- to hypoattenuated to muscle on CT and are not visible

Biodegradation of starch–graft–polystyrene and starch–graft–poly(methacrylic acid copolymers in model river water

Directory of Open Access Journals (Sweden)

Nikolić Vladimir

2013-01-01

Full Text Available In this paper the biodegradation study of grafted copolymers of polystyrene (PS and corn starch and poly(methacrylic acid and corn starch in model river water is described. These copolymers were obtained in the presence of different amine activators. The synthesized copolymers and products of degradation were characterized by Fourier Transform Infrared Spectroscopy (FTIR and Scanning Electron Microscopy (SEM. Biodegradation was monitored by mass decrease and number of microorganisms by Koch’s method. Biodegradation of both copolymers advanced with time, poly(methacrylic acid-graft-starch copolymers completely degraded after 21 day, and polystyrene-graft-starch partially degraded (45.78-93.09 % of total mass after 27 days. Differences in the degree of biodegradation are consequences of different structure of the samples, and there is a significant negative correlation between the share of polystyrene in copolymer and degree of biodegradation. The grafting degree of PS necessary to prevent biodegradation was 54 %. Based on experimental evidence, mechanisms of both biodegradation processes are proposed, and influence of degree of starch and synthetic component of copolymers on degradation were established. [Projekat Ministarstva nauke Republike Srbije, br. 172001 i br. 172062

Spectral Regularization Algorithms for Learning Large Incomplete Matrices.

Science.gov (United States)

Mazumder, Rahul; Hastie, Trevor; Tibshirani, Robert

2010-03-01

We use convex relaxation techniques to provide a sequence of regularized low-rank solutions for large-scale matrix completion problems. Using the nuclear norm as a regularizer, we provide a simple and very efficient convex algorithm for minimizing the reconstruction error subject to a bound on the nuclear norm. Our algorithm Soft-Impute iteratively replaces the missing elements with those obtained from a soft-thresholded SVD. With warm starts this allows us to efficiently compute an entire regularization path of solutions on a grid of values of the regularization parameter. The computationally intensive part of our algorithm is in computing a low-rank SVD of a dense matrix. Exploiting the problem structure, we show that the task can be performed with a complexity linear in the matrix dimensions. Our semidefinite-programming algorithm is readily scalable to large matrices: for example it can obtain a rank-80 approximation of a 10(6) × 10(6) incomplete matrix with 10(5) observed entries in 2.5 hours, and can fit a rank 40 approximation to the full Netflix training set in 6.6 hours. Our methods show very good performance both in training and test error when compared to other competitive state-of-the art techniques.

Vertical vs Lateral Macrophase Separation in Thin Films of Block Copolymer Mixtures

DEFF Research Database (Denmark)

Berezkin, Anatoly V.; Jung, Florian; Posselt, Dorthe

2017-01-01

Mixtures of two diblock copolymers of very different lengths may feature both macro- and microphase separation; however, not much is known about the mechanisms of separation in diblock copolymer thin films. In the present work, we study thin films of mixtures of two compositionally symmetric bloc...

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

International Nuclear Information System (INIS)

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)

Cytotoxicity of copolymer PHEMA-g-LDPE obtained for ionizing radiation

International Nuclear Information System (INIS)

Lorenzetti, Solange G.; Camillo, Maria A.P.; Higa, Olga Z.; Queiroz, Alvaro A.A. de

2005-01-01

Polymeric biomaterials are the polymers described in the literature which are employed in medicine and biotechnology. The aim of the work was the preparation of biocompatible polymeric surface for the posterior immobilization of protein compounds using grafted copolymers obtained by ionizing radiation. The copolymers was obtained by gamma irradiation induced grafting of 2-hydroxyethyl methacrylate (HEMA) onto low density polyethylene (LDPE) in different conditions.. The grafting yield ranged from 2% to 50%. The copolymers were analysed by infrared spectroscopy (FTIR). MEV micrographs showed a smooth surface for the virgin LDPE and rough surface for the copolymers due to the grafted PHEMA. The hydrophilic property appeared with the grafting increase of PHEMA onto LDPE. The diffusion coefficient was determined. Cytotoxicity assay was performed for the evaluation of biocompatibility. The method is based on the quantitative assesment of surviving viable cells upon exposure of CHO cells to the material extract and incubation with the supravital dye MTS. The amount of MTS, taken up by the population of cells is directly proportional to the number of viable cells in culture. The grafted polymers were not cytotoxic and will be used for the chemical immobilization of the enzyme phospholipase A2, purified from the rattlesnake venom. (author)

Age-related patterns of drug use initiation among polydrug using regular psychostimulant users.

Science.gov (United States)

Darke, Shane; Kaye, Sharlene; Torok, Michelle

2012-09-01

To determine age-related patterns of drug use initiation, drug sequencing and treatment entry among regular psychostimulant users. Cross-sectional study of 269 regular psychostimulant users, administered a structured interview examining onset of use for major licit and illicit drugs. The mean age at first intoxication was not associated with age or gender. In contrast, younger age was associated with earlier ages of onset for all of the illicit drug classes. Each additional year of age was associated with a 4 month increase in onset age for methamphetamine, and 3 months for heroin. By the age of 17, those born prior to 1961 had, on average, used only tobacco and alcohol, whereas those born between 1986 and 1990 had used nine different drug classes. The period between initial use and the transition to regular use, however, was stable. Age was also negatively correlated with both age at initial injection and regular injecting. Onset sequences, however, remained stable. Consistent with the age-related patterns of drug use, each additional year of age associated with a 0.47 year increase in the age at first treatment. While the age at first intoxication appeared stable, the trajectory through illicit drug use was substantially truncated. The data indicate that, at least among those who progress to regular illicit drug use, younger users are likely to be exposed to far broader polydrug use in their teens than has previously been the case. © 2012 Australasian Professional Society on Alcohol and other Drugs.

Selection of regularization parameter for l1-regularized damage detection

Science.gov (United States)

Hou, Rongrong; Xia, Yong; Bao, Yuequan; Zhou, Xiaoqing

2018-06-01

The l1 regularization technique has been developed for structural health monitoring and damage detection through employing the sparsity condition of structural damage. The regularization parameter, which controls the trade-off between data fidelity and solution size of the regularization problem, exerts a crucial effect on the solution. However, the l1 regularization problem has no closed-form solution, and the regularization parameter is usually selected by experience. This study proposes two strategies of selecting the regularization parameter for the l1-regularized damage detection problem. The first method utilizes the residual and solution norms of the optimization problem and ensures that they are both small. The other method is based on the discrepancy principle, which requires that the variance of the discrepancy between the calculated and measured responses is close to the variance of the measurement noise. The two methods are applied to a cantilever beam and a three-story frame. A range of the regularization parameter, rather than one single value, can be determined. When the regularization parameter in this range is selected, the damage can be accurately identified even for multiple damage scenarios. This range also indicates the sensitivity degree of the damage identification problem to the regularization parameter.

Immobilization of trichoderma REESEI (QM 9414) cells with paper covered with ionic copolymer by radiation polymerization

International Nuclear Information System (INIS)

Lu Zhaoxin

1992-01-01

Cationic-hydrophobic copolymer and anionic-hydrophobic copolymer was covered onto surface of paper by radiation polymerization. The paper covered with ionic copolymer was used as carrier of immobilizing Trichoderma reesei cells. Results showed that the cells were immobilized firmly on the carriers and not dislocated from the carriers by shaking. All of FPA of the cells immobilized with the carriers covered with cationic copolymer were higher than that of un-immobilized free cells. The carriers covered with anionic copolymer showed good effect on immobilization of the cells. The weight of immobilized cells increase as increasing the component of DEAEMA in poly (DEAEMA-ATMPT) or decreasing the component of AA in poly (AA-ATMPT). It also increase with the increase of water absorption in poly (DEAEMA-ATMPT) or decrease of water absorption in poly (AA-ATMPT). It shows the static interaction play an important role in the immobilization of cells with ionic copolymer materials

Synthesis and Characterization of Smart Block Copolymers for Biomineralization and Biomedical Applications

Energy Technology Data Exchange (ETDEWEB)

Kanapathipillai, Mathumai [Iowa State Univ., Ames, IA (United States)

2008-01-01

Self-assembly is a powerful tool in forming structures with nanoscale dimensions. Self-assembly of macromolecules provides an efficient and rapid pathway for the formation of structures from the nanometer to micrometer range that are difficult, if not impossible to obtain by conventional lithographic techniques [1]. Depending on the morphologies obtained (size, shape, periodicity, etc.) these self-assembled systems have already been applied or shown to be useful for a number of applications in nanotechnology [2], biomineralization [3, 4], drug delivery [5, 6] and gene therapy [7]. In this respect, amphiphilic block copolymers that self-organize in solution have been found to be very versatile [1]. In recent years, polymer-micellar systems have been designed that are adaptable to their environment and able to respond in a controlled manner to external stimuli. In short, synthesis of 'nanoscale objects' that exhibit 'stimulus-responsive' properties is a topic gathering momentum, because their behavior is reminiscent of that exhibited by proteins [8]. By integrating environmentally sensitive homopolymers into amphiphilic block copolymers, smart block copolymers with self assembled supramolecular structures that exhibit stimuli or environmentally responsive properties can be obtained [1]. Several synthetic polymers are known to have environmentally responsive properties. Changes in the physical, chemical or biochemical environment of these polymers results in modulation of the solubility or chain conformation of the polymer [9]. There are many common schemes of engineering stimuli responsive properties into materials [8, 9]. Polymers exhibiting lower critical solution temperature (LCST) are soluble in solvent below a specific temperature and phase separate from solvent above that temperature while polymers exhibiting upper critical solution temperatures (UCST) phase separate below a certain temperature. The solubility of polymers with ionizable

Rapid ordering of block copolymer thin films

International Nuclear Information System (INIS)

Majewski, Pawel W; Yager, Kevin G

2016-01-01

Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems. (topical review)

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer.

Science.gov (United States)

Huang, Weihuan; Luo, Chunxia; Zhang, Jilin; Han, Yanchun

2007-03-14

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.

Coarse-grained modeling of hybrid block copolymer system

Science.gov (United States)

Su, Yongrui

This thesis is comprised of three major projects of my research. In the first project, I proposed a nanoparticle model and combined it with the Theoretically Informed Coarse Grained (TICG) model for pure polymer systems and the grand canonical slip springs model developed in our group to build a new model for entangled nanocomposites. With Molecule Dynamics(MD) simulation, I studied the mechanic properties of the nanocomposites, for example the influence of nanoparticles size and volume fraction on entanglements, the diffusion of polymers and nanoparticles, and the influence of nanoparticles size and volume fraction on viscosity et al.. We found that the addition of small-size nanoparticles reduces the viscosity of the nanocomposites, which is in contrary to what Einstein predicted a century ago. However, when particle increases its size to micrometers the Einstein predictions is recovered. From our simulation, we believe that small-size nanoparticles can more effectively decrease the entanglements of nanocomposites than larger particles. The free volume effect introduced by small-size nanoparticles also helps decrease the viscosity of the whole system. In the second project, I combined the Ohta-Kawasaki (OK) model [3] and the Covariance Matrix Adaptation Evolutionary Strategy(CMA-ES) to optimize the block copolymer blends self-assembly in the hole-shrink process. The aim is to predict the optimal composition and the optimal surface energy to direct the block copolymer blends self-assembly process in the confined hole. After optimization in the OK model, we calibrated the optimal results by the more reliable TICG model and got the same morphology. By comparing different optimization process, we found that the homopolymers which are comprised of the same monomers as either block of the block copolymer can form a perfect perforated hole and might have better performance than the pure block copolymer. While homopolymers which are comprised of a third-party monomers

RANDNA: a random DNA sequence generator.

Science.gov (United States)

Piva, Francesco; Principato, Giovanni

2006-01-01

Monte Carlo simulations are useful to verify the significance of data. Genomic regularities, such as the nucleotide correlations or the not uniform distribution of the motifs throughout genomic or mature mRNA sequences, exist and their significance can be checked by means of the Monte Carlo test. The test needs good quality random sequences in order to work, moreover they should have the same nucleotide distribution as the sequences in which the regularities have been found. Random DNA sequences are also useful to estimate the background score of an alignment, that is a threshold below which the resulting score is merely due to chance. We have developed RANDNA, a free software which allows to produce random DNA or RNA sequences setting both their length and the percentage of nucleotide composition. Sequences having the same nucleotide distribution of exonic, intronic or intergenic sequences can be generated. Its graphic interface makes it possible to easily set the parameters that characterize the sequences being produced and saved in a text format file. The pseudo-random number generator function of Borland Delphi 6 is used, since it guarantees a good randomness, a long cycle length and a high speed. We have checked the quality of sequences generated by the software, by means of well-known tests, both by themselves and versus genuine random sequences. We show the good quality of the generated sequences. The software, complete with examples and documentation, is freely available to users from: http://www.introni.it/en/software.

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

DEFF Research Database (Denmark)

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...

Field-theoretic simulations of block copolymer nanocomposites in a constant interfacial tension ensemble.

Science.gov (United States)

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.

Mesoscopic multiphase structures and the interfaces of block and graft copolymers in bulk

International Nuclear Information System (INIS)

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)

Dissipative particle dynamics of triblock copolymer melts: A midblock conformational study at moderate segregation

Science.gov (United States)

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.

Formation and Characterization of Anisotropic Block Copolymer Gels

Science.gov (United States)

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.

Tuning the Optoelectronic Properties of Vinylene-Linked Donor−Acceptor Copolymers for Organic Photovoltaics

KAUST Repository

Ko, Sangwon; Mondal, Rajib; Risko, Chad; Lee, Jung Kyu; Hong, Sanghyun; McGehee, Michael D.; Brédas, Jean-Luc; Bao, Zhenan

2010-01-01

-property relationships in organic photovoltaic devices. Both alternating (P) and random copolymers (P1-P4) were prepared via Suzuki and Stille polycondensations, respectively. The cyclopentadithiophene copolymers (P2 and P4) have smaller electrochemical band gaps (1

Facile synthesis of main-chain degradable block copolymers for performance enhanced dismantlable adhesion.

Science.gov (United States)

Sato, Eriko; Hagihara, Takashi; Matsumoto, Akikazu

2012-04-01

Block copolymers consisting of readily degradable polyperoxides and non-degradable vinyl polymers as the block segments were successfully synthesized by reversible chain transfer catalyzed polymerization, which is one of living radical polymerization techniques. The block copolymers showed characteristic morphology and wettability being different from the polymer blends. When block copolymers containing polyperoxide and polymethacrylate blocks were heated below 150 °C, the polyperoxide blocks were completely degraded and the polymethacrylate blocks were recovered without degradation. Block copolymers containing a poly(2-ethylhexyl methacrylate) block were then investigated as a dismantlable adhesion material, which requires adequate bonding strength during use and easy debonding on demand. Among the several block copolymers, the one consisting of poly(2-ethylhexyl methacrylate) and polyperoxide from methyl sorbate (PPMS) (M(n) = 4900) exhibited good performance as a pressure-sensitive adhesive (PSA). After heating the test specimens in a temperature range from 60 to 100 °C, PSA performance, which was evaluated by 180° peel strength and shear holding power measurements, was significantly diminished. Especially, after heating at 100 °C for 1 h, spontaneous debonding of some test specimens was observed because of the evolution of volatile acetaldehyde from PPMS.

Synthesis and characterization of sugar-based methacrylates and their random copolymers by ATRP

Directory of Open Access Journals (Sweden)

G. Acik

2017-10-01

Full Text Available Various sugar-based methacrylate monomers have been prepared and randomly copolymerized with methyl methacrylate (MMA using classical atom transfer radical polymerization (ATRP. Firstly, four different sugar-based methacrylates are synthesized by two-step method: (i etherification of protected monosaccharides with epichlorohydrin and (ii following ring-opening reaction of obtained epoxides with methacrylic acid (MAA in the presence of triethylamine. Next, these monomers are copolymerized with MMA via ATRP at 90 °C to obtain corresponding random copolymers. The molecular weights of the copolymers are determined by both GPC (gel permeation chromatography and 1H-NMR (nuclear magnetic resonance spectroscopy analyses and found as 10600~16800 and 12200~18500 g/mol, respectively. Moreover, the copolymer compositions are also determined by 1H-NMR analysis using characteristic signals of the monomers and found as about 94.1~97.8%, which are good agreement with feeding ratio. In addition, the glass transition temperatures of copolymers are found as 101.2~102.9 °C by changing type and composition of sugar-based methacrylate monomers. Overall, a series of well-defined random copolymers comprising different sugar-based methacrylates and methyl methacrylates were successfully synthesized by classical ATRP method.

Cyclic olefin copolymer-silica nanocomposites foams

Czech Academy of Sciences Publication Activity Database

Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

2016-01-01

Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes

Science.gov (United States)

Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

Optimized star sensors laboratory calibration method using a regularization neural network.

Science.gov (United States)

Zhang, Chengfen; Niu, Yanxiong; Zhang, Hao; Lu, Jiazhen

2018-02-10

High-precision ground calibration is essential to ensure the performance of star sensors. However, the complex distortion and multi-error coupling have brought great difficulties to traditional calibration methods, especially for large field of view (FOV) star sensors. Although increasing the complexity of models is an effective way to improve the calibration accuracy, it significantly increases the demand for calibration data. In order to achieve high-precision calibration of star sensors with large FOV, a novel laboratory calibration method based on a regularization neural network is proposed. A multi-layer structure neural network is designed to represent the mapping of the star vector and the corresponding star point coordinate directly. To ensure the generalization performance of the network, regularization strategies are incorporated into the net structure and the training algorithm. Simulation and experiment results demonstrate that the proposed method can achieve high precision with less calibration data and without any other priori information. Compared with traditional methods, the calibration error of the star sensor decreased by about 30%. The proposed method can satisfy the precision requirement for large FOV star sensors.

Visualization of the distribution of surface-active block copolymers in PDMS-based coatings

DEFF Research Database (Denmark)

Noguer, A. Camós; Latipov, R.; Madsen, F. B.

2018-01-01

the distribution and release of these block copolymers from PDMS-based coatings has been previously reported. However, the distribution and behaviour of these compounds in the bulk of the PDMS coating are not fully understood. A novel fluorescent-labelled triblock PEG-b-PDMS-b-PEG copolymer was synthesized...... results in non-specific protein adsorption and wettability issues. Poly(ethylene glycol)-based surface-active block copolymers and surfactants have been added to PDMS coatings and films to impart biofouling resistance and hydrophilicity to the PDMS surface with successful results. Information regarding...

Self-Assembly of Rod-Coil Block Copolymers

National Research Council Canada - National Science Library

Jenekhe, S

1999-01-01

... the self-assembly of new rod-coil diblock, rod- coil-rod triblock, and coil-rod-coil triblock copolymers from solution and the resulting discrete and periodic mesostmctares with sizes in the 100...

Identifying the nature of surface chemical modification for directed self-assembly of block copolymers