Summary of compliant and multi-arm control at NASA. Langley Research Center

NASA Technical Reports Server (NTRS)

Harrison, Fenton W.

1992-01-01

The topics are presented in viewgraph form and include the: single arm system, single arm axis system, single arm control systems, single arm hand controller axis system, single arm position axis system, single arm vision axis system, single arm force axis system, multi-arm system, multi-arm axis system, and the dual arm hand control axis system with control signals.

Risk-aware multi-armed bandit problem with application to portfolio selection

PubMed Central

Huo, Xiaoguang

2017-01-01

Sequential portfolio selection has attracted increasing interest in the machine learning and quantitative finance communities in recent years. As a mathematical framework for reinforcement learning policies, the stochastic multi-armed bandit problem addresses the primary difficulty in sequential decision-making under uncertainty, namely the exploration versus exploitation dilemma, and therefore provides a natural connection to portfolio selection. In this paper, we incorporate risk awareness into the classic multi-armed bandit setting and introduce an algorithm to construct portfolio. Through filtering assets based on the topological structure of the financial market and combining the optimal multi-armed bandit policy with the minimization of a coherent risk measure, we achieve a balance between risk and return. PMID:29291122

Risk-aware multi-armed bandit problem with application to portfolio selection.

PubMed

Huo, Xiaoguang; Fu, Feng

2017-11-01

Sequential portfolio selection has attracted increasing interest in the machine learning and quantitative finance communities in recent years. As a mathematical framework for reinforcement learning policies, the stochastic multi-armed bandit problem addresses the primary difficulty in sequential decision-making under uncertainty, namely the exploration versus exploitation dilemma, and therefore provides a natural connection to portfolio selection. In this paper, we incorporate risk awareness into the classic multi-armed bandit setting and introduce an algorithm to construct portfolio. Through filtering assets based on the topological structure of the financial market and combining the optimal multi-armed bandit policy with the minimization of a coherent risk measure, we achieve a balance between risk and return.

Correcting for multiple-testing in multi-arm trials: is it necessary and is it done?

PubMed

Wason, James M S; Stecher, Lynne; Mander, Adrian P

2014-09-17

Multi-arm trials enable the evaluation of multiple treatments within a single trial. They provide a way of substantially increasing the efficiency of the clinical development process. However, since multi-arm trials test multiple hypotheses, some regulators require that a statistical correction be made to control the chance of making a type-1 error (false-positive). Several conflicting viewpoints are expressed in the literature regarding the circumstances in which a multiple-testing correction should be used. In this article we discuss these conflicting viewpoints and review the frequency with which correction methods are currently used in practice. We identified all multi-arm clinical trials published in 2012 by four major medical journals. Summary data on several aspects of the trial design were extracted, including whether the trial was exploratory or confirmatory, whether a multiple-testing correction was applied and, if one was used, what type it was. We found that almost half (49%) of published multi-arm trials report using a multiple-testing correction. The percentage that corrected was higher for trials in which the experimental arms included multiple doses or regimens of the same treatments (67%). The percentage that corrected was higher in exploratory than confirmatory trials, although this is explained by a greater proportion of exploratory trials testing multiple doses and regimens of the same treatment. A sizeable proportion of published multi-arm trials do not correct for multiple-testing. Clearer guidance about whether multiple-testing correction is needed for multi-arm trials that test separate treatments against a common control group is required.

Star polymer-based unimolecular micelles and their application in bio-imaging and diagnosis.

PubMed

Jin, Xin; Sun, Pei; Tong, Gangsheng; Zhu, Xinyuan

2018-02-03

As a novel kind of polymer with covalently linked core-shell structure, star polymers behave in nanostructure in aqueous medium at all concentration range, as unimolecular micelles at high dilution condition and multi-micelle aggregates in other situations. The unique morphologies endow star polymers with excellent stability and functions, making them a promising platform for bio-application. A variety of functions including imaging and therapeutics can be achieved through rational structure design of star polymers, and the existence of plentiful end-groups on shell offers the opportunity for further modification. In the last decades, star polymers have become an attracting platform on fabrication of novel nano-systems for bio-imaging and diagnosis. Focusing on the specific topology and physicochemical properties of star polymers, we have reviewed recent development of star polymer-based unimolecular micelles and their bio-application in imaging and diagnosis. The main content of this review summarizes the synthesis of integrated architecture of star polymers and their self-assembly behavior in aqueous medium, focusing especially on the recent advances on their bio-imaging application and diagnosis use. Finally, we conclude with remarks and give some outlooks for further exploration in this field. Copyright © 2018 Elsevier Ltd. All rights reserved.

Structure and rheology of star polymers in confined geometries: a mesoscopic simulation study.

PubMed

Zheng, Feiwo; Goujon, Florent; Mendonça, Ana C F; Malfreyt, Patrice; Tildesley, Dominic J

2015-11-28

Mesoscopic simulations of star polymer melts adsorbed onto solid surfaces are performed using the dissipative particle dynamics (DPD) method. A set of parameters is developed to study the low functionality star polymers under shear. The use of a new bond-angle potential between the arms of the star creates more rigid chains and discriminates between different functionalities at equilibrium, but still allows the polymers to deform appropriately under shear. The rheology of the polymer melts is studied by calculating the kinetic friction and viscosity and there is good agreement with experimental properties of these systems. The study is completed with predictive simulations of star polymer solutions in an athermal solvent.

Network formation and gelation in telechelic star polymers

NASA Astrophysics Data System (ADS)

Wadgaonkar, Indrajit; Chatterji, Apratim

2017-02-01

We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while the rest of the monomers are uncharged. Our work is motivated by the experimental observations [A. Kulkarni et al., Macromolecules 48, 6580 (2015)] in which rheological studies of telechelic star polymers of poly-(L-lactide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to 2000 times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective attractive Lennard-Jones potentials or dipolar potentials to model telechelic interactions. Instead we use explicit Coulomb positive and negative charges at the tip of polymer-arms of our bead-spring model of star polymers. By our simulations we show that the dipoles at the tip of star arms aggregate together to form clusters of dipoles. Each cluster has contributions from several stars, and in turn each star contributes to several clusters. Thus the entire polymer melt forms a connected network. Network forming tendencies decrease with a decrease of the value of the effective charge constituting the dipole: this can be experimentally realized by choosing a different ionomer for the star tip. We systematically varied the value of dipole charges, the fraction of star-arms with dipoles at the tip, and the length of the arms. The choice of explicit charges in our calculations enables us to make better quantitative predictions about the onset of gelation; moreover we get qualitatively distinct results about structural organization of dipoles within a dipole-cluster.

Network formation and gelation in telechelic star polymers.

PubMed

Wadgaonkar, Indrajit; Chatterji, Apratim

2017-02-28

We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while the rest of the monomers are uncharged. Our work is motivated by the experimental observations [A. Kulkarni et al., Macromolecules 48, 6580 (2015)] in which rheological studies of telechelic star polymers of poly-(L-lactide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to 2000 times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective attractive Lennard-Jones potentials or dipolar potentials to model telechelic interactions. Instead we use explicit Coulomb positive and negative charges at the tip of polymer-arms of our bead-spring model of star polymers. By our simulations we show that the dipoles at the tip of star arms aggregate together to form clusters of dipoles. Each cluster has contributions from several stars, and in turn each star contributes to several clusters. Thus the entire polymer melt forms a connected network. Network forming tendencies decrease with a decrease of the value of the effective charge constituting the dipole: this can be experimentally realized by choosing a different ionomer for the star tip. We systematically varied the value of dipole charges, the fraction of star-arms with dipoles at the tip, and the length of the arms. The choice of explicit charges in our calculations enables us to make better quantitative predictions about the onset of gelation; moreover we get qualitatively distinct results about structural organization of dipoles within a dipole-cluster.

The Pharmacokinetics and Biodistribution of a 64 kDa PolyPEG Star Polymer After Subcutaneous and Pulmonary Administration to Rats.

PubMed

Khor, Song Yang; Hu, Jinming; McLeod, Victoria M; Quinn, John F; Porter, Christopher J H; Whittaker, Michael R; Kaminskas, Lisa M; Davis, Thomas P

2016-01-01

PolyPEG star polymers have potential utility as cost-effective polymeric drug delivery vehicles, and as such, it is important to develop an understanding of their biopharmaceutical behavior. Moreover, although a number of studies have evaluated the utility of PolyPEG stars in vitro, investigation of these novel materials in vivo has been limited. Herein, we evaluated the pharmacokinetics of a 64 kDa tritiated PEG-based star polymer after subcutaneous and pulmonary administration in rats. After subcutaneous administration, the star polymer showed near complete bioavailability (∼80%) and a similar organ biodistribution profile to the polymer after intravenous administration. After intratracheal instillation to the lungs, the star polymer showed limited bioavailability (∼3%), and most of the administered radiolabel was recovered in lung tissue and feces after 6 d. The data reported here suggest that star polymers display similar pharmaceutical behavior to PEGylated dendrimers after subcutaneous and inhaled delivery and may therefore be used as similar, but more cost-effective drug delivery vehicles. Copyright © 2016. Published by Elsevier Inc.

Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution.

PubMed

Edwards-Gayle, Charlotte J C; Greco, Francesca; Hamley, Ian W; Rambo, Robert P; Reza, Mehedi; Ruokolainen, Janne; Skoulas, Dimitrios; Iatrou, Hermis

2018-01-08

We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials.

A supramolecular miktoarm star polymer based on porphyrin metal complexation in water.

PubMed

Hou, Zhanyao; Dehaen, Wim; Lyskawa, Joël; Woisel, Patrice; Hoogenboom, Richard

2017-07-25

A novel supramolecular miktoarm star polymer was successfully constructed in water from a pyridine end-decorated polymer (Py-PmDEGA) and a metalloporphyrin based star polymer (ZnTPP-(PEG) 4 ) via metal-ligand coordination. The Py-PmDEGA moiety was prepared via a combination of reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequent aminolysis and Michael addition reactions to introduce the pyridine end-group. The ZnTPP(PEG) 4 star-polymer was synthesized by the reaction between tetrakis(p-hydroxyphenyl)porphyrin and toluenesulfonyl-PEG, followed by insertion of a zinc ion into the porphyrin core. The formation of a well-defined supramolecular AB 4 -type miktoarm star polymer was unambiguously demonstrated via UV-Vis spectroscopic titration, isothermal titration calorimetry (ITC) and diffusion ordered NMR spectroscopy (DOSY).

Interaction of multiarmed spirals in bistable media.

PubMed

He, Ya-feng; Ai, Bao-quan; Liu, Fu-cheng

2013-05-01

We study the interaction of both dense and sparse multiarmed spirals in bistable media modeled by equations of the FitzHugh-Nagumo type. A dense one-armed spiral is characterized by its fixed tip. For dense multiarmed spirals, when the initial distance between tips is less than a critical value, the arms collide, connect, and disconnect continuously as the spirals rotate. The continuous reconstruction between the front and the back drives the tips to corotate along a rough circle and to meander zigzaggedly. The rotation frequency of tip, the frequency of zigzagged displacement, the frequency of spiral, the oscillation frequency of media, and the number of arms satisfy certain relations as long as the control parameters of the model are fixed. When the initial distance between tips is larger than the critical value, the behaviors of individual arms within either dense or sparse multiarmed spirals are identical to that of corresponding one-armed spirals.

Investigation of star polymer nanoshells for use in diagnostic imaging and photothermal cancer therapy applications

NASA Astrophysics Data System (ADS)

Gomez, Lizabeth

Gold nanoshells can be designed to possess high light scattering and strong absorption of near-infrared light. Thus, they have the potential to be used in biological applications as contrast agents for diagnostic imaging as well as for thermal ablation of tumor cells in future cancer treatments. In this study, gold nanoshells with dye-loaded star polymer cores were investigated. Uniform near-infrared gold nanoshells with 100 nm diameters were successfully generated using different batches of star polymer templates and were characterized by UV-visible spectroscopy and scanning electron microscopy. The star polymers used were block copolymer structures with a hydrophobic polystyrene (PS) core and a hydrophilic poly(N,N-dimethylaminoethylmethracrylate) (DMAEMA) outer shell. Within this work, a general procedure was established in order to achieve a desired gold nanoshell size regardless of the star polymer batch used, since the synthesis process conditions can cause star polymers to vary in size as well in the number and length of amino-functionalized arms. Control of the gold nanoshell diameter was optimized after an in-depth analysis of the synthesis parameters that affected the formation and final size of the dye-loaded star polymer gold nanoshells. The main parameters examined were pH of the gold seeds used to nucleate the templates and the ratio of star polymer to gold hydroxide used during the growth of the outer gold shell.

Molecular weight (hydrodynamic volume) dictates the systemic pharmacokinetics and tumour disposition of PolyPEG star polymers.

PubMed

Khor, Song Yang; Hu, Jinming; McLeod, Victoria M; Quinn, John F; Williamson, Mark; Porter, Christopher J H; Whittaker, Michael R; Kaminskas, Lisa M; Davis, Thomas P

2015-11-01

Herein we report for the first time the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers synthesised via a versatile arm-first reversible addition-fragmentation chain transfer (RAFT) polymerisation approach. The biopharmaceutical behaviour of three different molecular weight (49, 64 and 94kDa) POEGA stars was evaluated in rats and nude mice bearing human MDA MB-231 tumours after intravenous administration. The 94kDa star polymer exhibited a longer plasma exposure time than the 49kDa or 64kDa star polymer; an observation attributable to differences in the rates of both polymer biodegradation and urinary excretion. Tumour biodistribution also correlated with molecular weight and was greatest for the longest circulating 94kDa star. Different patterns of liver and spleen biodistribution were observed between mice and rats for the different sized polymers. The polymers were also well-tolerated in vivo and in vitro at therapeutic concentrations. Advances in nanotechnology has enabled scientists to produce nanoparticle as drug carriers in cancer therapeutics. In this article, the authors studied the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers of different size, after intravenous injections. This would allow the subsequent comparison to other drug delivery systems for better drug delivery. Copyright © 2015 Elsevier Inc. All rights reserved.

Effectively delivering a unique hsp90 inhibitor using star polymers.

PubMed

Kim, Seong Jong; Ramsey, Deborah M; Boyer, Cyrille; Davis, Thomas P; McAlpine, Shelli R

2013-07-25

We report the synthesis of a novel heat shock protein 90 (hsp90) inhibitor conjugated to a star polymer. Using reversible addition-fragmentation chain-transfer (RAFT) polymerization, we prepared star polymers comprised of PEG attached to a predesigned functional core. The stars were cross-linked using disulfide linkers, and a tagged version of our hsp90 inhibitor was conjugated to the polymer core to generate nanoparticles (14 nM). Dynamic light scattering showed that the nanoparticles were stable in cell growth media for 5 days, and HPLC analysis of compound-release at 3 different pH values showed that release was pH dependent. Cell cytotoxicity studies and confocal microscopy verify that our hsp90 inhibitor was delivered to cells using this nanoparticle delivery system. Further, delivery of our hsp90 inhibitor using star polymer induces apoptosis by a caspase 3-dependent pathway. These studies show that we can deliver our hsp90 inhibitor effectively using star polymers, and induce apoptosis by the same pathway as the parent compound.

A soluble star-shaped silsesquioxane-cored polymer-towards novel stabilization of pH-dependent high internal phase emulsions.

PubMed

Xing, Yuxiu; Peng, Jun; Xu, Kai; Gao, Shuxi; Gui, Xuefeng; Liang, Shengyuan; Sun, Longfeng; Chen, Mingcai

2017-08-30

A well-defined pH-responsive star-shaped polymer containing poly(N,N-dimethylaminoethyl methacrylate) (PDMA) arms and a cage-like methacryloxypropyl silsesquioxane (CMSQ-T 10 ) core was used as an interfacial stabilizer for emulsions consisting of m-xylene and water. We explored the properties of the CMSQ/PDMA star-shaped polymer using the characteristic results of nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), dynamic light scattering (DLS), and zeta potential and conductivity measurements. The interfacial tension results showed that the CMSQ/PDMA star-shaped polymer reduced the interfacial tension between water and oil in a pH-dependent manner. Gelled high internal phase emulsions (HIPEs) including o/w and w/o types were formed in the pH ranges of 1.2-5.8 and 9.1-12.3 with the CMSQ/PDMA star-shaped polymer as a stabilizer, when the oil fractions were 80-90 vol% and 10-20 vol%, respectively. The soluble star-shaped polymer aggregated spontaneously to form a microgel that adsorbed to the two immiscible phases. Images of the fluorescently labeled polymers demonstrated that there was a star-shaped polymer in the continuous phase, and the non-Pickering stabilization based on the percolating network of the star-shaped polymer also contributed to the stabilization of the HIPE. This pH-dependent HIPE was prepared with a novel stabilization mechanism consisting of microgel adsorption and non-Pickering stabilization. Moreover, the preparation of HIPEs provided the possibility of their application in porous materials and responsive materials.

Synthesis and Properties of Star HPMA Copolymer Nanocarriers Synthesised by RAFT Polymerisation Designed for Selective Anticancer Drug Delivery and Imaging.

PubMed

Chytil, Petr; Koziolová, Eva; Janoušková, Olga; Kostka, Libor; Ulbrich, Karel; Etrych, Tomáš

2015-06-01

High-molecular-weight star polymer drug nanocarriers intended for the treatment and/or visualisation of solid tumours were synthesised, and their physico-chemical and preliminary in vitro biological properties were determined. The water-soluble star polymer carriers were prepared by the grafting of poly(amido amine) (PAMAM) dendrimers by hetero-telechelic N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers, synthesised by the controlled radical Reversible Addition Fragmentation chain Transfer (RAFT) polymerisation. The well-defined star copolymers with Mw values ranging from 2 · 10(5) to 6 · 10(5) showing a low dispersity (approximately 1.2) were prepared in a high yield. A model anticancer drug, doxorubicin, was bound to the star polymer through a hydrazone bond, enabling the pH-controlled drug release in the target tumour tissue. The activated polymer arm ends of the star copolymer carrier enable a one-point attachment for the targeting ligands and/or a labelling moiety. In this study, the model TAMRA fluorescent dye was used to prove the feasibility of the polymer carrier visualisation by optical imaging in vitro. The tailor-made structure of the star polymer carriers should facilitate the synthesis of targeted polymer-drug conjugates, even polymer theranostics, for simultaneous tumour drug delivery and imaging. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel star-shaped poly(carboxylic acid) for resin-modified glass-ionomer restoratives.

PubMed

Weng, Y; Howard, L; Xie, D

2014-07-01

We have developed a novel glass-ionomer cement (GIC) system composed of photo-curable star-shaped poly(acrylic acid-co-itaconic acid)s. These polyacids were synthesized via a chain-transfer radical polymerization using a newly synthesized multi-arm chain-transfer agent. The star-shaped polyacids showed significantly lower viscosities in water as compared to the linear polyacids. Due to the lower viscosities, the molecular weight (MW) of the polyacids can be significantly increased for enhancing the mechanical strengths while keeping the ease of mixing and handling. The effects of MW, GM-tethering ratio, P/L ratio, and aging on the compressive properties of the experimental cements were significant. The light-cured experimental cements showed significantly improved mechanical strengths i.e. 49% in yield strength, 41% in modulus, 25% in CS, 20% in DTS, and 36% in FS, higher than commercial Fuji II LC. After aging in water for 1 month, the compressive strength of the novel light-cured experimental cement reached 343 MPa, which was 34% and 42% higher than Fuji II and Fuji II LC, respectively. This one-month aged experimental cement was also 23% higher than itself after one day aging, indicating that aging in water can significantly enhance salt-bridge formation for this novel star-shaped polyacid-comprised GIC.

A multi-stage drop-the-losers design for multi-arm clinical trials.

PubMed

Wason, James; Stallard, Nigel; Bowden, Jack; Jennison, Christopher

2017-02-01

Multi-arm multi-stage trials can improve the efficiency of the drug development process when multiple new treatments are available for testing. A group-sequential approach can be used in order to design multi-arm multi-stage trials, using an extension to Dunnett's multiple-testing procedure. The actual sample size used in such a trial is a random variable that has high variability. This can cause problems when applying for funding as the cost will also be generally highly variable. This motivates a type of design that provides the efficiency advantages of a group-sequential multi-arm multi-stage design, but has a fixed sample size. One such design is the two-stage drop-the-losers design, in which a number of experimental treatments, and a control treatment, are assessed at a prescheduled interim analysis. The best-performing experimental treatment and the control treatment then continue to a second stage. In this paper, we discuss extending this design to have more than two stages, which is shown to considerably reduce the sample size required. We also compare the resulting sample size requirements to the sample size distribution of analogous group-sequential multi-arm multi-stage designs. The sample size required for a multi-stage drop-the-losers design is usually higher than, but close to, the median sample size of a group-sequential multi-arm multi-stage trial. In many practical scenarios, the disadvantage of a slight loss in average efficiency would be overcome by the huge advantage of a fixed sample size. We assess the impact of delay between recruitment and assessment as well as unknown variance on the drop-the-losers designs.

Small cell foams containing a modified dense star polymer or dendrimer as a nucleating agent

DOEpatents

Hedstrand, David M.; Tomalia, Donald A.

1995-01-01

A small cell foam having a modified dense star polymer or dendrimer is described. This modified dense star polymer or dendrimer has a highly branched interior of one monomeric composition and an exterior structure of a different monomeric composition capable of providing a hydrophobic outer shell and a particle diameter of from about 5 to about 1,000 nm with a matrix polymer.

Small cell foams containing a modified dense star polymer or dendrimer as a nucleating agent

DOEpatents

Hedstrand, D.M.; Tomalia, D.A.

1995-02-28

A small cell foam having a modified dense star polymer or dendrimer is described. This modified dense star polymer or dendrimer has a highly branched interior of one monomeric composition and an exterior structure of a different monomeric composition capable of providing a hydrophobic outer shell and a particle diameter of from about 5 to about 1,000 nm with a matrix polymer.

Nano-Star-Shaped Polymers for Drug Delivery Applications.

PubMed

Yang, Da-Peng; Oo, Ma Nwe Nwe Linn; Deen, Gulam Roshan; Li, Zibiao; Loh, Xian Jun

2017-11-01

With the advancement of polymer engineering, complex star-shaped polymer architectures can be synthesized with ease, bringing about a host of unique properties and applications. The polymer arms can be functionalized with different chemical groups to fine-tune the response behavior or be endowed with targeting ligands or stimuli responsive moieties to control its physicochemical behavior and self-organization in solution. Rheological properties of these solutions can be modulated, which also facilitates the control of the diffusion of the drug from these star-based nanocarriers. However, these star-shaped polymers designed for drug delivery are still in a very early stage of development. Due to the sheer diversity of macromolecules that can take on the star architectures and the various combinations of functional groups that can be cross-linked together, there remain many structure-property relationships which have yet to be fully established. This review aims to provide an introductory perspective on the basic synthetic methods of star-shaped polymers, the properties which can be controlled by the unique architecture, and also recent advances in drug delivery applications related to these star candidates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A scattering function of star polymers including excluded volume effects

DOE PAGES

Li, Xin; Do, Changwoo; Liu, Yun; ...

2014-11-04

In this work we present a new model for the form factor of a star polymer consisting of self-avoiding branches. This new model incorporates excluded volume effects and is derived from the two point correlation function for a star polymer.. We compare this model to small angle neutron scattering (SANS) measurements from polystyrene (PS) stars immersed in a good solvent, tetrahydrofuran (THF). It is shown that this model provides a good description of the scattering signature originating from the excluded volume effect and it explicitly elucidates the connection between the global conformation of a star polymer and the local stiffnessmore » of its constituent branch.« less

Universal size properties of a star-ring polymer structure in disordered environments

NASA Astrophysics Data System (ADS)

Haydukivska, K.; Blavatska, V.

2018-03-01

We consider the complex polymer system, consisting of a ring polymer connected to the f1-branched starlike structure, in a good solvent in the presence of structural inhomogeneities. In particular cases f1=1 and f1=2 , such a system restores the synthesized tadpole-shaped polystyrenes [Doi et al., Macromolecules 46, 1075 (2013), 10.1021/ma302511j]. We assume that structural defects are correlated at large distances x according to a power law x-a. Applying the direct polymer renormalization approach, we evaluate the universal size characteristics such as the ratio of the radii of gyration of star-ring and star topologies, and compare the effective sizes of single arms in complex structures and isolated polymers of the same total molecular weight. The nontrivial impact of disorder on these quantities is analyzed.

Effective delivery of siRNA into cancer cells and tumors using well-defined biodegradable cationic star polymers.

PubMed

Boyer, Cyrille; Teo, Joann; Phillips, Phoebe; Erlich, Rafael B; Sagnella, Sharon; Sharbeen, George; Dwarte, Tanya; Duong, Hien T T; Goldstein, David; Davis, Thomas P; Kavallaris, Maria; McCarroll, Joshua

2013-06-03

Cancer is one of the most common causes of death worldwide. Two types of cancer that have high mortality rates are pancreatic and lung cancer. Despite improvements in treatment strategies, resistance to chemotherapy and the presence of metastases are common. Therefore, novel therapies which target and silence genes involved in regulating these processes are required. Short-interfering RNA (siRNA) holds great promise as a therapeutic to silence disease-causing genes. However, siRNA requires a delivery vehicle to enter the cell to allow it to silence its target gene. Herein, we report on the design and synthesis of cationic star polymers as novel delivery vehicles for siRNA to silence genes in pancreatic and lung cancer cells. Dimethylaminoethyl methacrylate (DMAEMA) was polymerized via reversible addition-fragmentation transfer polymerization (RAFT) and then chain extended in the presence of both cross-linkers N,N-bis(acryloyl)cistamine and DMAEMA, yielding biodegradable well-defined star polymers. The star polymers were characterized by transmission electron microscopy, dynamic light scattering, ζ potential, and gel permeation chromatography. Importantly, the star polymers were able to self-assemble with siRNA and form small uniform nanoparticle complexes. Moreover, the ratios of star polymer required to complex siRNA were nontoxic in both pancreatic and lung cancer cells. Treatment with star polymer-siRNA complexes resulted in uptake of siRNA into both cell lines and a significant decrease in target gene mRNA and protein levels. In addition, delivery of clinically relevant amounts of siRNA complexed to the star polymer were able to silence target gene expression by 50% in an in vivo tumor setting. Collectively, these results provide the first evidence of well-defined small cationic star polymers to deliver active siRNA to both pancreatic and lung cancer cells and may be a valuable tool to inhibit key genes involved in promoting chemotherapy drug resistance and metastases.

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Star polymers as unit cells for coarse-graining cross-linked networks

NASA Astrophysics Data System (ADS)

Molotilin, Taras Y.; Maduar, Salim R.; Vinogradova, Olga I.

2018-03-01

Reducing the complexity of cross-linked polymer networks by preserving their main macroscale properties is key to understanding them, and a crucial issue is to relate individual properties of the polymer constituents to those of the reduced network. Here we study polymer networks in a good solvent, by considering star polymers as their unit elements, and first quantify the interaction between their centers of masses. We then reduce the complexity of a network by replacing sets of its bridged star polymers by equivalent effective soft particles with dense cores. Our coarse graining allows us to approximate complex polymer networks by much simpler ones, keeping their relevant mechanical properties, as illustrated in computer experiments.

Macromolecular 'size' and 'hardness' drives structure in solvent-swollen blends of linear, cyclic, and star polymers.

PubMed

Gartner, Thomas E; Jayaraman, Arthi

2018-01-17

In this paper, we apply molecular simulation and liquid state theory to uncover the structure and thermodynamics of homopolymer blends of the same chemistry and varying chain architecture in the presence of explicit solvent species. We use hybrid Monte Carlo (MC)/molecular dynamics (MD) simulations in the Gibbs ensemble to study the swelling of ∼12 000 g mol -1 linear, cyclic, and 4-arm star polystyrene chains in toluene. Our simulations show that the macroscopic swelling response is indistinguishable between the various architectures and matches published experimental data for the solvent annealing of linear polystyrene by toluene vapor. We then use standard MD simulations in the NPT ensemble along with polymer reference interaction site model (PRISM) theory to calculate effective polymer-solvent and polymer-polymer Flory-Huggins interaction parameters (χ eff ) in these systems. As seen in the macroscopic swelling results, there are no significant differences in the polymer-solvent and polymer-polymer χ eff between the various architectures. Despite similar macroscopic swelling and effective interaction parameters between various architectures, the pair correlation function between chain centers-of-mass indicates stronger correlations between cyclic or star chains in the linear-cyclic blends and linear-star blends, compared to linear chain-linear chain correlations. Furthermore, we note striking similarities in the chain-level correlations and the radius of gyration of cyclic and 4-arm star architectures of identical molecular weight. Our results indicate that the cyclic and star chains are 'smaller' and 'harder' than their linear counterparts, and through comparison with MD simulations of blends of soft spheres with varying hardness and size we suggest that these macromolecular characteristics are the source of the stronger cyclic-cyclic and star-star correlations.

Near-IR-induced dissociation of thermally-sensitive star polymers.

PubMed

Dai, Yuqiong; Sun, Hao; Pal, Sunirmal; Zhang, Yunlu; Park, Sangwoo; Kabb, Christopher P; Wei, Wei David; Sumerlin, Brent S

2017-03-01

Responsive systems sensitive to near-infrared (NIR) light are promising for triggered release due to efficient deep tissue penetration of NIR irradiation relative to higher energy sources ( e.g. , UV), allowing for spatiotemporal control over triggering events with minimal potential for tissue damage. Herein, we report star polymers containing thermally-labile azo linkages that dissociate during conventional heating or during localized heating via the photothermal effect upon NIR irradiation. Controlled release during conventional heating was investigated for the star polymers loaded with a model dye, with negligible release being observed at 25 °C and >80% release at 90 °C. Star polymers co-loaded with NIR-responsive indocyanine green showed rapid dye release upon NIR irradiation ( λ ≥ 715 nm) due to the photothermally-induced degradation of azo linkages within the cores of the star polymers. This approach provides access to a new class of delivery and release systems that can be triggered by noninvasive external stimulation.

Osmotic pressure and virial coefficients of star and comb polymer solutions: dissipative particle dynamics.

PubMed

Wang, Tzu-Yu; Fang, Che-Ming; Sheng, Yu-Jane; Tsao, Heng-Kwong

2009-03-28

The effects of macromolecular architecture on the osmotic pressure pi and virial coefficients (B(2) and B(3)) of star and comb polymers in good solvents are studied by dissipative particle dynamics simulations for both dilute and semiconcentrated regimes. The dependence of the osmotic pressure on polymer concentration is directly calculated by considering two reservoirs separated by a semipermeable, fictitious membrane. Our simulation results show that the ratios A(n+1) identical with B(n+1)/R(g)(3n) are essentially constant and A(2) and A(3) are arm number (f) dependent, where R(g) is zero-density radius of gyration. The value of dimensionless virial ratio g = A(3)/A(2)(2) increases with arm number of stars whereas it is essentially arm number independent for comb polymers. In semiconcentrated regime the scaling relation between osmotic pressure and volume fraction, pi proportional to phi(lambda), still holds for both star and comb polymers. For comb polymers, the exponent lambda is close to lambda(*) (approximately = 2.73 for linear chains) and is independent of the arm number. However, for star polymers, the exponent lambda deviates from lambda(*) and actually grows with increasing the arm number. This may be attributed to the significant ternary interactions near the star core in the many-arm systems.

Structure of Irreversibly Adsorbed Star Polymers

NASA Astrophysics Data System (ADS)

Akgun, Bulent; Aykan, Meryem Seyma; Canavar, Seda; Satija, Sushil K.; Uhrig, David; Hong, Kunlun

Formation of irreversibly adsorbed polymer chains on solid substrates have a huge impact on the wetting, glass transition, aging and polymer chain mobility in thin films. In recent years there has been many reports on the formation, kinetics and dynamics of these layers formed by linear homopolymers. Recent studies showed that by varying the number of polymer arms and arm molecular weight one can tune the glass transition temperature of thin polymer films. Using polymer architecture as a tool, the behavior of thin films can be tuned between the behavior of linear chains and soft colloids. We have studied the effect of polymer chain architecture on the structure of dead layer using X-ray reflectivity (XR) and atomic force microscopy. Layer thicknesses and densities of flattened and loosely adsorbed chains has been measured for linear, 4-arm, and 8-arm star polymers with identical total molecular weight as a function of substrate surface energy, annealing temperature and annealing time. Star polymers have been synthesized using anionic polymerization. XR measurements showed that 8-arm star PS molecules form the densest and the thickest dead layers among these three molecules.

Mesomorphic properties of multi-arm chenodeoxycholic acid-derived liquid crystals

NASA Astrophysics Data System (ADS)

Dong, Liang; Yao, Miao; Wu, Shuang-jie; Yao, Dan-Shu; Hu, Jian-She; He, Xiao-zhi; Tian, Mei

2017-12-01

Four multi-arm liquid crystals (LCs) based on chenodeoxycholic acid, termed as 2G-PD, 2G-IB, 2G-BD and 5G-GC, respectively, have been synthesised by convergent method, which nematic LC, 6-(4-((4-ethoxybenzoyl)oxy)phenoxy)-6-oxohexanoic acid, was used as side arm, and chenodeoxycholic acid (CDCA) was used as the first core, 1,2-propanediol (PD), isosorbide (IB), 4,4‧-biphenyldiol (BD) and glucose (GC) were used as the second core, respectively. The first generation product, CDCA2EA, displayed cholesteric phase. The second generation products 2G-BD and 5G-GC displayed cholesteric phase, while 2G-PD and 2G-IB exhibited nematic phase. The multi-arm LC, 2G-IB, did not display cholesteric phase although the two cores were all chiral ones. The result indicated that chirality of the second core sometimes made the multi-arm LCs display nematic phase when cholesteric CDCA-derivative were introduced into the second core. Some attention should be paid on molecular conformation besides the introduction of chiral cores for multi-chiral-core LCs to obtain cholesteric phase.

Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry.

PubMed

Yu, Juan; Lu, Chuanwei; Wang, Chunpeng; Wang, Jifu; Fan, Yimin; Chu, Fuxiang

2017-11-15

Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1 H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions. Copyright © 2017. Published by Elsevier Ltd.

Overtaking method based on sand-sifter mechanism: Why do optimistic value functions find optimal solutions in multi-armed bandit problems?

PubMed

Ochi, Kento; Kamiura, Moto

2015-09-01

A multi-armed bandit problem is a search problem on which a learning agent must select the optimal arm among multiple slot machines generating random rewards. UCB algorithm is one of the most popular methods to solve multi-armed bandit problems. It achieves logarithmic regret performance by coordinating balance between exploration and exploitation. Since UCB algorithms, researchers have empirically known that optimistic value functions exhibit good performance in multi-armed bandit problems. The terms optimistic or optimism might suggest that the value function is sufficiently larger than the sample mean of rewards. The first definition of UCB algorithm is focused on the optimization of regret, and it is not directly based on the optimism of a value function. We need to think the reason why the optimism derives good performance in multi-armed bandit problems. In the present article, we propose a new method, which is called Overtaking method, to solve multi-armed bandit problems. The value function of the proposed method is defined as an upper bound of a confidence interval with respect to an estimator of expected value of reward: the value function asymptotically approaches to the expected value of reward from the upper bound. If the value function is larger than the expected value under the asymptote, then the learning agent is almost sure to be able to obtain the optimal arm. This structure is called sand-sifter mechanism, which has no regrowth of value function of suboptimal arms. It means that the learning agent can play only the current best arm in each time step. Consequently the proposed method achieves high accuracy rate and low regret and some value functions of it can outperform UCB algorithms. This study suggests the advantage of optimism of agents in uncertain environment by one of the simplest frameworks. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

Metal-Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis.

PubMed

Hosono, Nobuhiko; Gochomori, Mika; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu

2016-05-25

We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal-organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition-fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were grafted from the MOP core. On the other hand, the convergent route provided identical CSP architectures by simple mixing of a macroligand and copper ions. Isophthalic acid-terminated polymers (so-called macroligands) immediately formed the corresponding CSPs through a coordination reaction with copper(II) ions. This convergent route enabled us to obtain miktoarm CSPs with tunable chain compositions through ligand mixing alone. This powerful method allows instant access to a wide variety of multicomponent star polymers that conventionally have required highly skilled and multistep syntheses. MOP-core CSPs are a new class of star polymer that can offer a design strategy for highly processable porous soft materials by using coordination nanocages as a building component.

Characterizing DNA Star-Tile-Based Nanostructures Using a Coarse-Grained Model.

PubMed

Schreck, John S; Romano, Flavio; Zimmer, Matthew H; Louis, Ard A; Doye, Jonathan P K

2016-04-26

We use oxDNA, a coarse-grained model of DNA at the nucleotide level, to simulate large nanoprisms that are composed of multi-arm star tiles, in which the size of bulge loops that have been incorporated into the tile design is used to control the flexibility of the tiles. The oxDNA model predicts equilibrium structures for several different nanoprism designs that are in excellent agreement with the experimental structures as measured by cryoTEM. In particular we reproduce the chiral twisting of the top and bottom faces of the nanoprisms, as the bulge sizes in these structures are varied due to the greater flexibility of larger bulges. We are also able to follow how the properties of the star tiles evolve as the prisms are assembled. Individual star tiles are very flexible, but their structures become increasingly well-defined and rigid as they are incorporated into larger assemblies. oxDNA also finds that the experimentally observed prisms are more stable than their inverted counterparts, but interestingly this preference for the arms of the tiles to bend in a given direction only emerges after they are part of larger assemblies. These results show the potential for oxDNA to provide detailed structural insight as well as to predict the properties of DNA nanostructures and hence to aid rational design in DNA nanotechnology.

Accounting for correlation in network meta-analysis with multi-arm trials.

PubMed

Franchini, A J; Dias, S; Ades, A E; Jansen, J P; Welton, N J

2012-06-01

Multi-arm trials (trials with more than two arms) are particularly valuable forms of evidence for network meta-analysis (NMA). Trial results are available either as arm-level summaries, where effect measures are reported for each arm, or as contrast-level summaries, where the differences in effect between arms compare with the control arm chosen for the trial. We show that likelihood-based inference in both contrast-level and arm-level formats is identical if there are only two-arm trials, but that if there are multi-arm trials, results from the contrast-level format will be incorrect unless correlations are accounted for in the likelihood. We review Bayesian and frequentist software for NMA with multi-arm trials that can account for this correlation and give an illustrative example of the difference in estimates that can be introduced if the correlations are not incorporated. We discuss methods of imputing correlations when they cannot be derived from the reported results and urge trialists to report the standard error for the control arm even if only contrast-level summaries are reported. Copyright © 2012 John Wiley & Sons, Ltd. Copyright © 2012 John Wiley & Sons, Ltd.

Nanoparticle (star polymer) delivery of nitric oxide effectively negates Pseudomonas aeruginosa biofilm formation.

PubMed

Duong, Hien T T; Jung, Kenward; Kutty, Samuel K; Agustina, Sri; Adnan, Nik Nik M; Basuki, Johan S; Kumar, Naresh; Davis, Thomas P; Barraud, Nicolas; Boyer, Cyrille

2014-07-14

Biofilms are increasingly recognized as playing a major role in human infectious diseases, as they can form on both living tissues and abiotic surfaces, with serious implications for applications that rely on prolonged exposure to the body such as implantable biomedical devices or catheters. Therefore, there is an urgent need to develop improved therapeutics to effectively eradicate unwanted biofilms. Recently, the biological signaling molecule nitric oxide (NO) was identified as a key regulator of dispersal events in biofilms. In this paper, we report a new class of core cross-linked star polymers designed to store and release nitric oxide, in a controlled way, for the dispersion of biofilms. First, core cross-linked star polymers were prepared by reversible addition-fragmentation chain transfer polymerization (RAFT) via an arm first approach. Poly(oligoethylene methoxy acrylate) chains were synthesized by RAFT polymerization, and then chain extended in the presence of 2-vinyl-4,4-dimethyl-5-oxazolone monomer (VDM) with N,N-methylenebis(acrylamide) employed as a cross-linker to yield functional core cross-linked star polymers. Spermine was successfully attached to the star core by reaction with VDM. Finally, the secondary amine groups were reacted with NO gas to yield NO-core cross-linked star polymers. The core cross-linked star polymers were found to release NO in a controlled, slow delivery in bacterial cultures showing great efficacy in preventing both cell attachment and biofilm formation in Pseudomonas aeruginosa over time via a nontoxic mechanism, confining bacterial growth to the suspended liquid.

Self-perpetuating Spiral Arms in Disk Galaxies

NASA Astrophysics Data System (ADS)

D'Onghia, Elena; Vogelsberger, Mark; Hernquist, Lars

2013-03-01

The causes of spiral structure in galaxies remain uncertain. Leaving aside the grand bisymmetric spirals with their own well-known complications, here we consider the possibility that multi-armed spiral features originate from density inhomogeneities orbiting within disks. Using high-resolution N-body simulations, we follow the motions of stars under the influence of gravity, and show that mass concentrations with properties similar to those of giant molecular clouds can induce the development of spiral arms through a process termed swing amplification. However, unlike in earlier work, we demonstrate that the eventual response of the disk can be highly non-linear, significantly modifying the formation and longevity of the resulting patterns. Contrary to expectations, ragged spiral structures can thus survive at least in a statistical sense long after the original perturbing influence has been removed.

New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

PubMed

Min, Ke; Gao, Haifeng

2012-09-26

A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

Multivalent Nanoparticle Networks Enable Point of Care Detection of Human Phospholipase-A2 in Serum

PubMed Central

Burnapp, Mark; Bentham, Andrew; Hillier, David; Zabron, Abigail; Khan, Shahid; Tyreman, Matthew; Stevens, Molly M.

2017-01-01

A rapid and highly sensitive point of care (PoC) lateral flow assay for phospholipase-A2 (PLA2) is demonstrated in serum through the enzyme-triggered release of a new class of biotinylated multi-armed polymers from a liposome substrate. Signal from the enzyme activity is generated by the adhesion of polystreptavidin coated gold nanoparticle networks to the lateral flow device, which leads to the appearance of a red test line due to the localised surface plasmon resonance (LSPR) effect of the gold. The use of a liposome as the enzyme substrate and multivalent linkers to link the nanoparticles leads to amplification of the signal as the cleavage of a small amount of lipids is able to release a large amount of polymer linker and adhesion of an even larger amount of gold nanoparticles. By optimising the molecular weight and multivalency of these biotinylated polymer linkers the sensitivity of the device can be tuned to enable naked-eye detection of 1 nM human-PLA2 in serum within 10 minutes. This high sensitivity enabled the correct diagnosis of pancreatitis in diseased clinical samples against a set of healthy controls using PLA2 activity in a point of care device for the first time. PMID:25756526

Effect of chain topology on crystallization within nanoporous alumina

NASA Astrophysics Data System (ADS)

Yao, Yang; Suzuki, Yasuhito; Sakai, Takamasa; Seiwert, Jan; Frey, Holger; Steinhart, Martin; Butt, Hans-Juergen; Floudas, George

Polymer topology has inevitable influence on the structure, packing, and dynamic of chains. Herein, we investigate for the first time the impact of polymer architecture on crystallization under 2D confinement, the latter provided by nanoporous alumina (AAO). We employ two poly(ethylene oxide) (PEO) star polymers to study the effect of (i) end groups and (ii) molecular weight on polymer crystallization in the bulk and under confinement. Bulk end groups reduce the crystallization/melting temperatures and the corresponding equilibrium melting point. Under confinement, in the absence of catalyst, homogeneous nucleation prevails as with linear PEOs. The homogeneous nucleation temperatures for the star polymers agree with that of linear ones provided that the arm molecular weight is used instead. Long-range dynamics pertinent to star relaxation are affecting the homogeneous nucleation temperature. On the other hand, the segmental dynamics speed up on confinement. In addition to star PEO, we study the effect of another topology, i.e. hyperbranched PEO, on the nucleation mechanism.

Star-like supramolecular polymers fabricated by a Keplerate cluster with cationic terminated polymers and their self-assembly into vesicles.

PubMed

Zhang, Qian; He, Lipeng; Wang, Hui; Zhang, Cheng; Liu, Weisheng; Bu, Weifeng

2012-07-18

The electrostatic combination of a Keplerate cluster, [Mo(132)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-) with cationic terminated poly(styrene) yields polyoxometalate-based supramolecular star polymers, which can further self-assemble into vesicular aggregates in CHCl(3)-MeOH mixed solvent.

Fe3O4 nanoparticles modified by CD-containing star polymer for MRI and drug delivery.

PubMed

Cha, Ruitao; Li, Juanjuan; Liu, Yang; Zhang, Yifan; Xie, Qian; Zhang, Mingming

2017-10-01

Fe 3 O 4 nanoparticles with ultrasmall sizes show good T 1 or T 1 +T 2 contrast abilities, and have attracted considerable interest in the field of magnetic resonance imaging (MRI) contrast agents. For effective biomedical applications, the colloidal stability and biocompatibility of the Fe 3 O 4 nanoparticles need to be improved without reducing MRI relaxivity. In this paper, star polymers were used as coating materials to modify Fe 3 O 4 nanoparticles in view of their dense molecular architecture with moderate flexibility. The star polymer was composed of a β-cyclodextrin (β-CD) core and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) arms. Meanwhile, reduced glutathione (GSH), as a model drug, was also associated with the star polymer. Thus, a new platform for simultaneous diagnosis and treatment was achieved. Compared to the Fe 3 O 4 nanoparticles coated with linear polymers, the Fe 3 O 4 nanoparticles coated with star polymers (Fe 3 O 4 @GCP) possessed higher GSH association capacity and better stability in serum-containing solution. GSH could be released from Fe 3 O 4 @GCP nanoparticles in response to pH value of the solution. Since the sulfhydryl group on GSH is able to combine free radicals, Fe 3 O 4 @GCP nanoparticles exhibited less cytotoxicity compared to the Fe 3 O 4 nanoparticles without including GSH. Furthermore, the nanoparticles could also serve as good T 1 MRI contrast agent, and the MRI relaxivity of Fe 3 O 4 @GCP nanoparticles did not decrease after coated with the star polymer. These results indicate that the precisely designed Fe 3 O 4 @GCP nanoparticles could be used as a versatile promising theranostic nano-platform. Copyright © 2017 Elsevier B.V. All rights reserved.

Conformational and Structural Properties of High Functionality Dendrimer-like Star Polymers Synthesized from Living Polymerization Techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pople, John A

2001-03-22

The design, synthesis and solution properties of dendritic-linear hybrid macromolecules is described. The synthetic strategy employs living ring-opening polymerization in combination with selective and quantitative organic transformations for the preparation of new molecular architectures similar to classical star polymers and dendrimers. The polymers were constructed from high molecular weight poly(e-caprolactone) initiated from the surface hydroxyl groups of dendrimers derived from bis(hydroxymethyl) propionic acid (bis-MPA) in the presence of stannous 2-ethyl hexanoate (Sn(Oct)2). In this way, star and hyperstar poly(e-caprolactones) were elaborated depending on the generation of dendrimer employed. The ROP from these hydroxy groups was found to be a facilemore » process leading to controlled molecular weight, low dispersity products (Mw/Mn) < 1.15. In addition to the use of dendrimers as building blocks to star polymers, functional dendrons derived from bis-MPA were attached to chain ends of the star polymers, yielding structures that closely resemble that of the most advanced dendrimers. Measurements of the solution properties (hydrodynamic volume vs. molecular weight) on the dendritic-linear hybrids show a deviation from linearity, with a lower than expected hydrodynamic volume, analogous to the solution properties of dendrimers of high generation number. The onset of the deviation begins with the polymers initiated from the second generation dendrimer of bis-MPA and becomes more exaggerated with the higher generations. It was found that polymerization amplifies the nonlinear solution behavior of dendrimers. Small angle neutron scattering (SANS) measurements revealed that the radius of gyration scaled with arm functionality (f) as f 2/3, in accordance with the Daoud-Cotton model for many arm star polymer.« less

Source replenishment device for vacuum deposition

DOEpatents

Hill, Ronald A.

1988-01-01

A material source replenishment device for use with a vacuum deposition apparatus. The source replenishment device comprises an intermittent motion producing gear arrangement disposed within the vacuum deposition chamber. An elongated rod having one end operably connected to the gearing arrangement is provided with a multiarmed head at the opposite end disposed adjacent the heating element of the vacuum deposition apparatus. An inverted U-shaped source material element is releasably attached to the outer end of each arm member whereby said multiarmed head is moved to locate a first of said material elements above said heating element, whereupon said multiarmed head is lowered to engage said material element with the heating element and further lowered to release said material element on the heating element. After vaporization of said material element, second and subsequent material elements may be provided to the heating element without the need for opening the vacuum deposition apparatus to the atmosphere.

Source replenishment device for vacuum deposition

DOEpatents

Hill, R.A.

1986-05-15

A material source replenishment device for use with a vacuum deposition apparatus is described. The source replenishment device comprises an intermittent motion producing gear arrangement disposed within the vacuum deposition chamber. An elongated rod having one end operably connected to the gearing arrangement is provided with a multiarmed head at the opposite end disposed adjacent the heating element of the vacuum deposition apparatus. An inverted U-shaped source material element is releasably attached to the outer end of each arm member whereby said multiarmed head is moved to locate a first of said material elements above said heating element, whereupon said multiarmed head is lowered to engage said material element with the heating element and further lowered to release said material element on the heating element. After vaporization of said material element, second and subsequent material elements may be provided to the heating element without the need for opening the vacuum deposition apparatus to the atmosphere.

A comparative study of restricted randomization procedures for multiarm trials with equal or unequal treatment allocation ratios.

PubMed

Ryeznik, Yevgen; Sverdlov, Oleksandr

2018-06-04

Randomization designs for multiarm clinical trials are increasingly used in practice, especially in phase II dose-ranging studies. Many new methods have been proposed in the literature; however, there is lack of systematic, head-to-head comparison of the competing designs. In this paper, we systematically investigate statistical properties of various restricted randomization procedures for multiarm trials with fixed and possibly unequal allocation ratios. The design operating characteristics include measures of allocation balance, randomness of treatment assignments, variations in the allocation ratio, and statistical characteristics such as type I error rate and power. The results from the current paper should help clinical investigators select an appropriate randomization procedure for their clinical trial. We also provide a web-based R shiny application that can be used to reproduce all results in this paper and run simulations under additional user-defined experimental scenarios. Copyright © 2018 John Wiley & Sons, Ltd.

Arm retraction dynamics of entangled star polymers: A forward flux sampling method study

NASA Astrophysics Data System (ADS)

Zhu, Jian; Likhtman, Alexei E.; Wang, Zuowei

2017-07-01

The study of dynamics and rheology of well-entangled branched polymers remains a challenge for computer simulations due to the exponentially growing terminal relaxation times of these polymers with increasing molecular weights. We present an efficient simulation algorithm for studying the arm retraction dynamics of entangled star polymers by combining the coarse-grained slip-spring (SS) model with the forward flux sampling (FFS) method. This algorithm is first applied to simulate symmetric star polymers in the absence of constraint release (CR). The reaction coordinate for the FFS method is determined by finding good agreement of the simulation results on the terminal relaxation times of mildly entangled stars with those obtained from direct shooting SS model simulations with the relative difference between them less than 5%. The FFS simulations are then carried out for strongly entangled stars with arm lengths up to 16 entanglements that are far beyond the accessibility of brute force simulations in the non-CR condition. Apart from the terminal relaxation times, the same method can also be applied to generate the relaxation spectra of all entanglements along the arms which are desired for the development of quantitative theories of entangled branched polymers. Furthermore, we propose a numerical route to construct the experimentally measurable relaxation correlation functions by effectively linking the data stored at each interface during the FFS runs. The obtained star arm end-to-end vector relaxation functions Φ (t ) and the stress relaxation function G(t) are found to be in reasonably good agreement with standard SS simulation results in the terminal regime. Finally, we demonstrate that this simulation method can be conveniently extended to study the arm-retraction problem in entangled star polymer melts with CR by modifying the definition of the reaction coordinate, while the computational efficiency will depend on the particular slip-spring or slip-link model employed.

A Multi-Armed Bandit Approach to Following a Markov Chain

DTIC Science & Technology

2017-06-01

focus on the House to Café transition (p1,4). We develop a Multi-Armed Bandit approach for efficiently following this target, where each state takes the...and longitude (each state corresponding to a physical location and a small set of activities). The searcher would then apply our approach on this...the target’s transition probability and the true probability over time. Further, we seek to provide upper bounds (i.e., worst case bounds) on the

Accelerated Combinatorial High Throughput Star Polymer Synthesis via a Rapid One-Pot Sequential Aqueous RAFT (rosa-RAFT) Polymerization Scheme.

PubMed

Cosson, Steffen; Danial, Maarten; Saint-Amans, Julien Rosselgong; Cooper-White, Justin J

2017-04-01

Advanced polymerization methodologies, such as reversible addition-fragmentation transfer (RAFT), allow unprecedented control over star polymer composition, topology, and functionality. However, using RAFT to produce high throughput (HTP) combinatorial star polymer libraries remains, to date, impracticable due to several technical limitations. Herein, the methodology "rapid one-pot sequential aqueous RAFT" or "rosa-RAFT," in which well-defined homo-, copolymer, and mikto-arm star polymers can be prepared in very low to medium reaction volumes (50 µL to 2 mL) via an "arm-first" approach in air within minutes, is reported. Due to the high conversion of a variety of acrylamide/acrylate monomers achieved during each successive short reaction step (each taking 3 min), the requirement for intermediary purification is avoided, drastically facilitating and accelerating the star synthesis process. The presented methodology enables RAFT to be applied to HTP polymeric bio/nanomaterials discovery pipelines, in which hundreds of complex polymeric formulations can be rapidly produced, screened, and scaled up for assessment in a wide range of applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Studies of Three-Arm Star Block Copolymers Exposed to Extreme Stretch Suggests a Persistent Polymer Tube

NASA Astrophysics Data System (ADS)

Mortensen, Kell; Borger, Anine L.; Kirkensgaard, Jacob J. K.; Garvey, Christopher J.; Almdal, Kristoffer; Dorokhin, Andriy; Huang, Qian; Hassager, Ole

2018-05-01

We present structural small-angle neutron scattering studies of a three-armed polystyrene star polymer with short deuterated segments at the end of each arm. We show that the form factor of the three-armed star molecules in the relaxed state agrees with that of the random phase approximation of Gaussian chains. Upon exposure to large extensional flow conditions, the star polymers change conformation resulting in a highly stretched structure that mimics a fully extended three-armed tube model. All three arms are parallel to the flow, one arm being either in positive or negative stretching direction, while the two other arms are oriented parallel, right next to each other in the direction opposite to the first arm.

Universal shape characteristics for the mesoscopic star-shaped polymer via dissipative particle dynamics simulations

NASA Astrophysics Data System (ADS)

Kalyuzhnyi, O.; Ilnytskyi, J. M.; Holovatch, Yu; von Ferber, C.

2018-05-01

In this paper we study the shape characteristics of star-like polymers in various solvent quality using a mesoscopic level of modeling. The dissipative particle dynamics simulations are performed for the homogeneous and four different heterogeneous star polymers with the same molecular weight. We analyse the gyration radius and asphericity at the poor, good and θ-solvent regimes. Detailed explanation based on interplay between enthalpic and entropic contributions to the free energy and analyses on of the asphericity of individual branches are provided to explain the increase of the apsphericity in θ-solvent regime.

White polymer light-emitting diodes based on star-shaped polymers with an orange dendritic phosphorescent core.

PubMed

Zhu, Minrong; Li, Yanhu; Cao, Xiaosong; Jiang, Bei; Wu, Hongbin; Qin, Jingui; Cao, Yong; Yang, Chuluo

2014-12-01

A series of new star-shaped polymers with a triphenylamine-based iridium(III) dendritic complex as the orange-emitting core and poly(9,9-dihexylfluorene) (PFH) chains as the blue-emitting arms is developed towards white polymer light-emitting diodes (WPLEDs). By fine-tuning the content of the orange phosphor, partial energy transfer and charge trapping from the blue backbone to the orange core is realized to achieve white light emission. Single-layer WPLEDs with the configuration of ITO (indium-tin oxide)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer/CsF/Al exhibit a maximum current efficiency of 1.69 cd A(-1) and CIE coordinates of (0.35, 0.33), which is very close to the pure white-light point of (0.33, 0.33). To the best of our knowledge, this is the first report on star-shaped white-emitting single polymers that simultaneously consist of fluorescent and phosphorescent species. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lymphatic trafficking kinetics and near-infrared imaging using star polymer architectures with controlled anionic character

PubMed Central

Bagby, Taryn R.; Cai, Shuang; Duan, Shaofeng; Yang, Qiuhong; Thati, Sharadvi; Berkland, Cory; Aires, Daniel J.; Forrest, M. Laird

2015-01-01

Targeted lymphatic delivery of nanoparticles for drug delivery and imaging is primarily dependent on size and charge. Prior studies have observed increased lymphatic uptake and retentions of over 48 hrs for negatively charged particles compared to neutral and positively charged particles. We have developed new polymeric materials that extend retention over a more pharmaceutically relevant 7-day period. We used whole body fluorescence imaging to observe in mice the lymphatic trafficking of a series of anionic star poly-(6-O-methacryloyl-D-galactose) polymer-NIR dye (IR820) conjugates. The anionic charge of polymers was increased by modifying galactose moieties in the star polymers with succinic anhydride. Increasing anionic nature was associated with enhanced lymphatic uptake up to a zeta potential of ca. -40 mV; further negative charge did not affect lymphatic uptake. Compared to the 20% acid-conjugate, the 40 to 90% acid-star-polymer conjugates exhibited a 2.5- to 3.5-fold increase in lymphatic uptake in both the popliteal and iliac nodes. The polymer conjugates exhibited node half-lives of 2 to 20 hrs in the popliteal nodes and 19 to 114 hrs in the deeper iliac nodes. These polymer conjugates can deliver drugs or imaging agents with rapid lymphatic uptake and prolonged deep-nodal retention; thus they may provide a useful vehicle for sustained intralymphatic drug delivery with low toxicity. PMID:22546180

Combining living anionic polymerization with branching reactions in an iterative fashion to design branched polymers.

PubMed

Higashihara, Tomoya; Sugiyama, Kenji; Yoo, Hee-Soo; Hayashi, Mayumi; Hirao, Akira

2010-06-16

This paper reviews the precise synthesis of many-armed and multi-compositional star-branched polymers, exact graft (co)polymers, and structurally well-defined dendrimer-like star-branched polymers, which are synthetically difficult, by a commonly-featured iterative methodology combining living anionic polymerization with branched reactions to design branched polymers. The methodology basically involves only two synthetic steps; (a) preparation of a polymeric building block corresponding to each branched polymer and (b) connection of the resulting building unit to another unit. The synthetic steps were repeated in a stepwise fashion several times to successively synthesize a series of well-defined target branched polymers. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Small cell foams and blends and a process for their preparation

DOEpatents

Hedstrand, D.M.; Tomalia, D.A.

1995-02-07

Dense star polymers or dendrimers, modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, act as molecular nucleating agents. These modified dense star polymers or dendrimers are particularly effective for the production of small cell foams.

Small cell foams and blends and a process for their preparation

DOEpatents

Hedstrand, David M.; Tomalia, Donald A.

1995-01-01

Dense star polymers or dendrimers, modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, act as molecular nucleating agents. These modified dense star polymers or dendrimers are particularly effective for the production of small cell foams.

Star PolyMOCs with Diverse Structures, Dynamics, and Functions by Three-Component Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yufeng; Gu, Yuwei; Keeler, Eric G.

2016-12-05

We report star polymer metal–organic cage (polyMOC) materials whose structures, mechanical properties, functionalities, and dynamics can all be precisely tailored through a simple three-component assembly strategy. The star polyMOC network is composed of tetra-arm star polymers functionalized with ligands on the chain ends, small molecule ligands, and palladium ions; polyMOCs are formed via metal–ligand coordination and thermal annealing. The ratio of small molecule ligands to polymer-bound ligands determines the connectivity of the MOC junctions and the network structure. The use of large M12L24 MOCs enables great flexibility in tuning this ratio, which provides access to a rich spectrum of materialmore » properties including tunable moduli and relaxation dynamics.« less

Enzymatically Crosslinked Emulsion Gels Using Star-Polymer Stabilizers.

PubMed

Ma, Kai; An, Zesheng

2016-10-01

A novel type of emulsion gel based on star-polymer-stabilized emulsions is highlighted, which contains discrete hydrophobic oil and hydrophilic aqueous solution domains. Well-defined phenol-functionalized core-crosslinked star polymers are synthesized via reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization and are used as stabilizers for oil-in-water emulsions. Horseradish-peroxidase-catalyzed polymerization of the phenol moieties in the presence of H 2 O 2 enables rapid formation of crosslinked emulsion gels under mild conditions. The crosslinked emulsion gels exhibit enhanced mechanical strength, as well as widely tunable composition. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structured copolymers and their use as absorbents, gels and carriers of metal ions

DOEpatents

Hedstrand, David M.; Helmer, Bradley J.; Tomalia, Donald A.

1996-01-01

Dense star polymers or dendrimers having a highly branched interior structure capable of associating or chelating with metal ions are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell. The modified dendrimers are useful for dispersing metal ions in a non-aqueous polymer matrix. Also dense star polymers or dendrimers having a highly branched hydrophilic interior structure are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, which modified polymers are useful as gels and surfactants.

Structured copolymers and their use as absorbents, gels and carriers of metal ions

DOEpatents

Hedstrand, D.M.; Helmer, B.J.; Tomalia, D.A.

1996-10-01

Dense star polymers or dendrimers having a highly branched interior structure capable of associating or chelating with metal ions are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell. The modified dendrimers are useful for dispersing metal ions in a non-aqueous polymer matrix. Also dense star polymers or dendrimers having a highly branched hydrophilic interior structure are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, which modified polymers are useful as gels and surfactants.

Self-assembly of star micelle into vesicle in solvents of variable quality: the star micelle retains its core-shell nanostructure in the vesicle.

PubMed

Liu, Nijuan; He, Qun; Bu, Weifeng

2015-03-03

Intra- and intermolecular interactions of star polymers in dilute solutions are of fundamental importance for both theoretical interest and hierarchical self-assembly into functional nanostructures. Here, star micelles with a polystyrene corona and a small ionic core bearing platinum(II) complexes have been regarded as a model of star polymers to mimic their intra- and interstar interactions and self-assembled behaviors in solvents of weakening quality. In the chloroform/methanol mixture solvents, the star micelles can self-assemble to form vesicles, in which the star micelles shrink significantly and are homogeneously distributed on the vesicle surface. Unlike the morphological evolution of conventional amphiphiles from micellar to vesicular, during which the amphiphilic molecules are commonly reorganized, the star micelles still retain their core-shell nanostructures in the vesicles and the coronal chains of the star micelle between the ionic cores are fully interpenetrated.

Trends in the application of dynamic allocation methods in multi-arm cancer clinical trials.

PubMed

Pond, Gregory R; Tang, Patricia A; Welch, Stephen A; Chen, Eric X

2010-06-01

Dynamic allocation (DA) methods which attempt to balance baseline prognostic factors between treatment arms, can be used in multi-arm clinical trials to sequentially allocate patients to treatment. Although some experts express concern regarding the validity of inference from trials using DA, others believe DA methods produce more credible results. A review of published multi-arm cancer clinical trials was conducted to explore the frequency of DA use in oncology. Multi-arm phase III clinical trials of at least 100 patients per arm, published in 13 major oncology journals from 1995-2005 were manually reviewed. Information about reported use of DA methods, or randomization via random permuted blocks (PB), was extracted along with trial characteristics. Of 476 published clinical trials, 112 (23.5%) reported using some form of DA method, while 103 (21.6%) reported using PB methods. Most trials (403 or 84.7%) reported stratifying on at least one baseline factor. The mean number of stratification factors was 2.70 per trial, and 78.6% of DA trials reported 3 or more stratification factors compared with 30.2% of non-DA trials (p < 0.001). The frequency of DA use increased over time, with 20.2%, 21.3%, 25.8%, 28.8% and 38.9% of trials reported use in 1995-2001, 2002, 2003, 2004, and 2005, respectively. Use of DA methods was more frequently reported in trials involving an academic co-operative group (28.4% vs. 13.8%), however, no difference was observed between industry-funded and other-funded trials (24.0% vs. 23.2%) or geographical region (19.7% of North American trials, 26.2% of European trials and 21.7% of multinational/other trials). As a retrospective analysis, the true frequency of DA use is likely underreported. Few trials gave complete details of the allocation method used, thus it is possible some manuscripts reported incorrect allocation methods. Journals were selected which were assumed to publish most large, multi-arm clinical trials in cancer from 1995-2005, however, some trials were likely reported in journals other than what was reviewed. DA methods are frequently used in multi-arm cancer clinical trials. The use of DA appears to becoming more common over time and are used more frequently when an academic cooperative group is involved. No relationship between industry funded trials or geographic region and allocation method was observed. Clinical Trials 2010; 7: 227-234. http://ctj.sagepub.com.

Multiarm spirals on the periphery of disc galaxies

NASA Astrophysics Data System (ADS)

Lubov, Spiegel; Evgeny, Polyachenko

2018-04-01

Spiral patterns in some disc galaxies have two arms in the centre, and three or more arms on the periphery. The same result is also obtained in numerical simulations of stellar and gaseous discs.We argue that such patterns may occur due to fast cooling of the gas, resulting in formation of giant molecular clouds. The timescale of this process is 50 Myr, the factor of 10 shorter than of ordinary secular instability. The giant molecular clouds give rise to multiarm spirals through the mechanism of swing amplification.

Broadband and stable acoustic vortex emitter with multi-arm coiling slits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Xue; Liang, Bin, E-mail: liangbin@nju.edu.cn, E-mail: eleqc@nus.edu.sg, E-mail: jccheng@nju.edu.cn; Zou, Xin-ye

2016-05-16

We present the analytical design and experimental realization of a scheme based on multi-arm coiling slits to generate the stable acoustic vortices in a broadband. The proposed structure is able to spiral the acoustic wave spatially and generate the twisted acoustic vortices with invariant topological charge for a long propagation distance. Compared with conventional methods which require the electronic control of a bulky loudspeaker, this scheme provides an effective and compact solution to generate acoustic vortices with controllable topological charge in the broadband, which offers more initiatives in the demanding applications.

Integral equation theory study on the phase separation in star polymer nanocomposite melts.

PubMed

Zhao, Lei; Li, Yi-Gui; Zhong, Chongli

2007-10-21

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Polyphosphazene Based Star-Branched and Dendritic Molecular Brushes.

PubMed

Henke, Helena; Posch, Sandra; Brüggemann, Oliver; Teasdale, Ian

2016-05-01

A new synthetic procedure is described for the preparation of poly(organo)phosphazenes with star-branched and star dendritic molecular brush type structures, thus describing the first time it has been possible to prepare controlled, highly branched architectures for this type of polymer. Furthermore, as a result of the extremely high-arm density generated by the phosphazene repeat unit, the second-generation structures represent quite unique architectures for any type of polymer. Using two relativity straight forward iterative syntheses it is possible to prepare globular highly branched polymers with up to 30 000 functional end groups, while keeping relatively narrow polydispersities (1.2-1.6). Phosphine mediated polymerization of chlorophosphoranimine is first used to prepare three-arm star polymers. Subsequent substitution with diphenylphosphine moieties gives poly(organo)phosphazenes to function as multifunctional macroinitiators for the growth of a second generation of polyphosphazene arms. Macrosubstitution with Jeffamine oligomers gives a series of large, water soluble branched macromolecules with high-arm density and hydrodynamic diameters between 10 and 70 nm. © 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Doxorubicin-loaded micelles based on multiarm star-shaped PLGA-PEG block copolymers: influence of arm numbers on drug delivery.

PubMed

Ma, Guilei; Zhang, Chao; Zhang, Linhua; Sun, Hongfan; Song, Cunxian; Wang, Chun; Kong, Deling

2016-01-01

Star-shaped block copolymers based on poly(D,L-lactide-co-glycolide) (PLGA) and poly(ethylene glycol) (PEG) (st-PLGA-PEG) were synthesized with structural variation on arm numbers in order to investigate the relationship between the arm numbers of st-PLGA-PEG copolymers and their micelle properties. st-PLGA-PEG copolymers with arm numbers 3, 4 and 6 were synthesized by using different cores such as trimethylolpropane, pentaerythritol and dipentaerythritol, and were characterized by nuclear magnetic resonance and gel permeation chromatography. The critical micelle concentration decreased with increasing arm numbers in st-PLGA-PEG copolymers. The doxorubicin-loaded st-PLGA-PEG micelles were prepared by a modified nanoprecipitation method. Micellar properties such as particle size, drug loading content and in vitro drug release behavior were investigated as a function of the number of arms and compared with each other. The doxorubicin-loaded 4-arm PLGA-PEG micelles were found to have the highest cellular uptake efficiency and cytotoxicity compared with 3-arm PLGA-PEG micelles and 6-arm PLGA-PEG micelles. The results suggest that structural tailoring of arm numbers from st-PLGA-PEG copolymers could provide a new strategy for designing drug carriers of high efficiency. Structural tailoring of arm numbers from star shaped-PLGA-PEG copolymers (3-arm/4-arm/6-arm-PLGA-PEG) could provide a new strategy for designing drug carriers of high efficiency.

The Ultra-filtration of Macromolecules with Different Conformations and Configurations through Nanopores

NASA Astrophysics Data System (ADS)

Ge, Hui

This Ph. D. thesis presents our study on the ultrafiltration of polymers with different configurations and conformations; namly, theoretically, the passing of polymer chains through a nanopore under an elongational flow filed has been studied for years, but experimental studies are rare because of two following reasons: (1) lacks a precise method to investigate how individual single polymer chain pass through a nanopore; (2) it is difficult, if not impossible, to obtain a set of polymer samples with a narrow molar mass distribution and a uniform structures; except for linear chains. The central question in this study is to find the critical (minimum) flow rate (qc) for each kind of chains, at which the chains can pass through a given nanopore. A comparison of the measured and calculated qc leads to a better understanding how different chains are deformed, stretched and pulled through a nanopore. We have developed a novel method of combinating static and dynamic laser light scattering (LLS) to precisely measure the relative retention concentration ((C0 - C)/C0). Chapter 1 briefly introduces the theoretical background of how applications and lists some of resent research progresses in this area. Polymer with various configurations and conformations pass through nanopores; including polymer linear chains, stars polymer, branched polymers, polymer micelles are introduced. Among them, the de Gennes and Brochard-Wyart's predictions of polymer linear and star chains passing through nanopores are emphasized, in which they predicted that qc of linear chain is qc ≃ kBT/(3pieta), where kB, T and eta are the Boltzmann constant, the absolutely temperature, and the viscosity of solvent, respectively, independent of both the chain length and the pore size; and for star chains passing through nanopores, there exist a optimal entering arm numbers, namely, the star chains passing through nanopores. Chapter 2 details basic theory of static and dynamic laser light scattering (LLS), including its instrumentation and our ultrafiltration setup. Chapter 3 briefly introduces the sample preparation, including the history and mechanism of anionic living polymerization, as well as how we used a novel home-made set-up to prepare linear polystyrene with different chain lengths and star polystyrene with various arm numbers and lengths. Chapter 4 summarizes our measured critical flow rates (qc) of linear polymer chains with different lengths for nanopores with different sizes, since the flow rate is directly related to the hydrodynamic force, we have developed a sensitive method (down to tens fN) to directly assess how much the hydrodynamic force (Fh) is required to overcome the weak entropy elasticity and stretch individual coiled chains in solution. Our method is completely different from the using existing optical tweezers or AFM, because they measure the relatively stronger enthalpy elasticity. Our results confirm that qc is indeed independent of the chain length, but decreases as the pore size increases. The value of qc is ˜10--200 times smaller than kBT/(3pieta). Such a discrepancy has been attributed to the rough assumption made by de Gennes and his coworkers; namely, each chain segment "blob" confined inside the pore is not a hard sphere so that the effective length along the flow direction is much longer than the pore diameter. Finally, using the solution temperature, we varied the chain conformation, our result shows that q c has a minimum which is near, but not exactly located at the theta temperature, might leading to a better way to determine the true ideal state of a polymer solution, at which all viral coefficients, not only the second vanish. Chapter 5 uses polymer solutions made of different mixtures of linear and star chains, we have demonstrated that flushing these solution mixtures through a nanopore with a properly chosen flow rate can effectively and cleanly separate linear and star chains no matter whether linear chains are larger or smaller than star chains. Chapter 6 further investigates how star-like polystyrene pass through a given nanopore under the flow field. Star polystyrene chains with different arm lengths (LA) and numbers (f) passing through a nanopore (20 nm) under an elongational flow field was investigated in terms of the flow-rate dependent relative retention ((C0 - C)/C0), where C 0 and C are the polymer concentrations before and after the ultrafiltration. Our results reveal that for a given arm length (LA), the critical flow rate (qc,star), below which star chains are blocked, dramatically increases with the total arm numbers (f); but for a given f, is nearly independent on LA, contradictory to the previous prediction made by de Gennes and Brochard-Wyart. We have revised their theory in the region fin < fout and also accounted for the effective length of each blob, where fin and fout are the numbers of arms inside and outside the pore, respectively. In the revision, we show that qc,star is indeed independent of LA but related to f and f in in two different ways, depending on whether fin ≤ f/2 or ≥ f/2. A comparison of our experimental and calculated results reveals that most of star chains pass through the nanopores with fin ˜ f/2. Further study of the temperature dependent (C0 - C)/C 0 of polystyrene in cyclohexane reveals that there exists a minimum of qc,star at ˜38 °C, close to its theta temperature (-34.5 °C).

[A Multi-arm Placebo-controlled Study with Glutamic Acid Conducted in Rostock in 1953/1954].

PubMed

Häßler, Frank; Weirich, Steffen

2017-09-01

A Multi-arm Placebo-controlled Study with Glutamic Acid Conducted in Rostock in 1953/1954 Glutamic acid was commonly used in the treatment of intellectually disabled children in the 50s. Koch reported first results of an observation of 140 children treated with glutamic acid in 1952. In this line is the multi-arm placebo-controlled study reported here. The original study protocols were available. 58 children with speech problems who attending a school of special needs received glutamic acid, or vitamin B, or St.-John's-wort. The effect of glutamic acid was in few cases an improvement of attention. On the other hand restlessness and stutter increased. The majority of all reported a weight loss. The treatment with vitamin B showed a positive effect concerning concentration. The treatment with St.-John's wort was stopped caused by headache and vomiting in eight of nine cases. The results of the study reported here are unpublished. The reason may be that until the 60s the effects of glutamic acid in the treatment of intellectually disabled children were in generally overestimated.

The KALI multi-arm robot programming and control environment

NASA Technical Reports Server (NTRS)

Backes, Paul; Hayati, Samad; Hayward, Vincent; Tso, Kam

1989-01-01

The KALI distributed robot programming and control environment is described within the context of its use in the Jet Propulsion Laboratory (JPL) telerobot project. The purpose of KALI is to provide a flexible robot programming and control environment for coordinated multi-arm robots. Flexibility, both in hardware configuration and software, is desired so that it can be easily modified to test various concepts in robot programming and control, e.g., multi-arm control, force control, sensor integration, teleoperation, and shared control. In the programming environment, user programs written in the C programming language describe trajectories for multiple coordinated manipulators with the aid of KALI function libraries. A system of multiple coordinated manipulators is considered within the programming environment as one motion system. The user plans the trajectory of one controlled Cartesian frame associated with a motion system and describes the positions of the manipulators with respect to that frame. Smooth Cartesian trajectories are achieved through a blending of successive path segments. The manipulator and load dynamics are considered during trajectory generation so that given interface force limits are not exceeded.

Bayesian adaptive bandit-based designs using the Gittins index for multi-armed trials with normally distributed endpoints.

PubMed

Smith, Adam L; Villar, Sofía S

2018-01-01

Adaptive designs for multi-armed clinical trials have become increasingly popular recently because of their potential to shorten development times and to increase patient response. However, developing response-adaptive designs that offer patient-benefit while ensuring the resulting trial provides a statistically rigorous and unbiased comparison of the different treatments included is highly challenging. In this paper, the theory of Multi-Armed Bandit Problems is used to define near optimal adaptive designs in the context of a clinical trial with a normally distributed endpoint with known variance. We report the operating characteristics (type I error, power, bias) and patient-benefit of these approaches and alternative designs using simulation studies based on an ongoing trial. These results are then compared to those recently published in the context of Bernoulli endpoints. Many limitations and advantages are similar in both cases but there are also important differences, specially with respect to type I error control. This paper proposes a simulation-based testing procedure to correct for the observed type I error inflation that bandit-based and adaptive rules can induce.

Star-shaped Polymers through Simple Wavelength-Selective Free-Radical Photopolymerization.

PubMed

Eibel, Anna; Fast, David E; Sattelkow, Jürgen; Zalibera, Michal; Wang, Jieping; Huber, Alex; Müller, Georgina; Neshchadin, Dmytro; Dietliker, Kurt; Plank, Harald; Grützmacher, Hansjörg; Gescheidt, Georg

2017-11-06

Star-shaped polymers represent highly desired materials in nanotechnology and life sciences, including biomedical applications (e.g., diagnostic imaging, tissue engineering, and targeted drug delivery). Herein, we report a straightforward synthesis of wavelength-selective multifunctional photoinitiators (PIs) that contain a bisacylphosphane oxide (BAPO) group and an α-hydroxy ketone moiety within one molecule. By using three different wavelengths, these photoactive groups can be selectively addressed and activated, thereby allowing the synthesis of ABC-type miktoarm star polymers through a simple, highly selective, and robust free-radical polymerization method. The photochemistry of these new initiators and the feasibility of this concept were investigated in unprecedented detail by using various spectroscopic techniques. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterization of Stimuli-Responsive Star-Like Polypept(o)ides: Introducing Biodegradable PeptoStars.

PubMed

Holm, Regina; Weber, Benjamin; Heller, Philipp; Klinker, Kristina; Westmeier, Dana; Docter, Dominic; Stauber, Roland H; Barz, Matthias

2017-06-01

Star-like polymers are one of the smallest systems in the class of core crosslinked polymeric nanoparticles. This article reports on a versatile, straightforward synthesis of three-arm star-like polypept(o)ide (polysarcosine-block-polylysine) polymers, which are designed to be either stable or degradable at elevated levels of glutathione. Polypept(o)ides are a recently introduced class of polymers combining the stealth-like properties of the polypeptoid polysarcosine with the functionality of polypeptides, thus enabling the synthesis of materials completely based on endogenous amino acids. The star-like homo and block copolymers are synthesized by living nucleophilic ring opening polymerization of the corresponding N-carboxyanhydrides (NCAs) yielding polymeric stars with precise control over the degree of polymerization (X n = 25, 50, 100), Poisson-like molecular weight distributions, and low dispersities (Đ = 1.06-1.15). Star-like polypept(o)ides display a hydrodynamic radius of 5 nm (μ 2 < 0.05) as determined by dynamic light scattering (DLS). While star-like polysarcosines and polypept(o)ides based on disulfide containing initiators are stable in solution, degradation occurs at 100 × 10 -3 m glutathione concentration. The disulfide cleavage yields the respective polymeric arms, which possess Poisson-like molecular weight distributions and low dispersities (Đ = 1.05-1.12). Initial cellular uptake and toxicity studies reveal that PeptoStars are well tolerated by HeLa, HEK 293, and DC 2.4 cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Simvastatin-Loaded Nanoparticles Based on Cholic Acid-Core Star-Shaped PLGA for Breast Cancer Treatment.

PubMed

Wu, Yanping; Wang, Zhongyuan; Liu, Gan; Zeng, Xiaowei; Wang, Xusheng; Gao, Yongfeng; Jiang, Lijuan; Shi, Xiaojun; Tao, Wei; Huang, Laiqiang; Mei, Lin

2015-07-01

A novel nanocarrier system of cholic acid (CA) core, star-shaped polymer consisting of poly(D,L-lactide-co-glycolide) (PLGA) was developed for sustained and controlled delivery of simvastatin for chemotherapy of breast adenocarcinoma. The star-shaped polymer CA-PLGA with three branch arms was synthesized successfully through the core-first approach. The simvastatin-loaded star-shaped CA-PLGA nanoparticles were prepared through a modified nanoprecipitation method. The data showed that the fluorescence star-shaped CA-PLGA nanoparticles could be internalized into MDA-MB-231 and MDA-MB-468 human breast cancer cells. The simvastatin-loaded star-shaped CA-PLGA nanoparticles achieved significantly higher level of cytotoxicity than pristine simvastatin and simvastatin-loaded linear PLGA nanoparticles. Moreover, the expression of the cell cycle protein cyclin D1 was dramatically inhibited by simvastatin in both cells, with simvastatin-loaded star-shaped CA-PLGA nanoparticles having the greatest effect. MDA-MB-231 xenograft tumor model on BALB/c nude mice showed that simvastatin-loaded star-shaped CA-PLGA nanoformulations could effectively inhibit the growth of tumor over a longer period of time than pristine simvastatin and simvastatin-loaded linear PLGA nanoformulations at the same dose. In agreement with these, the nuclear expression of proliferation marker Ki-67 in simvastatin-loaded star-shaped CA-PLGA nanoparticles group was reduced to a most extent among four groups through tumor frozen section immunohistochemistry. In conclusion, the star-shaped CA-PLGA polymers could serve as a novel polymeric nanocarrier for breast cancer chemotherapy.

Emerging synthetic strategies for core cross-linked star (CCS) polymers and applications as interfacial stabilizers: bridging linear polymers and nanoparticles.

PubMed

Chen, Qijing; Cao, Xueteng; Xu, Yuanyuan; An, Zesheng

2013-10-01

Core cross-linked star (CCS) polymers become increasingly important in polymer science and are evaluated in many value-added applications. However, limitations exist to varied degrees for different synthetic methods. It is clear that improvement in synthetic efficiency is fundamental in driving this field moving even further. Here, the most recent advances are highlighted in synthetic strategies, including cross-linking with cross-linkers of low solubility, polymerization-induced self-assembly in aqueous-based heterogeneous media, and cross-linking via dynamic covalent bonds. The understanding of CCS polymers is also further refined to advocate their role as an intermediate between linear polymers and polymeric nanoparticles, and their use as interfacial stabilizers is rationalized within this context. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precisely Size-Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star-Like Block Copolymers.

PubMed

Chen, Yihuang; Yoon, Young Jun; Pang, Xinchang; He, Yanjie; Jung, Jaehan; Feng, Chaowei; Zhang, Guangzhao; Lin, Zhiqun

2016-12-01

In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., "hairs") with even length. Interestingly, amphiphilic star-like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer "hairs" are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long-term stability. This amphiphilic star-like block copolymer nanoreactor-based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self-assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer Vesicle Sensor for Visual and Sensitive Detection of SO2 in Water.

PubMed

Huang, Tong; Hou, Zhilin; Xu, Qingsong; Huang, Lei; Li, Chuanlong; Zhou, Yongfeng

2017-01-10

This study reports the first polymer vesicle sensor for the visual detection of SO 2 and its derivatives in water. A strong binding ability between tertiary alkanolamines and SO 2 has been used as the driving force for the detection by the graft of tertiary amine alcohol (TAA) groups onto an amphiphilic hyperbranched multiarm polymer, which can self-assemble into vesicles with enriched TAA groups on the surface. The polymer vesicles will undergo proton exchange with cresol red (CR) to produce CR-immobilized vesicles (CR@vesicles). Subsequently, through competitive binding with the TAA groups between CR and SO 2 or HSO 3 - , the CR@vesicles (purple) can quickly change into SO 2 @vesicles (colorless) with the release of protonated CR (yellow). Such a fast purple to yellow transition in the solution allows the visual detection of SO 2 or its derivatives in water by the naked eye. A visual test paper for SO 2 gas has also been demonstrated by the adsorption of CR@vesicles onto paper. Meanwhile, the detection limit of CR@vesicles for HSO 3 - is approximately 25 nM, which is improved by approximately 30 times when compared with that of small molecule-based sensors with a similar structure (0.83 μM). Such an enhanced detection sensitivity should be related to the enrichment of TAA groups as well as the CR in CR@vesicles. In addition, the CR@vesicle sensors also show selectivity and specificity for the detection of SO 2 or HSO 3 - among anions such as F - , Br - , Cl - , SO 4 2- , NO 2 - , C 2 O 4 2- , S 2 O 3 2- , SCN - , AcO - , SO 3 2- , S 2- , and HCO 3 - .

Free Surface Relaxations of Star-Shaped Polymer Films

DOE PAGES

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley; ...

2017-11-28

Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature Tmore » $$bulk\\atop{g}$$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm M arm < M e (M e is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$$bulk\\atop{g}$$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above T g and at length and time scales not associated with the glass transition has not previously been reported for polymers.« less

Compressible or incompressible blend of interacting monodisperse star and linear polymers near a surface.

PubMed

Batman, Richard; Gujrati, P D

2008-03-28

We consider a lattice model of a mixture of repulsive, attractive, or neutral monodisperse star (species A) and linear (species B) polymers with a third monomeric species C, which may represent free volume. The mixture is next to a hard, infinite plate whose interactions with A and C can be attractive, repulsive, or neutral. These two interactions are the only parameters necessary to specify the effect of the surface on all three components. We numerically study monomer density profiles using the method of Gujrati and Chhajer that has already been previously applied to study polydisperse and monodisperse linear-linear blends next to surfaces. The resulting density profiles always show an enrichment of linear polymers in the immediate vicinity of the surface due to entropic repulsion of the star core. However, the integrated surface excess of star monomers is sometimes positive, indicating an overall enrichment of stars. This excess increases with the number of star arms only up to a certain critical number and decreases thereafter. The critical arm number increases with compressibility (bulk concentration of C). The method of Gujrati and Chhajer is computationally ultrafast and can be carried out on a personal computer (PC), even in the incompressible case, when simulations are unfeasible. Calculations of density profiles usually take less than 20 min on PCs.

Novel polymers and method of preparing same

NASA Technical Reports Server (NTRS)

Hirshfield, S. M. (Inventor)

1973-01-01

Polymers are prepared with terminal functional groups by reacting a compound selected from the group consisting of lithium p-lithiophenoxide and tetrabutylammonium p-lithiophenoxide as an initiator with material such as butadiene. The resulting functionally terminated new polymers are then capable of reacting with coupling agents to form star polymers.

Optimism in the face of uncertainty supported by a statistically-designed multi-armed bandit algorithm.

PubMed

Kamiura, Moto; Sano, Kohei

2017-10-01

The principle of optimism in the face of uncertainty is known as a heuristic in sequential decision-making problems. Overtaking method based on this principle is an effective algorithm to solve multi-armed bandit problems. It was defined by a set of some heuristic patterns of the formulation in the previous study. The objective of the present paper is to redefine the value functions of Overtaking method and to unify the formulation of them. The unified Overtaking method is associated with upper bounds of confidence intervals of expected rewards on statistics. The unification of the formulation enhances the universality of Overtaking method. Consequently we newly obtain Overtaking method for the exponentially distributed rewards, numerically analyze it, and show that it outperforms UCB algorithm on average. The present study suggests that the principle of optimism in the face of uncertainty should be regarded as the statistics-based consequence of the law of large numbers for the sample mean of rewards and estimation of upper bounds of expected rewards, rather than as a heuristic, in the context of multi-armed bandit problems. Copyright © 2017 Elsevier B.V. All rights reserved.

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions.

PubMed

Chandran, Sivasurender; Saw, Shibu; Kandar, A K; Dasgupta, C; Sprung, M; Basu, J K

2015-08-28

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP:PS size ratios, ξ = 0.14 and 2.76 (where, ξ = Mg/Mm, Mg and Mm being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with ξ = 0.14 could be modeled reasonably well, while the structure of blends with ξ = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with ξ = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with ξ = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to understand not only the structural behavior of PGNPs but also possibly their dynamics and thermo-mechanical properties as well.

Mechanisms of the self-organization of star-shaped polymers with a varied structure of branching center based on fullerene C{sub 60} in solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lebedev, V. T., E-mail: vlebedev@pnpi.spb.ru; Toeroek, Gy.; Vinogradova, L. V.

The self-organization of star-shaped polymers in toluene has been studied by small-angle neutron scattering. Polystyrene stars with a mono-C{sub 60} branching center are ordered into globular clusters ({approx}1700 nm in diameter), whereas stars with a double (C{sub 60}-C{sub 60}) center are ordered into anisotropic structures (superchains), which are linked (depending on the concentration) into triads (chain clusters {approx}2500 nm in diameter). On the contrary, heteroarm polystyrene and poly-2-vinylpyridine stars with a C{sub 60} center are weakly associated into dimers. Moderately polar stars with arms composed of polystyrene and diblock copolymer (poly-2-vinylpyridine-poly-tret-butyl methacrylate) form short chains composed of four macromolecules, whilemore » stars of higher polarity based on polystyrene and poly-tret-butyl methacrylate form clusters containing {approx}12 macromolecules {approx}50 nm in diameter. Thus, by varying the structure of the center and the arm polarity, one can control the modes of star structuring.« less

Thiol-Reactive Star Polymers Display Enhanced Association with Distinct Human Blood Components.

PubMed

Glass, Joshua J; Li, Yang; De Rose, Robert; Johnston, Angus P R; Czuba, Ewa I; Khor, Song Yang; Quinn, John F; Whittaker, Michael R; Davis, Thomas P; Kent, Stephen J

2017-04-12

Directing nanoparticles to specific cell types using nonantibody-based methods is of increasing interest. Thiol-reactive nanoparticles can enhance the efficiency of cargo delivery into specific cells through interactions with cell-surface proteins. However, studies to date using this technique have been largely limited to immortalized cell lines or rodents, and the utility of this technology on primary human cells is unknown. Herein, we used RAFT polymerization to prepare pyridyl disulfide (PDS)-functionalized star polymers with a methoxy-poly(ethylene glycol) brush corona and a fluorescently labeled cross-linked core using an arm-first method. PDS star polymers were examined for their interaction with primary human blood components: six separate white blood cell subsets, as well as red blood cells and platelets. Compared with control star polymers, thiol-reactive nanoparticles displayed enhanced association with white blood cells at 37 °C, particularly the phagocytic monocyte, granulocyte, and dendritic cell subsets. Platelets associated with more PDS than control nanoparticles at both 37 °C and on ice, but they were not activated in the duration examined. Association with red blood cells was minor but still enhanced with PDS nanoparticles. Thiol-reactive nanoparticles represent a useful strategy to target primary human immune cell subsets for improved nanoparticle delivery.

Self-Assembly and Responsiveness of Polypeptide-Based Star and Triblock Copolymers

NASA Astrophysics Data System (ADS)

Savin, Daniel

This study involves the bottom-up design and tunability of responsive, peptide-based block polymers. The self-assembly of amphiphilic block polymers is dictated primarily by the balance between the hydrophobic core volume and the hydrophilic corona. In these studies, amphiphilic triblock and star copolymers containing poly(lysine) (PK), poly(leucine) (PL) and poly(glutamic acid) (PE) were synthesized and their solution properties studied using dynamic light scattering, circular dichroism spectroscopy and transmission electron microscopy. The peptide block in these structures can serve to introduce pH responsiveness (in the case of PK and PE), or can facilitate the formation of elongated or kinetically-trapped structures (in the case of PL.) This talk will present some recent studies in solution morphology transitions that occur in these materials under varying solution conditions. As the topological complexity of the polymers increases from diblock to linear triblock or star polymers, the solution morphology and response becomes much more complex. We present a systematic series of structures, with increasing complexity, that have applications as passive and active delivery vehicles, hydrogels, and responsive viscosity modifiers. NSF CHE-1539347.

Topological analysis of long-chain branching patterns in polyolefins.

PubMed

Bonchev, D; Markel, E; Dekmezian, A

2001-01-01

Patterns in molecular topology and complexity for long-chain branching are quantitatively described. The Wiener number, the topological complexity index, and a new index of 3-starness are used to quantify polymer structure. General formulas for these indices were derived for the cases of 3-arm star, H-shaped, and B-arm comb polymers. The factors affecting complexity in monodisperse polymer systems are ranked as follows: number of arms > arm length > arm central position approximately equal to arm clustering > total molecular weight approximately equal to backbone molecular weight. Topological indices change rapidly and then plateau as the molecular weight of branches on a polyolefin backbone increases from 0 to 5 kD. Complexity calculations relate 2-arm or 3-arm comb structures to the corresponding 3-arm stars of equivalent complexity but much higher molecular weight. In a subsequent paper, we report the application of topological analysis for developing structure/property relationships for monodisperse polymers. While the focus of the present work is on the description of monodisperse, well-defined architectures, the methods may be extended to the description of polydisperse systems.

Quantum-enhanced multiparameter estimation in multiarm interferometers

PubMed Central

Ciampini, Mario A.; Spagnolo, Nicolò; Vitelli, Chiara; Pezzè, Luca; Smerzi, Augusto; Sciarrino, Fabio

2016-01-01

Quantum metrology is the state-of-the-art measurement technology. It uses quantum resources to enhance the sensitivity of phase estimation over that achievable by classical physics. While single parameter estimation theory has been widely investigated, much less is known about the simultaneous estimation of multiple phases, which finds key applications in imaging and sensing. In this manuscript we provide conditions of useful particle (qudit) entanglement for multiphase estimation and adapt them to multiarm Mach-Zehnder interferometry. We theoretically discuss benchmark multimode Fock states containing useful qudit entanglement and overcoming the sensitivity of separable qudit states in three and four arm Mach-Zehnder-like interferometers - currently within the reach of integrated photonics technology. PMID:27381743

Simple artificial neural networks that match probability and exploit and explore when confronting a multiarmed bandit.

PubMed

Dawson, Michael R W; Dupuis, Brian; Spetch, Marcia L; Kelly, Debbie M

2009-08-01

The matching law (Herrnstein 1961) states that response rates become proportional to reinforcement rates; this is related to the empirical phenomenon called probability matching (Vulkan 2000). Here, we show that a simple artificial neural network generates responses consistent with probability matching. This behavior was then used to create an operant procedure for network learning. We use the multiarmed bandit (Gittins 1989), a classic problem of choice behavior, to illustrate that operant training balances exploiting the bandit arm expected to pay off most frequently with exploring other arms. Perceptrons provide a medium for relating results from neural networks, genetic algorithms, animal learning, contingency theory, reinforcement learning, and theories of choice.

The effect of polymer architecture on the interdiffusion in thin polymer films

NASA Astrophysics Data System (ADS)

Caglayan, Ayse; Yuan, Guangcui; Satija, Sushil K.; Uhrig, David; Hong, Kunlun; Akgun, Bulent

Branched polymer chains have been traditionally used in industrial applications as additives. Recently they have found applications in electrochromic displays, lithography, biomedical coatings and targeting multidrug resistant bacteria. In some of these applications where they are confined in thin layers, it is important to understand the relation between the mobility and polymer chain architecture to optimize the processing conditions. Earlier interdiffusion measurements on linear and cyclic polymer chains demonstrated the key role of chain architecture on mobility. We have determined the vertical diffusion coefficients of the star polystyrene chains in thin films as a function of number of polymer arms, molecular weight per arm, and film thickness using neutron reflectivity (NR) and compare our results with linear chains of identical total molecular weight. Bilayer samples of 4-arm and 8-arm protonated polystyrenes (hPS) and deuterated polystyrenes (dPS) were used to elucidate the effect of polymer chain architecture on polymer diffusion. NR measurements indicate that the mobility of polymer chains in thin films get faster as the number of polymer arms increases and the arm molecular weight decreases. Both star polymers showed faster interdiffusion compared to their linear analog. Diffusion coefficient of branched PS chains has a weak dependence on the film thickness.

Study of the antibacterial and antifungal activities of synthetic benzyl bromides, ketones, and corresponding chalcone derivatives.

PubMed

Shakhatreh, Muhamad Ali K; Al-Smadi, Mousa L; Khabour, Omar F; Shuaibu, Fatima A; Hussein, Emad I; Alzoubi, Karem H

2016-01-01

Several applications of chalcones and their derivatives encouraged researchers to increase their synthesis as an alternative for the treatment of pathogenic bacterial and fungal infections. In the present study, chalcone derivatives were synthesized through cross aldol condensation reaction between 4-( N , N -dimethylamino)benzaldehyde and multiarm aromatic ketones. The multiarm aromatic ketones were synthesized through nucleophilic substitution reaction between 4-hydroxy acetophenone and benzyl bromides. The benzyl bromides, multiarm aromatic ketones, and corresponding chalcone derivatives were evaluated for their activities against eleven clinical pathogenic Gram-positive, Gram-negative bacteria, and three pathogenic fungi by the disk diffusion method. The minimum inhibitory concentration was determined by the microbroth dilution technique. The results of the present study demonstrated that benzyl bromide derivatives have strong antibacterial and antifungal properties as compared to synthetic chalcone derivatives and ketones. Benzyl bromides (1a and 1c) showed high ester activity against Gram-positive bacteria and fungi but moderate activity against Gram-negative bacteria. Therefore, these compounds may be considered as good antibacterial and antifungal drug discovery. However, substituted ketones (2a-b) as well as chalcone derivatives (3a-c) showed no activity against all the tested strains except for ketone (2c), which showed moderate activity against Candida albicans .

Study of the antibacterial and antifungal activities of synthetic benzyl bromides, ketones, and corresponding chalcone derivatives

PubMed Central

Shakhatreh, Muhamad Ali K; Al-Smadi, Mousa L; Khabour, Omar F; Shuaibu, Fatima A; Hussein, Emad I; Alzoubi, Karem H

2016-01-01

Several applications of chalcones and their derivatives encouraged researchers to increase their synthesis as an alternative for the treatment of pathogenic bacterial and fungal infections. In the present study, chalcone derivatives were synthesized through cross aldol condensation reaction between 4-(N,N-dimethylamino)benzaldehyde and multiarm aromatic ketones. The multiarm aromatic ketones were synthesized through nucleophilic substitution reaction between 4-hydroxy acetophenone and benzyl bromides. The benzyl bromides, multiarm aromatic ketones, and corresponding chalcone derivatives were evaluated for their activities against eleven clinical pathogenic Gram-positive, Gram-negative bacteria, and three pathogenic fungi by the disk diffusion method. The minimum inhibitory concentration was determined by the microbroth dilution technique. The results of the present study demonstrated that benzyl bromide derivatives have strong antibacterial and antifungal properties as compared to synthetic chalcone derivatives and ketones. Benzyl bromides (1a and 1c) showed high ester activity against Gram-positive bacteria and fungi but moderate activity against Gram-negative bacteria. Therefore, these compounds may be considered as good antibacterial and antifungal drug discovery. However, substituted ketones (2a–b) as well as chalcone derivatives (3a–c) showed no activity against all the tested strains except for ketone (2c), which showed moderate activity against Candida albicans. PMID:27877017

Fabrication of injectable high strength hydrogel based on 4-arm star PEG for cartilage tissue engineering.

PubMed

Wang, Jianqi; Zhang, Fengjie; Tsang, Wing Pui; Wan, Chao; Wu, Chi

2017-03-01

Hydrogels prepared from poly(ethylene glycol) (PEG) are widely applied in tissue engineering, especially those derived from a combination of functional multi-arm star PEG and linear crosslinker, with an expectation to form a structurally ideal network. However, the poor mechanical strength still renders their further applications. Here we examined the relationship between the dynamics of the pre-gel solution and the mechanical property of the resultant hydrogel in a system consisting of 4-arm star PEG functionalized with vinyl sulfone and short dithiol crosslinker. A method to prepare mechanically strong hydrogel for cartilage tissue engineering is proposed. It is found that when gelation takes place at the overlap concentration, at which a slow relaxation mode just appears in dynamic light scattering (DLS), the resultant hydrogel has a local maximum compressive strength ∼20 MPa, while still keeps ultralow mass concentration and Young's modulus. Chondrocyte-laden hydrogel constructed under this condition was transplanted into the subcutaneous pocket and an osteochondral defect model in SCID mice. The in vivo results show that chondrocytes can proliferate and maintain their phenotypes in the hydrogel, with the production of abundant extracellular matrix (ECM) components, formation of typical chondrocyte lacunae structure and increase in Young's modulus over 12 weeks, as indicated by histological, immunohistochemistry, gene expression analyses and mechanical test. Moreover, newly formed hyaline cartilage was observed to be integrated with the host articular cartilage tissue in the defects injected with chondrocytes/hydrogel constructs. The results suggest that this hydrogel is a promising candidate scaffold for cartilage tissue engineering. Copyright © 2016 Elsevier Ltd. All rights reserved.

RAFT polymerization and some of its applications.

PubMed

Moad, Graeme; Rizzardo, Ezio; Thang, San H

2013-08-01

Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Solvent on the Drug-Loading Process of Amphiphilic Nanogel Star Polymers.

PubMed

Carr, Amber C; Piunova, Victoria A; Maarof, Hasmerya; Rice, Julia E; Swope, William C

2018-05-31

We present an all-atom molecular dynamics study of the effect of a range of organic solvents (dichloromethane, diethyl ether, toluene, methanol, dimethyl sulfoxide, and tetrahydrofuran) on the conformations of a nanogel star polymeric nanoparticle with solvophobic and solvophilic structural elements. These nanoparticles are of particular interest for drug delivery applications. As drug loading generally takes place in an organic solvent, this work serves to provide insight into the factors controlling the early steps of that process. Our work suggests that nanoparticle conformational structure is highly sensitive to the choice of solvent, providing avenues for further study as well as predictions for both computational and experimental explorations of the drug-loading process. Our findings suggest that when used in the drug-loading process, dichloromethane, tetrahydrofuran, and toluene allow for a more extensive and increased drug-loading into the interior of nanogel star polymers of the composition studied here. In contrast, methanol is more likely to support shallow or surface loading and, consequently, faster drug release rates. Finally, diethyl ether should not work in a formulation process since none of the regions of the nanogel star polymer appear to be sufficiently solvated by it.

Host-guest interaction induced supramolecular amphiphilic star architecture and uniform nanovesicle formation for anticancer drug delivery

NASA Astrophysics Data System (ADS)

Zhu, Jing-Ling; Liu, Kerh Li; Wen, Yuting; Song, Xia; Li, Jun

2016-01-01

A star polymer of poly[(R,S)-3-hydroxybutyrate] (PHB) with adamantyl end-terminals extended from an α-cyclodextrin (α-CD) core is designed. It subsequently self-assembles to form controllable and uniform nanovesicles induced by host-guest interactions between heptakis(2,6-di-O-methyl)-β-CD and the adamantyl ends. The nanovesicles are suitable for loading and intracellular delivery of the anticancer drug doxorubicin.A star polymer of poly[(R,S)-3-hydroxybutyrate] (PHB) with adamantyl end-terminals extended from an α-cyclodextrin (α-CD) core is designed. It subsequently self-assembles to form controllable and uniform nanovesicles induced by host-guest interactions between heptakis(2,6-di-O-methyl)-β-CD and the adamantyl ends. The nanovesicles are suitable for loading and intracellular delivery of the anticancer drug doxorubicin. Electronic supplementary information (ESI) available: Polymer synthesis, characterization, preparation of drug-loaded nanovesicles, intracellular drug release and cytotoxicity assays, TEM and DLS measurements. See DOI: 10.1039/c5nr06744h

Cyclodextrin-based star polymers as a versatile platform for nanochemotherapeutics: Enhanced entrapment and uptake of idarubicin.

PubMed

Nafee, N; Hirosue, M; Loretz, B; Wenz, G; Lehr, C-M

2015-05-01

A series of cyclodextrin-based star polymers were synthesized using β-cyclodextrin (CD) as hydrophilic core, methyl methacrylate (MMA) and tert-butyl acrylate (tBA) as hydrophobic arms. Star polymers, either homopolymers or random/block copolymers, showed narrow molecular weight distributions. Grafting hydrophobic arms created CD-based nanoparticles (CD-NPs) in the size range (130-200nm) with narrow PdI <0.15 and slightly negative ζ-potential. Particle surface could be modified with chitosan to impart a positive surface charge. Colloidal stability of CD-NPs was a function of pH as revealed by the pH-titration curves. CD-NPs were used as carrier for the chemotherapeutic drug idarubicin (encapsulation efficiency, EE ∼40%) ensuring prolonged release profile (∼80% after 48h). For cell-based studies, coumarin-6 was encapsulated as a fluorescent marker (EE ∼75%). Uptake studies carried out on A549 and Caco-2 cell lines proved the uptake of coumarin-loaded NPs as a function of time and preferential localization in the cytoplasm. Uptake kinetics revealed no saturation or plateau over 6h. Chitosan-modified NPs showed significantly improved, concentration-dependent cellular uptake. Meanwhile, CD-NPs were non-cytotoxic on both cell lines over the concentration range (0.25-3mg/ml) as studied by MTT and LDH assays. In conclusion, CD star polymers can be considered a versatile platform for a new class of biocompatible nanochemotherapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

PubMed

Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

2014-11-04

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

Dual functional star polymers for lubricants

DOE PAGES

Cosimbescu, Lelia; Robinson, Joshua W.; Zhou, Yan; ...

2016-09-12

Star-shaped poly(alkyl methacrylate)s (PAMAs) with a three arm architecturewere designed, prepared and their performance as a dual additive (viscosity index improver and friction modifier) for engine oils was evaluated. Furthermore, the structure property relationships between the macromolecular structure and lubricant performance were studied, such as molecular weight and polarity effects on the viscosity index. Several copolymers of dodecylmethacrylate with polar methacrylates in various amounts and various topologies, were synthesized as model compounds. Star polymers with a polar content of at least 10% in a block or tapered block topology effectively reduced the friction coefficient in both mixed and boundary lubricationmore » regimes. Furthermore, a polar content of 20% was efficient in reducing friction in both random and block topologies.« less

Mode Theory of Multi-Armed Spiral Antennas and Its Application to Electronic Warfare Antennas

NASA Astrophysics Data System (ADS)

Radway, Matthew J.

Since their invention about 55 years ago, spiral antennas have earned a reputation for providing stable impedance and far-field patterns over multi-decade frequency ranges. For the first few decades these antennas were researched for electronic warfare receiving applications, primarily in the 2-18 GHz range. This research was often done under conditions of secrecy, and often by private contractors who did not readily share their research, and now have been defunct for decades. Even so, the body of literature on the two-armed variant of these antennas is rich, often leading non-specialists to the misconception that these antennas are completely understood. Furthermore, early work was highly experimental in nature, and was conducted before modern data collection and postprocessing capabilities were widespread, which limited the range of the studies. Recent research efforts have focused on extending the application of spirals into new areas, as well as applying exotic materials to `improve' their performance and reduce their size. While interesting results have been obtained, in most instances these were incomplete, often compromising the frequency independent nature of these antennas. This thesis expands the role of the multi-armed spiral outside of its traditional niche of receive-only monopulse direction finding. As a first step, careful study of the spiral-antenna mode theory is undertaken with particular attention paid to the concepts of mode filtering and modal decomposition. A technique for reducing the modal impedance of high arm-count spirals is introduced. The insights gained through this theoretical study are first used to improve the far-field performance of the coiled-arm spiral antenna. Specifically, expanding the number of arms on a coiled arm spiral from two to four while providing proper excitation enables dramatically improved broadside axial ratio and azimuthal pattern uniformity. The multiarming technique is then applied to the design of an antenna with exceptionally stable and clean radiation patterns without use of an absorbing cavity. The multiarming technique allows the spiral to retain its pattern integrity at frequencies well below those of comparable two-armed spiral antennas. A quadrifilar helix-type of end-loading is applied to the end of the spiral, resulting in dramatically-improved low-frequency gain. Careful application of resistive end-loading allows good impedance matching at frequencies as low as one-half of the Mode 1 cutoff frequency, while providing acceptable radiation efficiency due to effective use of the available antenna volume. A novel dual-layering technique for reducing the spiral's modal impedance is presented, allowing the antenna to present a good impedance match to a 50 ohm system. The third application of mode theory has been to exploit the wideband multi-mode capability of the multi-armed spiral antenna to implement a simple wide-band radiation pattern nulling technique on a multi-armed spiral antenna. It is shown that wideband nulling is possible and that, in contrast to traditional array antennas, grating lobes do not appear even over extremely wide bandwidths. Simple techniques for addressing the phenomenon of null rotation with frequency are discussed. Finally, mode theory has been used to analyze beamformer non-idealities. This has led to the revelation that the spectral distribution of beamformer errors is at least as important as the magnitude of those errors. Proper choice of beamformer topology can result in noticeable improvement in the antenna performance.

Star Polymers Reduce Islet Amyloid Polypeptide Toxicity via Accelerated Amyloid Aggregation.

PubMed

Pilkington, Emily H; Lai, May; Ge, Xinwei; Stanley, William J; Wang, Bo; Wang, Miaoyi; Kakinen, Aleksandr; Sani, Marc-Antonie; Whittaker, Michael R; Gurzov, Esteban N; Ding, Feng; Quinn, John F; Davis, Thomas P; Ke, Pu Chun

2017-12-11

Protein aggregation into amyloid fibrils is a ubiquitous phenomenon across the spectrum of neurodegenerative disorders and type 2 diabetes. A common strategy against amyloidogenesis is to minimize the populations of toxic oligomers and protofibrils by inhibiting protein aggregation with small molecules or nanoparticles. However, melanin synthesis in nature is realized by accelerated protein fibrillation to circumvent accumulation of toxic intermediates. Accordingly, we designed and demonstrated the use of star-shaped poly(2-hydroxyethyl acrylate) (PHEA) nanostructures for promoting aggregation while ameliorating the toxicity of human islet amyloid polypeptide (IAPP), the peptide involved in glycemic control and the pathology of type 2 diabetes. The binding of PHEA elevated the β-sheet content in IAPP aggregates while rendering a new morphology of "stelliform" amyloids originating from the polymers. Atomistic molecular dynamics simulations revealed that the PHEA arms served as rodlike scaffolds for IAPP binding and subsequently accelerated IAPP aggregation by increased local peptide concentration. The tertiary structure of the star nanoparticles was found to be essential for driving the specific interactions required to impel the accelerated IAPP aggregation. This study sheds new light on the structure-toxicity relationship of IAPP and points to the potential of exploiting star polymers as a new class of therapeutic agents against amyloidogenesis.

Preparation and characterization of conjugated polyamidoamine-MPEG-methotrexate for potential drug delivery system

NASA Astrophysics Data System (ADS)

Mohd Sabri, Siti Noorzidah bt; Abu, Norhidayah; Mastor, Azreena; Hisham, Siti Farhana; Noorsal, Kartini

2012-07-01

Star polymers have unique characteristics due to their well-defined size and tailor ability which makes these polymers attractive candidates as carriers in drug delivery system applications. This work focuses on attaching a drug to the star polymer (polyamidoamine). The conjugation of polyamidoamine (PAMAM, generation 4) with methotrexate (MTX) (model drug) was studied in which monomethyl polyethylene glycol (MPEG) was used as a linker to reduce the toxicity of dendrimer. Conjugation starts with attaching the drug to the linker and followed by further conjugation with the polyamidoamine (PAMAM) dendrimer. The conjugation of PAMAM-PEG-MTX was confirmed through UV-Vis, FTIR, 1H NMR and DSC. The loading capacities and release profile of this conjugate were determined using 1H NMR and UV spectrometer.

Instrumentation and analysis of frost heave mitigation on WY-70, Encampment, WY.

DOT National Transportation Integrated Search

2014-05-01

This project investigated a novel procedure to reduce or prevent subgrade freezing non-destructively by injecting a two-part polymer foam at : the top of the subgrade. Controlled injection of Uretek Star, expanding structural polymer foam, created a ...

Method of Preparing Polymers with Low Melt Viscosity

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor)

2001-01-01

This invention is an improvement in standard polymerizations procedures, i.e., addition-type and step-growth type polymerizations, wherein monomers are reacted to form a growing polymer chain. The improvement includes employing an effective amount of a trifunctional monomer (such as a trifunctional amine anhydride, or phenol) in the polymerization procedure to form a mixture of polymeric materials consisting of branced polymers, star-shaped polymers, and linear polymers. This mixture of polymeric materials has a lower melt temperature and a lower melt viscosity than corresponding linear polymeric materials of equivalent molecular weight.

Multiarm-polyethylene glycol-polyglutamic acid peptide dendrimer: Design, synthesis, and dissolving thrombus.

PubMed

Zhang, Shao-Fei; Lü, Shaoyu; Gao, Chunmei; Yang, Jiandong; Yan, Xiang; Li, Tao; Wen, Na; Huang, Mengjie; Liu, Mingzhu

2018-06-01

Thrombotic events affect many individuals in a number of ways, all of which can cause significant morbidity and mortality. Nattokinase (NK), as a novel thrombolytic drug, has been used for thrombolytic therapy. It not only possesses plasminogen activator activity, but also directly digests fibrin through limited proteolysis. However, it may undergo inactivation and denaturation in the harsh external environment. In this study, a multiarm-polyethylene glycol-polyglutamic acid peptide dendrimer was fabricated and used as a carrier for NK protection and delivery. Different arm numbers of polyethylene glycol-polyglutamic acid peptide dendrimers (x-PEG(G 3 ) x , x = 2, 4, 6, 8) were designed, prepared, and characterized by 1 H NMR and FTIR. Then, x-PEG(G 3 ) x were loaded with NK to form nanocomposites. Their size and morphology were determined by dynamic light scattering and transmission electron microscopy. Enzyme activity was evaluated via UV-Vis absorbance spectra, fluorescence spectra, circular dichroism spectra, and zeta potential measurements. The study reveals that the obtained x-PEG(G 3 ) x /NK nanocomposites possess high enzyme activity. In addition, the nanocomposites show increased viability of rat macrophage cells, and excellent thrombolysis ability in vitro and in vivo. This work establishes a multiarm-polyethylene glycol-polyglutamic acid peptide dendrimer with potential application in NK carrier and thrombolytic therapy. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 1687-1696, 2018. © 2018 Wiley Periodicals, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley

The surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 K above the bulk glass transition temperature Tgbulk. This behavior, exhibited by star-shaped polystyrenes with functionality f=8 arms and molecular weights per arm Marm

Injection threshold for a star polymer inside a nanopore

NASA Astrophysics Data System (ADS)

Brochard-Wyart, Françoise; de Gennes, Pierre-Gilles

A linear, flexible polymer (in dilute solution with a good solvent) enters a pore (of diameter D smaller than its gyration radius R) only when the suction flux J is larger than a threshold value Jcl ≅ kT/η (T: temperature; η: solvent viscosity). We discuss here the case of an f arm star polymer (f >> 1). The results suggest that permeation through nanopores may provide an interesting characterization of mixtures containing linear and branched polymers with the same overall molecular weight. Un polymère linéaire flexible (en solution diluée dans un bon solvant) ne pénètre dans un pore (de diamètre D inférieure à son rayon de gyration R) que si le flux d'entraînement J est supérieur à une valeur seuil Jcl ≅ kT/η (T : température ; η: viscosité du solvant). Nous étendons ici la discussion au cas d'une étoile à f branches (f >> 1). Les résultats suggèrent que la perméation dans des nanopores peut être une méthode utile pour caractériser des mélanges de polymères linéaires et branchés de même masse moléculaire globale.

Online matching with queueing dynamics.

DOT National Transportation Integrated Search

2016-12-01

We consider a variant of the multiarmed bandit problem where jobs queue for service, and service rates of different servers may be unknown. We study algorithms that minimize queue-regret: the (expected) difference between the queue-lengths obtained b...

Factorial versus multi-arm multi-stage designs for clinical trials with multiple treatments.

PubMed

Jaki, Thomas; Vasileiou, Despina

2017-02-20

When several treatments are available for evaluation in a clinical trial, different design options are available. We compare multi-arm multi-stage with factorial designs, and in particular, we will consider a 2 × 2 factorial design, where groups of patients will either take treatments A, B, both or neither. We investigate the performance and characteristics of both types of designs under different scenarios and compare them using both theory and simulations. For the factorial designs, we construct appropriate test statistics to test the hypothesis of no treatment effect against the control group with overall control of the type I error. We study the effect of the choice of the allocation ratios on the critical value and sample size requirements for a target power. We also study how the possibility of an interaction between the two treatments A and B affects type I and type II errors when testing for significance of each of the treatment effects. We present both simulation results and a case study on an osteoarthritis clinical trial. We discover that in an optimal factorial design in terms of minimising the associated critical value, the corresponding allocation ratios differ substantially to those of a balanced design. We also find evidence of potentially big losses in power in factorial designs for moderate deviations from the study design assumptions and little gain compared with multi-arm multi-stage designs when the assumptions hold. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd.

Radiation and Scattering Compact Antenna Laboratory (RASCAL) Capabilities Brochure

DTIC Science & Technology

2016-09-06

Array Measurements Integrated Measurement of Subsystems with Digital Backends RADIATION AND SCATTERING COMPACT ANTENNA LABORATORY...hardware gating to eliminate sources of error within the range itself. Processing is also available for multi-arm spiral antennas for the generation

pH-induced inversion of water-in-oil emulsions to oil-in-water high internal phase emulsions (HIPEs) using core cross-linked star (CCS) polymer as interfacial stabilizer.

PubMed

Chen, Qijing; Deng, Xiaoyong; An, Zesheng

2014-06-01

A pH-responsive core cross-linked star (CCS) polymer containing poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) arms was used as an interfacial stabilizer for emulsions containing toluene (80 v%) and water (20 v%). In the pH range of 12.1-9.3, ordinary water-in-oil emulsions were formed. Intermediate multiple emulsions of oil-in-water-in-oil and water-in-oil-in-water were formed at pH 8.6 and 7.5, respectively. Further lowering the pH resulted in the formation of gelled high internal phase emulsions of oil-in-water type in the pH range of 6.4-0.6. The emulsion behavior was correlated with interfacial tension, conductivity and configuration of the CCS polymer at different pH. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and supramolecular assembly of biomimetic polymers

NASA Astrophysics Data System (ADS)

Marciel, Amanda Brittany

A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic oligopeptides nanostructures using microscale extensional flows. This strategy enabled reproducible, reliable fabrication of aligned hierarchical constructs that do not form spontaneously in solution. In this way, fluidic-directed assembly of supramolecular structures allows for unprecedented manipulation at the nano- and mesoscale, which has the potential to provide rapid and efficient control of functional materials properties.

Detailed Quantitative Classifications of Galaxy Morphology

NASA Astrophysics Data System (ADS)

Nair, Preethi

2018-01-01

Understanding the physical processes responsible for the growth of galaxies is one of the key challenges in extragalactic astronomy. The assembly history of a galaxy is imprinted in a galaxy’s detailed morphology. The bulge-to-total ratio of galaxies, the presence or absence of bars, rings, spiral arms, tidal tails etc, all have implications for the past merger, star formation, and feedback history of a galaxy. However, current quantitative galaxy classification schemes are only useful for broad binning. They cannot classify or exploit the wide variety of galaxy structures seen in nature. Therefore, comparisons of observations with theoretical predictions of secular structure formation have only been conducted on small samples of visually classified galaxies. However large samples are needed to disentangle the complex physical processes of galaxy formation. With the advent of large surveys, like the Sloan Digital Sky Survey (SDSS) and the upcoming Large Synoptic Survey Telescope (LSST) and WFIRST, the problem of statistics will be resolved. However, the need for a robust quantitative classification scheme will still remain. Here I will present early results on promising machine learning algorithms that are providing detailed classifications, identifying bars, rings, multi-armed spiral galaxies, and Hubble type.

Synthesis of pH-responsive β-CD-based star polymer and impact of its self-assembly behavior on pectinase activity.

PubMed

Hu, Dong; Yang, Hong; Liu, Jiangtao; Lei, Zhongli

2017-03-01

A novel type of pH-responsive star polymer based on β-cyclodextrin (β-CD) was synthesized and further covalently conjugated with enzyme. The impact of its self-assembly behavior on enzyme activity was investigated. In our design, azide containing the polymer (N 3 ) 7 -β-CD-(PtBA) 14 was synthesized via atom transfer radical polymerization of tert-butyl acrylate using (N 3 ) 7 -β-CD-(Br) 14 as the multifunctional initiator. The final product (N 3 ) 7 -β-CD-(PAA) 14 was obtained via hydrolysis and covalently conjugating pectinase onto pH-responsive polyacrylic acid (PAA) arms. PAA can change its conformation with the self-assembly by altered pH, leading its nanostructure into micellar nanoparticles in aqueous solution and further affecting the activity of immobilized pectinase. The results were proved by fluorescence spectroscopy and dynamic light scattering. This system proves that the activity of immobilized enzyme can be tailored predictably, and this pH-responsive polymer holds great potential for controllable delivery of enzymes. © 2016 International Union of Biochemistry and Molecular Biology, Inc.

The influence of polymer architecture on the assembly of poly(ethylene oxide) grafted C60 fullerene clusters in aqueous solution: a molecular dynamics simulation study.

PubMed

Hooper, Justin B; Bedrov, Dmitry; Smith, Grant D

2009-03-28

The effect of polymer architecture on the aggregation behavior of C60 fullerenes tethered with a single chain of poly(ethylene oxide) (PEO) in aqueous solution has been investigated using coarse-grained, implicit solvent molecular dynamics simulations. The PEO-grafted fullerenes were comprised of a single tether of 60 repeat units represented as a linear polymer, a three-arm star (20 repeat units/arm) or a six-arm star (10 repeat units/arm). Additionally, the influence of arm length on self-assembly of the PEO-fullerene conjugates was investigated for the three-arm stars. Self-assembly is driven by favorable fullerene-fullerene and fullerene-PEO interactions. Our simulations reveal that it should be possible to control the size and geometry of the self-assembled fullerene aggregates in water through variation of PEO architecture and PEO molecular weight. We found that aggregate size and shape could be understood qualitatively in terms of the packing parameter concept that has been employed for diblock polymer and surfactant self-assembly. Higher molecular weight PEO (longer arms) and more compact PEO (more arms for the same molecular weight) resulted in greater steric repulsion between fullerenes, engendering greater aggregate surface curvature and hence the formation of smaller, more spherically shaped aggregates. Finally, weak attractive interactions between PEO and the fullerenes were found to play an important role in determining aggregate shape, size and the dynamics of self-assembly.

Force-induced desorption of 3-star polymers: a self-avoiding walk model

NASA Astrophysics Data System (ADS)

Janse van Rensburg, E. J.; Whittington, S. G.

2018-05-01

We consider a simple cubic lattice self-avoiding walk model of 3-star polymers adsorbed at a surface and then desorbed by pulling with an externally applied force. We determine rigorously the free energy of the model in terms of properties of a self-avoiding walk, and show that the phase diagram includes four phases, namely a ballistic phase where the extension normal to the surface is linear in the length, an adsorbed phase and a mixed phase, in addition to the free phase where the model is neither adsorbed nor ballistic. In the adsorbed phase all three branches or arms of the star are adsorbed at the surface. In the ballistic phase two arms of the star are pulled into a ballistic phase, while the remaining arm is in a free phase. In the mixed phase two arms in the star are adsorbed while the third arm is ballistic. The phase boundaries separating the ballistic and mixed phases, and the adsorbed and mixed phases, are both first order phase transitions. The presence of the mixed phase is interesting because it does not occur for pulled, adsorbed self-avoiding walks. In an atomic force microscopy experiment it would appear as an additional phase transition as a function of force.

Mirrors Containing Biomimetic Shape-Control Actuators

NASA Technical Reports Server (NTRS)

Bar-Cohen, Yoseph; Mouroulis, Pantazis; Bao, Xiaoqi; Sherrit, Stewart

2003-01-01

Curved mirrors of a proposed type would comprise lightweight sheets or films containing integral, biologically inspired actuators for controlling their surface figures. These mirrors could be useful in such applications as collection of solar energy, focusing of radio beams, and (provided sufficient precision could be achieved) imaging. These mirrors were originally intended for use in outer space, but it should also be possible to develop terrestrial versions. Several prior NASA Tech Briefs articles have described a variety of approaches to the design of curved, lightweight mirrors containing integral shape-control actuators. The primary distinction between the present approach and the prior approaches lies in the actuator design concept, which involves shapes and movements reminiscent of those of a variety of small, multi-armed animals. The shape and movement of an actuator of this type can also be characterized as reminiscent of that of an umbrella. This concept can be further characterized as a derivative of that of multifinger grippers, the fingers of which are bimorph bending actuators (see Figure 1). The fingers of such actuators can be strips containing any of a variety of materials that have been investigated for use as actuators, including such electroactive polymers as ionomeric polymer/metal composites (IPMCs), ferroelectric polymers, and grafted elastomers. A mirror according to this proposal would be made from a sheet of one of the actuator composites mentioned above. The design would involve many variables, including the pre-curvature and stiffness of the mirror sheet, the required precision of figure control, the required range of variation in focal length (see Figure 2), the required precision of figure control for imaging or non-imaging use, the bending and twisting moments needed to effect the required deformations, and voltage-tomoment coefficients of the actuators, and the voltages accordingly required for actuation. A typical design would call for segmentation of the electrodes on the actuators so that voltages could be applied locally to effect local bending for fine adjustment of the surface figure.

Lung-MAP Launches: First Precision Medicine Trial From National Clinical Trials Network

Cancer.gov

A unique public-private collaboration today announced the initiation of the Lung Cancer Master Protocol (Lung-MAP) trial, a multi-drug, multi-arm, biomarker-driven clinical trial for patients with advanced squamous cell lung cancer. Squamous cell carcinom

The tracer diffusion coefficient of soft nanoparticles in a linear polymer matrix

DOE PAGES

Imel, Adam E.; Rostom, Sahar; Holley, Wade; ...

2017-03-09

The diffusion properties of nanoparticles in polymer nanocomposites are largely unknown and are often difficult to determine experimentally. To address this shortcoming, we have developed a novel method to determine the tracer diffusion coefficient of soft polystyrene nanoparticles in a linear polystyrene matrix. Monitoring the interdiffusion of soft nanoparticles into a linear polystyrene matrix provides the mutual diffusion coefficient of this system, from which the tracer diffusion coefficient of the soft nanoparticle can be determined using the slow mode theory. Utilizing this protocol, the role of nanoparticle molecular weight and rigidity on its tracer diffusion coefficient is provided. These resultsmore » demonstrate that the diffusive behavior of these soft nanoparticles differ from that of star polymers, which is surprising since our recent studies suggest that the nanoparticle interacts with a linear polymer similarly to that of a star polymer. It appears that these deformable nanoparticles mostly closely mimic the diffusive behavior of fractal macromolecular architectures or microgels, where the transport of the nanoparticle relies on the cooperative motion of neighboring linear chains. Finally, the less cross-linked, and thus more deformable, nanoparticles diffuse faster than the more highly crosslinked nanoparticles, presumably because the increased deformability allows the nanoparticle to distort and fit into available space.« less

Octopus-inspired multi-arm robotic swimming.

PubMed

Sfakiotakis, M; Kazakidi, A; Tsakiris, D P

2015-05-13

The outstanding locomotor and manipulation characteristics of the octopus have recently inspired the development, by our group, of multi-functional robotic swimmers, featuring both manipulation and locomotion capabilities, which could be of significant engineering interest in underwater applications. During its little-studied arm-swimming behavior, as opposed to the better known jetting via the siphon, the animal appears to generate considerable propulsive thrust and rapid acceleration, predominantly employing movements of its arms. In this work, we capture the fundamental characteristics of the corresponding complex pattern of arm motion by a sculling profile, involving a fast power stroke and a slow recovery stroke. We investigate the propulsive capabilities of a multi-arm robotic system under various swimming gaits, namely patterns of arm coordination, which achieve the generation of forward, as well as backward, propulsion and turning. A lumped-element model of the robotic swimmer, which considers arm compliance and the interaction with the aquatic environment, was used to study the characteristics of these gaits, the effect of various kinematic parameters on propulsion, and the generation of complex trajectories. This investigation focuses on relatively high-stiffness arms. Experiments employing a compliant-body robotic prototype swimmer with eight compliant arms, all made of polyurethane, inside a water tank, successfully demonstrated this novel mode of underwater propulsion. Speeds of up to 0.26 body lengths per second (approximately 100 mm s(-1)), and propulsive forces of up to 3.5 N were achieved, with a non-dimensional cost of transport of 1.42 with all eight arms and of 0.9 with only two active arms. The experiments confirmed the computational results and verified the multi-arm maneuverability and simultaneous object grasping capability of such systems.

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Probing the self-assembled nanostructures of functional polymers with synchrotron grazing incidence X-ray scattering.

PubMed

Ree, Moonhor

2014-05-01

For advanced functional polymers such as biopolymers, biomimic polymers, brush polymers, star polymers, dendritic polymers, and block copolymers, information about their surface structures, morphologies, and atomic structures is essential for understanding their properties and investigating their potential applications. Grazing incidence X-ray scattering (GIXS) is established for the last 15 years as the most powerful, versatile, and nondestructive tool for determining these structural details when performed with the aid of an advanced third-generation synchrotron radiation source with high flux, high energy resolution, energy tunability, and small beam size. One particular merit of this technique is that GIXS data can be obtained facilely for material specimens of any size, type, or shape. However, GIXS data analysis requires an understanding of GIXS theory and of refraction and reflection effects, and for any given material specimen, the best methods for extracting the form factor and the structure factor from the data need to be established. GIXS theory is reviewed here from the perspective of practical GIXS measurements and quantitative data analysis. In addition, schemes are discussed for the detailed analysis of GIXS data for the various self-assembled nanostructures of functional homopolymers, brush, star, and dendritic polymers, and block copolymers. Moreover, enhancements to the GIXS technique are discussed that can significantly improve its structure analysis by using the new synchrotron radiation sources such as third-generation X-ray sources with picosecond pulses and partial coherence and fourth-generation X-ray laser sources with femtosecond pulses and full coherence. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley

Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature Tmore » $$bulk\\atop{g}$$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm M arm < M e (M e is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$$bulk\\atop{g}$$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above T g and at length and time scales not associated with the glass transition has not previously been reported for polymers.« less

Photoinduced smart, self-healing polymer sealant for photovoltaics.

PubMed

Banerjee, Sanjib; Tripathy, Ranjan; Cozzens, David; Nagy, Tibor; Keki, Sandor; Zsuga, Miklos; Faust, Rudolf

2015-01-28

Polyisobutylene (PIB)-based polymer networks potentially useful as smart coatings for photovoltaic devices have been developed. Low molecular weight coumarin functional triarm star PIB was synthesized via a single step SN2 reaction of bromoallyl functional triarm star PIB with 4-methylumbelliferone or umbelliferone in the presence of sodium hydride. Quantitative end functionality was confirmed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. UVA (λmax = 365 nm) induced reversible photodimerization of the coumarin moieties resulted in cross-linked elastomeric films exhibiting self-healing behavior. The extent of photodimerization/photoscission was monitored by UV-vis spectroscopy. The low oxygen (1.9 × 10(-16) mol m m(-2) s(-1) Pa(-1)) and moisture (46 × 10(-16) mol m m(-2) s(-1) Pa(-1)) permeability of the cross-linked polymer films suggest excellent barrier properties of the cross-linked polymer films. The self-healing process was studied by atomic force microscopy (AFM). For this, mechanical cuts were introduced in the cross-linked PIB films through micromachining with an AFM tip and the rate of healing induced by UV, sunlight, or both was followed by taking AFM images of the film at different time intervals during the repair process.

Multi-Armed Bandits for Intelligent Tutoring Systems

ERIC Educational Resources Information Center

Clement, Benjamin; Roy, Didier; Oudeyer, Pierre-Yves; Lopes, Manuel

2015-01-01

We present an approach to Intelligent Tutoring Systems which adaptively personalizes sequences of learning activities to maximize skills acquired by students, taking into account the limited time and motivational resources. At a given point in time, the system proposes to the students the activity which makes them progress faster. We introduce two…

High-functionality star-branched macromolecules: polymer size and virial coefficients.

PubMed

Randisi, Ferdinando; Pelissetto, Andrea

2013-10-21

We perform high-statistics Monte Carlo simulations of a lattice model to compute the radius of gyration Rg, the center-to-end distance, the monomer distribution, and the second and third virial coefficients of star polymers for a wide range of functionalities f, 6 ≤ f ≤ 120. We consider systems with a large number L of monomers per arm (100 is approximately < L is approximately < 1000 for f ≤ 40 and 100 is approximately < L is approximately < 400 for f = 80, 120), which allows us to determine accurately all quantities in the scaling regime. Results are extrapolated to determine the behavior of the different quantities in the limit f → ∞. Structural results are finally compared with the predictions of the Daoud-Cotton model. It turns out that the blob picture of a star polymer is essentially correct up to the corona radius Rc, which depends on f and which varies from 0.7Rg for f = 6 to 1.0Rg for f = 40. The outer region (r > Rc), in which the monomer distribution decays exponentially, shrinks as f increases, but it does not disappear in the scaling regime even in the limit f → ∞. We also consider the Daoud-Cotton scaling relation Rg (2)~f(1-ν)L(2ν), which is found to hold only for f > 100.

Thermoresponsive Supramolecular Chemotherapy by "V"-Shaped Armed β-Cyclodextrin Star Polymer to Overcome Drug Resistance.

PubMed

Fan, Xiaoshan; Cheng, Hongwei; Wang, Xiaoyuan; Ye, Enyi; Loh, Xian Jun; Wu, Yun-Long; Li, Zibiao

2018-04-01

Pump mediated drug efflux is the key reason to result in the failure of chemotherapy. Herein, a novel star polymer β-CD-v-(PEG-β-PNIPAAm) 7 consisting of a β-CD core, grafted with thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm) and biocompatible poly(ethylene glycol) (PEG) in the multiple "V"-shaped arms is designed and further fabricated into supramolecular nanocarriers for drug resistant cancer therapy. The star polymer could encapsulate chemotherapeutics between β-cyclodextrin and anti-cancer drug via inclusion complex (IC). Furthermore, the temperature induced chain association of PNIPAAm segments facilitated the IC to form supramolecular nanoparticles at 37 °C, whereas the presence of PEG impart great stability to the self-assemblies. When incubated with MDR-1 membrane pump regulated drug resistant tumor cells, much higher and faster cellular uptake of the supramolecular nanoparticles were detected, and the enhanced intracellular retention of drugs could lead to significant inhibition of cell growth. Further in vivo evaluation showed high therapeutic efficacy in suppressing drug resistant tumor growth without a significant impact on the normal functions of main organs. This work signifies thermo-responsive supramolecular chemotherapy is promising in combating pump mediated drug resistance in both in vitro and in vivo models, which may be encouraging for the advanced drug delivery platform design to overcome drug resistant cancer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wobbling The Galactic Disk with Bombardment of Satellite Galaxies

NASA Astrophysics Data System (ADS)

D'Onghia, Elena

We propose to assess the effect of impacts of large visible satellite galaxies on a disk, as well as the relevance of the continuing bombardment of the Galactic disk by dark matter clumps as predicted by the current cosmological framework that can wobble the disk, heating it and eventually exciting ragged spiral structures. In particular, we make detailed predictions for observable features such as spiral arms, rings and their associated stars in galactic disks and relate them to the physical processes that drive their formation and evolution in our Milky Way galaxy and nearby spirals. To do this, we will combine analytic methods and numerical simulations that allow us to calculate observables, which we will compare to present and forthcoming observations. Our methodology utilizes a combination of state of the art hydrodynamic simulations of galaxy evolution and multi- wavelength radiative transfer simulations. Our primary goals are: (1) To identify the physical processes that are responsible for spiral structure formation observed in our Milky Way and nearby disk galaxies, from the flocculent to grand- designed spiral galaxies and to provide observable signatures to be compared with data on nearby galaxies combining maps of 24 micron emission (Spitzer) and cold gas, CO (Heracles) and HI (THINGS). (2) To explore different morphologies of spiral galaxies: from the multi-armed galaxies to the Milky Way sized galaxies with few arms. (3) For a Milky Way disk we will assess the effect of impacts of substructures passing through the disk to origin the asymmetry in the number density of stars recently discovered from SDSS and SEGUE data and confirmed from RAVE data. We will also investigate the disk heating in the vertical plane due to the formation of vertical oscillations that are produced by the impact and migration of stars in the disk as consequence of the heating as compared to the classical stellar migration mechanism. (4) We will measure the spiral pattern speed and the velocity ellipsoid of the stars, and we will determine the contribution of the spiral arms to the heating of the stellar disk and to the radial migration of stars in the disk when the disk is perturbed by internal agents as giant molecular clouds. Our methodology has the potential to discern the detailed physical processes occurring in stellar disks with higher detail compared to previous simulations done in isolation or cosmological simulations of individual galaxies. The results of our work will provide a comprehensive guide for interpreting observations from upcoming GAIA, SDSS-IV, Spitzer and HST and future observations with JWST.

Interfacial properties of hydrosoluble polymers. Final report, June 15, 1993--June 15, 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-12-31

During this period, the authors treated a myriad of problems associated with the interfacial properties of macromolecules. Many of them concerned indirect interactions between surfaces engendered by intervening species. The issues ranged from colloidal forces to membrane induced coupling between embedded macromolecules (membrane-bound proteins). This report presents summaries of the following papers published as a result of this study: membrane interactions with polymers and colloids; escape transitions and force laws for compressed polymer mushrooms; interaction between finite-sized particles and end grafted polymers; one long chain among shorter chains--the Flory approach revisited; conformation of star polymers in high molecular weight solvents;more » membrane-induced interactions between inclusions; filled polymer brushes--a hydrodynamic analogy; polymer adsorption at liquid/air interfaces under lateral pressure; flow induced instability of the interface between a fluid and a gel at low Reynolds number; and fluctuation-induced forces in stacked fluid membranes.« less

Combined collapse by bridging and self-adhesion in a prototypical polymer model inspired by the bacterial nucleoid

NASA Astrophysics Data System (ADS)

Scolari, Vittore F.; Cosentino Lagomarsino, Marco

Recent experimental results suggest that the E. coli chromosome feels a self-attracting interaction of osmotic origin, and is condensed in foci by bridging interactions. Motivated by these findings, we explore a generic modeling framework combining solely these two ingredients, in order to characterize their joint effects. Specifically, we study a simple polymer physics computational model with weak ubiquitous short-ranged self attraction and stronger sparse bridging interactions. Combining theoretical arguments and simulations, we study the general phenomenology of polymer collapse induced by these dual contributions, in the case of regularly-spaced bridging. Our results distinguish a regime of classical Flory-like coil-globule collapse dictated by the interplay of excluded volume and attractive energy and a switch-like collapse where bridging interaction compete with entropy loss terms from the looped arms of a star-like rosette. Additionally, we show that bridging can induce stable compartmentalized domains. In these configurations, different "cores" of bridging proteins are kept separated by star-like polymer loops in an entropically favorable multi-domain configuration, with a mechanism that parallels micellar polysoaps. Such compartmentalized domains are stable, and do not need any intra-specific interactions driving their segregation. Domains can be stable also in presence of uniform attraction, as long as the uniform collapse is above its theta point.

Putting Bandits into Context: How Function Learning Supports Decision Making

ERIC Educational Resources Information Center

Schulz, Eric; Konstantinidis, Emmanouil; Speekenbrink, Maarten

2018-01-01

The authors introduce the contextual multi-armed bandit task as a framework to investigate learning and decision making in uncertain environments. In this novel paradigm, participants repeatedly choose between multiple options in order to maximize their rewards. The options are described by a number of contextual features which are predictive of…

Multi-Armed RCTs: A Design-Based Framework. NCEE 2017-4027

ERIC Educational Resources Information Center

Schochet, Peter Z.

2017-01-01

Design-based methods have recently been developed as a way to analyze data from impact evaluations of interventions, programs, and policies (Imbens and Rubin, 2015; Schochet, 2015, 2016). The estimators are derived using the building blocks of experimental designs with minimal assumptions, and are unbiased and normally distributed in large samples…

Local heterogeneities in cardiac systems suppress turbulence by generating multi-armed rotors

NASA Astrophysics Data System (ADS)

Zhang, Zhihui; Steinbock, Oliver

2016-05-01

Ventricular fibrillation is an extremely dangerous cardiac arrhythmia that is linked to rotating waves of electric activity and chaotically moving vortex lines. These filaments can pin to insulating, cylindrical heterogeneities which swiftly become the new rotation backbone of the local wave field. For thin cylinders, the stabilized rotation is sufficiently fast to repel the free segments of the turbulent filament tangle and annihilate them at the system boundaries. The resulting global wave pattern is periodic and highly ordered. Our cardiac simulations show that also thicker cylinders can establish analogous forms of tachycardia. This process occurs through the spontaneous formation of pinned multi-armed vortices. The observed number of wave arms N depends on the cylinder radius and is associated to stability windows that for N = 2, 3 partially overlap. For N = 1, 2, we find a small gap in which the turbulence is removed but the pinned rotor shows complex temporal dynamics. The relevance of our findings to human cardiology are discussed in the context of vortex pinning to more complex-shaped anatomical features and remodeled myocardium.

Hybrid position/force control of multi-arm cooperating robots

NASA Technical Reports Server (NTRS)

Hayati, Samad

1986-01-01

This paper extends the theory of hybrid position/force control to the case of multi-arm cooperating robots. Cooperation between n robot arms is achieved by controlling each arm such that the burden of actuation is shared between the arms in a nonconflicting way as they control the position of and force on a designated point on an object. The object, which may or may not be in contact with a rigid environment, is assumed to be held rigidly by n robot end-effectors. Natural and artificial position and force constraints are defined for a point on the object and two selection matrices are obtained to control the arms. The position control loops are designed based on each manipulator's Cartesian space dynamic equations. In the position control subspace, a feature is provided which allows the robot arms to exert additional forces/torques to achieve compression, tension, or torsion in the object without affecting the execution of the motion trajectories. In the force control subspace, a method is introduced to minimize the total force/torque magnitude square while realizing the net desired force/torque on the environment.

Nash Equilibrium of Social-Learning Agents in a Restless Multiarmed Bandit Game.

PubMed

Nakayama, Kazuaki; Hisakado, Masato; Mori, Shintaro

2017-05-16

We study a simple model for social-learning agents in a restless multiarmed bandit (rMAB). The bandit has one good arm that changes to a bad one with a certain probability. Each agent stochastically selects one of the two methods, random search (individual learning) or copying information from other agents (social learning), using which he/she seeks the good arm. Fitness of an agent is the probability to know the good arm in the steady state of the agent system. In this model, we explicitly construct the unique Nash equilibrium state and show that the corresponding strategy for each agent is an evolutionarily stable strategy (ESS) in the sense of Thomas. It is shown that the fitness of an agent with ESS is superior to that of an asocial learner when the success probability of social learning is greater than a threshold determined from the probability of success of individual learning, the probability of change of state of the rMAB, and the number of agents. The ESS Nash equilibrium is a solution to Rogers' paradox.

Contextual Multi-armed Bandits under Feature Uncertainty

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yun, Seyoung; Nam, Jun Hyun; Mo, Sangwoo

We study contextual multi-armed bandit problems under linear realizability on rewards and uncertainty (or noise) on features. For the case of identical noise on features across actions, we propose an algorithm, coined NLinRel, having O(T⁷/₈(log(dT)+K√d)) regret bound for T rounds, K actions, and d-dimensional feature vectors. Next, for the case of non-identical noise, we observe that popular linear hypotheses including NLinRel are impossible to achieve such sub-linear regret. Instead, under assumption of Gaussian feature vectors, we prove that a greedy algorithm has O(T²/₃√log d)regret bound with respect to the optimal linear hypothesis. Utilizing our theoretical understanding on the Gaussian case,more » we also design a practical variant of NLinRel, coined Universal-NLinRel, for arbitrary feature distributions. It first runs NLinRel for finding the ‘true’ coefficient vector using feature uncertainties and then adjust it to minimize its regret using the statistical feature information. We justify the performance of Universal-NLinRel on both synthetic and real-world datasets.« less

Flexible sequential designs for multi-arm clinical trials.

PubMed

Magirr, D; Stallard, N; Jaki, T

2014-08-30

Adaptive designs that are based on group-sequential approaches have the benefit of being efficient as stopping boundaries can be found that lead to good operating characteristics with test decisions based solely on sufficient statistics. The drawback of these so called 'pre-planned adaptive' designs is that unexpected design changes are not possible without impacting the error rates. 'Flexible adaptive designs' on the other hand can cope with a large number of contingencies at the cost of reduced efficiency. In this work, we focus on two different approaches for multi-arm multi-stage trials, which are based on group-sequential ideas, and discuss how these 'pre-planned adaptive designs' can be modified to allow for flexibility. We then show how the added flexibility can be used for treatment selection and sample size reassessment and evaluate the impact on the error rates in a simulation study. The results show that an impressive overall procedure can be found by combining a well chosen pre-planned design with an application of the conditional error principle to allow flexible treatment selection. Copyright © 2014 John Wiley & Sons, Ltd.

Multi-armed poly(L-glutamic acid)-graft-oligoethylenimine copolymers as efficient nonviral gene delivery vectors.

PubMed

Chen, Lei; Tian, Huayu; Chen, Jie; Chen, Xuesi; Huang, Yubin; Jing, Xiabin

2010-01-01

The application of polyethylenimine (PEI) in gene delivery has been severely limited by significant cytotoxicity that results from a nondegradable methylene backbone and high cationic charge density. It is therefore necessary to develop novel biodegradable PEI derivates for low-toxic, highly efficient gene delivery. A series of novel cationic copolymers with various charge density were designed and synthesized by grafting different kinds of oligoethylenimine (OEI) onto a determinate multi-armed poly(L-glutamic acid) backbone. The molecular structures of multi-armed poly(L-glutamic acid)-graft-OEI (MP-g-OEI) copolymers were characterized using nuclear magnetic resonance, viscosimetry and gel permeation chromatography. Moreover, the MP-g-OEI/DNA complexes were measured by a gel retardation assay, dynamic light scattering and atomic force microscopy to determine DNA binding ability, particle size, zeta potential, complex formation and shape, respectively. MP-g-OEI copolymers were also evaluated in Chinese hamster ovary and human embryonic kidney-293 cells for their cytotoxicity and transfection efficiency. The particle sizes of MP-g-OEI/DNA complexes were in a range of 109.6-182.6 nm and the zeta potentials were in a range of 29.2-44.5 mV above the N/P ratio of 5. All the MP-g-OEI copolymers exhibited lower cytotoxicity and higher gene transfection efficiency than PEI25k in the absence and presence of serum with different cell lines. Importantly, the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed that the cytotoxicity of MP-g-OEI copolymers varied with their molecular weight and charge density, and two of MP-g-OEI copolymers (OEI600-MP and OEI1800-MP) could achieve optimal transfection efficiency at a similar low N/P ratio as that for PEI25k. MP-g-OEI copolymers demonstrated considerable potential as nonviral vectors for gene therapy. Copyright 2009 John Wiley & Sons, Ltd.

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.

PubMed

Krüger, Andreas J D; Köhler, Jens; Cichosz, Stefan; Rose, Jonas C; Gehlen, David B; Haraszti, Tamás; Möller, Martin; De Laporte, Laura

2018-06-19

Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.

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

PubMed

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 release from the doxorubicin (DOX)-loaded supramolecular star-shaped micelles due to the oxidation-induced dissociation of β-CD/Fc pair and the consequent loss of the colloidal stability of the star-shaped micelles. Studies of the delivery efficacy by an in vitro cytotoxicity study further indicated that higher DBs and longer hydrophilic arm compromised the therapeutic efficacy of the DOX-loaded supramolecular star-shaped micelles, resulting in significantly reduced cytotoxicity, as measured by increased IC 50 value. Overall, our results revealed that the screening of hydrophilic block by DB and MW for an optimized star-shaped copolymer should balance the stability versus therapeutic efficacy tradeoff for a comprehensive consideration. Therefore, the 12-arm star-shaped copolymer with POEGMA 30 is the best formulation tested. Copyright © 2017 Elsevier Inc. All rights reserved.

Novel polyelectrolytes

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor)

1978-01-01

Cationic polyelectrolytes are formed by the polymerization in absence of oxygen of a monomer of the general formula: ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers. Segments of the linear polymer may be attached to or formed in the presence of polyfunctional reactive tertiary amines or halogen polymeric substrates or polyfunctional lower molecular reactive polyfunctional substrates to form branched or star polyelectrolytes by a quaternization polymerization reaction.

Effects of star-shape poly(alkyl methacrylate) arm uniformity on lubricant properties

DOE PAGES

Robinson, Joshua W.; Qu, Jun; Erck, Robert; ...

2016-03-29

Star-shaped poly(alkyl methacrylate)s (PAMAs) were prepared and blended into an additive-free engine oil to assess the structure property relationship between macromolecular structure and lubricant performance. These additives were designed with a comparable number of repeating units per arm and the number of arms was varied between 3 and 6. Well-defined star-shaped PAMAs were synthesized by atom transfer radical polymerization (ATRP) via a core-first strategy from multi-functional headgroups. Observations of the polymer-oil blends suggest that stars with less than four arms are favorable as a viscosity index improver (VII), and molecular weight dominates viscosity-related effects over other structural features. Star-shaped PAMAs,more » as oil additives, effectively reduce the friction coefficient in both mixed and boundary lubrication regime. Several analogs outperformed commercial VIIs in both viscosity and friction performance. Furthermore, increased wear rates were observed for these star-shaped PAMAs in the boundary lubrication regime suggesting pressure-sensitive conformations may exist.« less

Multiblob coarse-graining for mixtures of long polymers and soft colloids

NASA Astrophysics Data System (ADS)

Locatelli, Emanuele; Capone, Barbara; Likos, Christos N.

2016-11-01

Soft nanocomposites represent both a theoretical and an experimental challenge due to the high number of the microscopic constituents that strongly influence the behaviour of the systems. An effective theoretical description of such systems invokes a reduction of the degrees of freedom to be analysed, hence requiring the introduction of an efficient, quantitative, coarse-grained description. We here report on a novel coarse graining approach based on a set of transferable potentials that quantitatively reproduces properties of mixtures of linear and star-shaped homopolymeric nanocomposites. By renormalizing groups of monomers into a single effective potential between a f-functional star polymer and an homopolymer of length N0, and through a scaling argument, it will be shown how a substantial reduction of the to degrees of freedom allows for a full quantitative description of the system. Our methodology is tested upon full monomer simulations for systems of different molecular weight, proving its full predictive potential.

Self-Consistent Field Theories for the Role of Large Length-Scale Architecture in Polymers

NASA Astrophysics Data System (ADS)

Wu, David

At large length-scales, the architecture of polymers can be described by a coarse-grained specification of the distribution of branch points and monomer types within a molecule. This includes molecular topology (e.g., cyclic or branched) as well as distances between branch points or chain ends. Design of large length-scale molecular architecture is appealing because it offers a universal strategy, independent of monomer chemistry, to tune properties. Non-linear analogs of linear chains differ in molecular-scale properties, such as mobility, entanglements, and surface segregation in blends that are well-known to impact rheological, dynamical, thermodynamic and surface properties including adhesion and wetting. We have used Self-Consistent Field (SCF) theories to describe a number of phenomena associated with large length-scale polymer architecture. We have predicted the surface composition profiles of non-linear chains in blends with linear chains. These predictions are in good agreement with experimental results, including from neutron scattering, on a range of well-controlled branched (star, pom-pom and end-branched) and cyclic polymer architectures. Moreover, the theory allows explanation of the segregation and conformations of branched polymers in terms of effective surface potentials acting on the end and branch groups. However, for cyclic chains, which have no end or junction points, a qualitatively different topological mechanism based on conformational entropy drives cyclic chains to a surface, consistent with recent neutron reflectivity experiments. We have also used SCF theory to calculate intramolecular and intermolecular correlations for polymer chains in the bulk, dilute solution, and trapped at a liquid-liquid interface. Predictions of chain swelling in dilute star polymer solutions compare favorably with existing PRISM theory and swelling at an interface helps explain recent measurements of chain mobility at an oil-water interface. In collaboration with: Renfeng Hu, Colorado School of Mines, and Mark Foster, University of Akron. This work was supported by NSF Grants No. CBET- 0730692 and No. CBET-0731319.

Measuring the change in hydration of a polypeptide-based block polymer vesicle as a function of pH

NASA Astrophysics Data System (ADS)

Smith, Ian; Charlier, Alban; Shishlov, Alexander; Savin, Daniel

Amphiphilic AB2 star polymers undergo directed self-assembly into vesicles in aqueous solution. The overall structure of the assembly is responsive to a change in solution pH by incorporating an ionizable polypeptide as the A-block and two lipid-like tails for the B-blocks. Herein, we present some recent results in the solution characterization of polyglutamate-octadecanethiol2 (PE-DDT2) star polymers using static and dynamic light scattering, as well as transmission electron microscopy. An increase in pH will induce a transition in secondary structure of the PE block from an α-helix to an extended coil, thereby perturbing the morphological structure and resulting in an expansion of the vesicle. The magnitude of this response is much larger than what is expected based on the conformational transition of the peptide. The mechanism of this process can be probed by measuring the change in hydration at the surface of the hydrophobic bilayer. Towards this end, we utilize 2,4,6-trichloro-1,3,5-triazine (TCT) as a modular linker to install spin labels into the assembly as a mechanism to directly interrogate local hydrophobicity using electron paramagnetic resonance (EPR). NSF 1539347.

Porous Polystyrene Monoliths and Microparticles Prepared from Core Cross-linked Star (CCS) Polymers-Stabilized Emulsions.

PubMed

Chen, Qijing; Shi, Ting; Han, Fei; Li, Zihan; Lin, Chao; Zhao, Peng

2017-08-17

A hydrophobic CCS polymer of poly(benzyl methacrylate) (PBzMA) was prepared in toluene by reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization. The CCS polymer, with poly(benzyl methacrylate) as the arm and crosslinked N, N'-bis(acryloyl)cystamine (BAC) as the core, was confirmed by characterization with gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Three kinds of oils (toluene, anisole and styrene) were chosen to study the emulsification properties of PBzMA CCS polymer. The oils can be emulsified by CCS polymer to form water-in-oil (w/o) emulsions. Moreover, w/o high internal phase emulsions (HIPEs) can be obtained with the increase of toluene and styrene volume fractions from 75% to 80%. Porous polystyrene monolith and microparticles were prepared from the emulsion templates and characterized by the scanning electronic microscopy (SEM). With the internal phase volume fraction increased, open-pore porous monolith was obtained.

Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Yihuang; Wang, Zewei; He, Yanjie; Yoon, Young Jun; Jung, Jaehan; Zhang, Guangzhao; Lin, Zhiqun

2018-02-01

The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.

A multi-armed bandit approach to superquantile selection

DTIC Science & Technology

2017-06-01

decision learning, machine learning, intelligence processing, intelligence cycle, quantitative finance. 15. NUMBER OF PAGES 73 16. PRICE CODE 17...fulfillment of the requirements for the degree of MASTER OF SCIENCE IN OPERATIONS RESEARCH from the NAVAL POSTGRADUATE SCHOOL June 2017 Approved by...Roberto S. Szechtman Thesis Advisor Michael P. Atkinson Second Reader Patricia A. Jacobs Chair, Operations Research Department iii THIS PAGE

Multiple spiral patterns in the transitional disk of HD 100546

NASA Astrophysics Data System (ADS)

Boccaletti, A.; Pantin, E.; Lagrange, A.-M.; Augereau, J.-C.; Meheut, H.; Quanz, S. P.

2013-12-01

Context. Protoplanetary disks around young stars harbor many structures related to planetary formation. Of particular interest, spiral patterns were discovered among several of these disks and are expected to be the sign of gravitational instabilities leading to giant planet formation or gravitational perturbations caused by already existing planets. In this context, the star HD 100546 presents some specific characteristics with a complex gaseous and dusty disk that includes spirals, as well as a possible planet in formation. Aims: The objective of this study is to analyze high-contrast and high angular resolution images of this emblematic system to shed light on critical steps in planet formation. Methods: We retrieved archival images obtained at Gemini in the near IR (Ks band) with the instrument NICI and processed the data using an advanced high contrast imaging technique that takes advantage of the angular differential imaging. Results: These new images reveal the spiral pattern previously identified with Hubble Space Telescope (HST) with an unprecedented resolution, while the large-scale structure of the disk is mostly cancelled by the data processing. The single pattern to the southeast in HST images is now resolved into a multi-armed spiral pattern. Using two models of a gravitational perturber orbiting in a gaseous disk, we attempted to constrain the characteristics of this perturber, assuming that each spiral is independent, and drew qualitative conclusions. The non-detection of the northeast spiral pattern observed in HST allows putting a lower limit on the intensity ratio between the two sides of the disk, which if interpreted as forward scattering, yields a larger anisotropic scattering than is derived in the visible. Also, we find that the spirals are likely to be spatially resolved with a thickness of about 5-10 AU. Finally, we did not detect the candidate planet in formation recently discovered in the Lp band, with a mass upper limit of 16-18 MJ. Based on data retrieved from the Gemini archive.

The role of nanoparticle rigidity on the diffusion of linear polystyrene in a polymer nanocomposite

DOE PAGES

Miller, Brad; Imel, Adam E.; Holley, Wade; ...

2015-11-12

The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanoparticle rigidity or softness on the impact of the presence of that nanoparticle on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of 10 nm soft nanoparticles in a polymer matrix (R g ~ 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transitionmore » temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Furthermore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.« less

The role of nanoparticle rigidity on the diffusion of linear polystyrene in a polymer nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Brad; Imel, Adam E.; Holley, Wade

The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanoparticle rigidity or softness on the impact of the presence of that nanoparticle on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of 10 nm soft nanoparticles in a polymer matrix (R g ~ 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transitionmore » temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Furthermore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.« less

Constructing honeycomb micropatterns on nonplanar substrates with high glass transition temperature polymers.

PubMed

Ding, Jianyun; Gong, Jianliang; Bai, Hua; Li, Lei; Zhong, Yawen; Ma, Zhi; Svrcek, Vladimir

2012-08-15

In Qiao's previous report, only star polymers with T(g) (glass transition temperature) below 48°C were found forming homogeneous honeycomb coatings on the nonplanar substrates. The polymers with high T(g) are believed not able to duplicate nonplanar substrate due to their brittleness. This article presents a comprehensive study on the construction of macroporous polymeric films on various nonplanar substrates with static breath figure (BF) technique, using linear polymers with high T(g). Two kinds of linear polymers with high T(g), polystyrene-b-poly(acrylic acid) and polystyrene without polar end groups, are employed to prepare 3-dimensional macroporous films on different nonplanar substrates. Scanning electronic microscopy views on the side wall in addition to views in-plane prove that polymer films with BF array perfectly replicated the surface features of these substrates. The formation processes of macropores on these substrates are analyzed in detail, and it demonstrates that neither molecular topography nor T(g) of polymers is the critical factor contouring nonplanar substrate. A new hypothesis involving polymer plasticization and conformation during the solvent evaporation is formulated. Crown Copyright © 2012. Published by Elsevier Inc. All rights reserved.

Doxorubicin-loaded aromatic imine-contained amphiphilic branched star polymer micelles: synthesis, self-assembly, and drug delivery

PubMed Central

Qiu, Liang; Hong, Chun-Yan; Pan, Cai-Yuan

2015-01-01

Redox-and pH-sensitive branched star polymers (BSPs), BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAIGP)ns, have been successively prepared by two steps of reversible addition–fragmentation chain transfer (RAFT) polymerization. The first step is RAFT polymerization of 2-(N,N-dimethylaminoethyl)methacrylate (DMAEMA) and p-(methacryloxyethoxy) benzaldehyde (MAEBA) in the presence of divinyl monomer, 2,2′-dithiodiethoxyl dimethacrylate (DTDMA). The resultant branched polymers were used as a macro-RAFT agent in the subsequent RAFT polymerization. After hydrolysis of the BSPs to form BP(DMAEMA-co-MAEBA-co-DTDMA)(PMAGP)ns (BSP-H), the anticancer drug doxorubicin (DOX) was covalently linked to branched polymer chains by reaction of primary amine of DOX and aldehyde groups in the polymer chains. Their compositions, structures, molecular weights, and molecular weight distributions were respectively characterized by nuclear magnetic resonance spectra and gel permeation chromatography measurements. The DOX-loaded micelles were fabricated by self-assembly of DOX-containing BSPs in water, which were characterized by transmission electron microscopy and dynamic light scattering. Aromatic imine linkage is stable in neutral water, but is acid-labile; controlled release of DOX from the BSP-H-DOX micelles was realized at pH values of 5 and 6, and at higher acidic solution, fast release of DOX was observed. In vitro cytotoxicity experiment results revealed low cytotoxicity of the BSPs and release of DOX from micelles in HepG2 and HeLa cells. Confocal laser fluorescence microscopy observations showed that DOX-loaded micelles have specific interaction with HepG2 cells. Thus, this type of BSP micelle is an efficient drug delivery system. PMID:26056444

Control of free-flying space robot manipulator systems

NASA Technical Reports Server (NTRS)

Cannon, Robert H., Jr.

1977-01-01

To accelerate the development of multi-armed, free-flying satellite manipulators, a fixed-base cooperative manipulation facility is being developed. The work performed on multiple arm cooperation on a free-flying robot is summarized. Research is also summarized on global navigation and control of free-flying space robots. The Locomotion Enhancement via Arm Pushoff (LEAP) approach is described and progress to date is presented.

Simulating the thermodynamics of charging in weak polyelectrolytes: the Debye-Hückel limit

NASA Astrophysics Data System (ADS)

Rathee, Vikramjit S.; Sikora, Benjamin J.; Sidky, Hythem; Whitmer, Jonathan K.

2018-01-01

The coil-globule transition in weak (annealed) polyelectrolytes involves a subtle balance of pH, charge strength, and solvation forces. In this work, we utilize a coarse-grained hybrid grand-canonical Monte Carlo and molecular dynamics approach to explore the swelling behavior of weak linear and star polyelectrolytes under different ionic screening conditions and pH. Importantly, we are able to quantify topology-dependent effects in charging which arise at the core of star polymers. Our results are suggestive of suppression of charging in star weak polyelectrolytes in comparison to linear weak polyelectrolytes. Furthermore, we characterize the coil-globule transition in linear and star weak polyelectrolyte through expanded ensemble density-of-states simulations which suggest a change from a first order to second order phase transition moving from linear to star polyelectrolytes. Lastly, we characterize the inhomogeneous charging across the weak star polyelectrolyte through observed shifts in {{Δ }}{{{pK}}}{{o}}, and compare with experimental work. We discuss these results in relation to surfaces functionalized by weak polyelectrolyte brushes and weak polyelectrolyte-based drug delivery applications.

Polymer architectures via mass spectrometry and hyphenated techniques: A review.

PubMed

Crotty, Sarah; Gerişlioğlu, Selim; Endres, Kevin J; Wesdemiotis, Chrys; Schubert, Ulrich S

2016-08-17

This review covers the application of mass spectrometry (MS) and its hyphenated techniques to synthetic polymers of varying architectural complexities. The synthetic polymers are discussed as according to their architectural complexity from linear homopolymers and copolymers to stars, dendrimers, cyclic copolymers and other polymers. MS and tandem MS (MS/MS) has been extensively used for the analysis of synthetic polymers. However, the increase in structural or architectural complexity can result in analytical challenges that MS or MS/MS cannot overcome alone. Hyphenation to MS with different chromatographic techniques (2D × LC, SEC, HPLC etc.), utilization of other ionization methods (APCI, DESI etc.) and various mass analyzers (FT-ICR, quadrupole, time-of-flight, ion trap etc.) are applied to overcome these challenges and achieve more detailed structural characterizations of complex polymeric systems. In addition, computational methods (software: MassChrom2D, COCONUT, 2D maps etc.) have also reached polymer science to facilitate and accelerate data interpretation. Developments in technology and the comprehension of different polymer classes with diverse architectures have significantly improved, which allow for smart polymer designs to be examined and advanced. We present specific examples covering diverse analytical aspects as well as forthcoming prospects in polymer science. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and characterization of star-shaped oligo(ethylene glycol) with tyrosine derived moieties under variation of their molecular weight.

PubMed

Julich-Gruner, Konstanze K; Roch, Toralf; Ma, Nan; Neffe, Axel T; Lendlein, Andreas

2015-01-01

Desamino tyrosine (DAT) and desamino tyrosyl tyrosine (DATT) can be used to functionalize the end groups of water soluble polymers. The phenolic groups may enable physical interactions by π- π interaction and hydrogen bonds, which might lead to the formation of a hydrogel by physical crosslinking. However, using star-shaped oligo(ethylene glycols) (sOEG) with a molecular weight of 5 kDa for functionalization with DAT or DATT resulted in the formation of surfactants and not in hydrogels.As the molecular weight of the sOEG polymer chain can have an influence on forming physical cross links, DAT(T)-fuctionalization of sOEGs with higher molecular weight was investigated, the polymers were structurally characterized and for their mechanical properties were evaluated by rheological measurements.Aqueous solutions of DAT(T)-sOEGs with 10 and 20 kDa showed lower storage and loss moduli compared to unfunctionalized sOEGs indicating also the formation of surfactants. Cell-based assays showed that all sOEG solutions did not impair cell viability and were free of endotoxins, which could otherwise induce uncontrolled immune responses.Conclusively, our data suggested that the sOEG solutions have surface active properties without inducing unwanted cellular responses, which is required e.g. in pharmaceutical applications to solubilize hydophobic substances.

Nanofibrous hollow microspheres self-assembled from star-shaped polymers as injectable cell carriers for knee repair.

PubMed

Liu, Xiaohua; Jin, Xiaobing; Ma, Peter X

2011-05-01

To repair complexly shaped tissue defects, an injectable cell carrier is desirable to achieve an accurate fit and to minimize surgical intervention. However, the injectable carriers available at present have limitations, and are not used clinically for cartilage regeneration. Here, we report nanofibrous hollow microspheres self-assembled from star-shaped biodegradable polymers as an injectable cell carrier. The nanofibrous hollow microspheres, integrating the extracellular-matrix-mimicking architecture with a highly porous injectable form, were shown to efficiently accommodate cells and enhance cartilage regeneration, compared with control microspheres. The nanofibrous hollow microspheres also supported a significantly larger amount of, and higher-quality, cartilage regeneration than the chondrocytes-alone group in an ectopic implantation model. In a critical-size rabbit osteochondral defect-repair model, the nanofibrous hollow microspheres/chondrocytes group achieved substantially better cartilage repair than the chondrocytes-alone group that simulates the clinically available autologous chondrocyte implantation procedure. These results indicate that the nanofibrous hollow microspheres are an excellent injectable cell carrier for cartilage regeneration.

Light-emitting block copolymers composition, process and use

DOEpatents

Ferraris, John P.; Gutierrez, Jose J.

2006-11-14

Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

Smoking and the bandit: a preliminary study of smoker and nonsmoker differences in exploratory behavior measured with a multiarmed bandit task.

PubMed

Addicott, Merideth A; Pearson, John M; Wilson, Jessica; Platt, Michael L; McClernon, F Joseph

2013-02-01

Advantageous decision-making is an adaptive trade-off between exploring alternatives and exploiting the most rewarding option. This trade-off may be related to maladaptive decision-making associated with nicotine dependence; however, explore/exploit behavior has not been previously investigated in the context of addiction. The explore/exploit trade-off is captured by the multiarmed bandit task, in which different arms of a slot machine are chosen to discover the relative payoffs. The goal of this study was to preliminarily investigate whether smokers differ from nonsmokers in their degree of exploratory behavior. Smokers (n = 18) and nonsmokers (n = 17) completed a 6-armed bandit task as well as self-report measures of behavior and personality traits. Smokers were found to exhibit less exploratory behavior (i.e., made fewer switches between slot machine arms) than nonsmokers within the first 300 trials of the bandit task. The overall proportion of exploratory choices negatively correlated with self-reported measures of delay aversion and nonplanning impulsivity. These preliminary results suggest that smokers make fewer initial exploratory choices on the bandit task. The bandit task is a promising measure that could provide valuable insights into how nicotine use and dependence is associated with explore/exploit decision-making. (c) 2013 APA, all rights reserved.

Smoking and the bandit: A preliminary study of smoker and non-smoker differences in exploratory behavior measured with a multi-armed bandit task

PubMed Central

Addicott, Merideth A.; Pearson, John M.; Wilson, Jessica; Platt, Michael L.; McClernon, F. Joseph

2014-01-01

Advantageous decision-making is an adaptive trade-off between exploring alternatives and exploiting the most rewarding option. This trade-off may be related to maladaptive decision-making associated with nicotine dependence; however, explore/exploit behavior has not been previously investigated in the context of addiction. The explore/exploit trade-off is captured by the multi-armed bandit task, in which different arms of a slot machine are chosen to discover the relative payoffs. The goal of this study was to preliminarily investigate whether smokers differ from non-smokers in their degree of exploratory behavior. Smokers (n = 18) and non-smokers (n = 17) completed a six-armed bandit task as well as self-report measures of behavior and personality traits. Smokers were found to exhibit less exploratory behavior (i.e. made fewer switches between slot machine arms) than non-smokers within the first 300 trials of the bandit task. The overall proportion of exploratory choices negatively correlated with self-reported measures of delay aversion and nonplanning impulsivity. These preliminary results suggest that smokers make fewer initial exploratory choices on the bandit task. The bandit task is a promising measure that could provide valuable insights into how nicotine use and dependence is associated with explore/exploit decision-making. PMID:23245198

Rational geometrical engineering of palladium sulfide multi-arm nanostructures as a superior bi-functional electrocatalyst.

PubMed

Nandan, R; Nanda, K K

2017-08-31

Geometrical tunability offers sharp edges and an open-armed structure accompanied with a high electrochemical active surface area to ensure the efficient and effective utilization of materials by exposing the electrochemical active sites for facile accessibility of reactant species. Herein, we report a one-step, single-pot, surfactant-free, electroless, and economic route to synthesize palladium sulfide nanostructures with different geometries at mild temperatures and their catalytic properties towards the oxygen reduction reaction (ORR) and methanol electro-oxidation (MOR). For ORR, the positive on-set, half wave potentials, smaller Tafel slope, high electrochemical active surface area, large roughness factor, and better cyclic stability of the proposed nanostructures as compared to those of the commercial state-of-the-art Pt-C/PdS catalysts suggest their superiority in an alkaline medium. In addition, high mass activity (J f ∼ 715 mA mg -1 ), in comparison with that of the commercial state-of-the-art Pt-C/PdS catalysts (J f ∼ 138/41 mA mg -1 , respectively), and high J f /J b (1.52) along with the superior operational stability of the multi-arm palladium sulfide nanostructures towards MOR advocates the bi-functional behavior of the catalyst and its potential as a promising Pt-free anode/cathode electrocatalyst in fuel cells.

Dual-arm manipulators with adaptive control

NASA Technical Reports Server (NTRS)

Seraji, Homayoun (Inventor)

1991-01-01

The described and improved multi-arm invention of this application presents three strategies for adaptive control of cooperative multi-arm robots which coordinate control over a common load. In the position-position control strategy, the adaptive controllers ensure that the end-effector positions of both arms track desired trajectories in Cartesian space despite unknown time-varying interaction forces exerted through a load. In the position-hybrid control strategy, the adaptive controller of one arm controls end-effector motions in the free directions and applied forces in the constraint directions; while the adaptive controller of the other arm ensures that the end-effector tracks desired position trajectories. In the hybrid-hybrid control strategy, the adaptive controllers ensure that both end-effectors track reference position trajectories while simultaneously applying desired forces on the load. In all three control strategies, the cross-coupling effects between the arms are treated as disturbances which are compensated for by the adaptive controllers while following desired commands in a common frame of reference. The adaptive controllers do not require the complex mathematical model of the arm dynamics or any knowledge of the arm dynamic parameters or the load parameters such as mass and stiffness. Circuits in the adaptive feedback and feedforward controllers are varied by novel adaptation laws.

Robustness, Death of Spiral Wave in the Network of Neurons under Partial Ion Channel Block

NASA Astrophysics Data System (ADS)

Ma, Jun; Huang, Long; Wang, Chun-Ni; Pu, Zhong-Sheng

2013-02-01

The development of spiral wave in a two-dimensional square array due to partial ion channel block (Potassium, Sodium) is investigated, the dynamics of the node is described by Hodgkin—Huxley neuron and these neurons are coupled with nearest neighbor connection. The parameter ratio xNa (and xK), which defines the ratio of working ion channel number of sodium (potassium) to the total ion channel number of sodium (and potassium), is used to measure the shift conductance induced by channel block. The distribution of statistical variable R in the two-parameter phase space (parameter ratio vs. poisoning area) is extensively calculated to mark the parameter region for transition of spiral wave induced by partial ion channel block, the area with smaller factors of synchronization R is associated the parameter region that spiral wave keeps alive and robust to the channel poisoning. Spiral wave keeps alive when the poisoned area (potassium or sodium) and degree of intoxication are small, distinct transition (death, several spiral waves coexist or multi-arm spiral wave emergence) occurs under moderate ratio xNa (and xK) when the size of blocked area exceeds certain thresholds. Breakup of spiral wave occurs and multi-arm of spiral waves are observed when the channel noise is considered.

Method and apparatus for adaptive force and position control of manipulators

NASA Technical Reports Server (NTRS)

Seraji, Homayoun (Inventor)

1995-01-01

The described and improved multi-arm invention of this application presents three strategies for adaptive control of cooperative multi-arm robots which coordinate control over a common load. In the position-position control strategy, the adaptive controllers ensure that the end-effector positions of both arms track desired trajectories in Cartesian space despite unknown time-varying interaction forces exerted through a load. In the position-hybrid control strategy, the adaptive controller of one arm controls end-effector motions in the free directions and applied forces in the constraint directions; while the adaptive controller of the other arm ensures that the end-effector tracks desired position trajectories. In the hybrid-hybrid control strategy, the adaptive controllers ensure that both end-effectors track reference position trajectories while simultaneously applying desired forces on the load. In all three control strategies, the cross-coupling effects between the arms are treated as disturbances which are compensated for by the adaptive controllers while following desired commands in a common frame of reference. The adaptive controllers do not require the complex mathematical model of the arm dynamics or any knowledge of the arm dynamic parameters or the load parameters such as mass and stiffness. Circuits in the adaptive feedback and feedforward controllers are varied by novel adaptation laws.

Feasibility of polymer gel-based measurements of radiation isocenter accuracy in magnetic fields

NASA Astrophysics Data System (ADS)

Dorsch, S.; Mann, P.; Lang, C.; Haering, P.; Runz, A.; Karger, C. P.

2018-06-01

For conventional irradiation devices, the radiation isocenter accuracy is determined by star shot measurements on films. In magnetic resonance (MR)-guided radiotherapy devices, the results of this test may be altered by the magnetic field and the need to align the radiation and imaging isocenter may require a modification of measurement procedures. Polymer dosimetry gels (PG) may offer a way to perform both, the radiation and imaging isocenter test, however, first it has to be shown that PG reveal results comparable to the conventionally applied films. Therefore, star shot measurements were performed at a linear accelerator using PG as well as radiochromic films. PG were evaluated using MR imaging and the isocircle radius and the distance between the isocircle center and the room isocenter were determined. Two different types of experiments were performed: i) a standard star-shot isocenter test and (ii) a star shot, where the detectors were placed between the pole shoes of an experimental electro magnet operated either at 0 T or 1 T. For the standard star shot, PG evaluation was independent of the time delay after irradiation (1 h, 24 h, 48 h and 216 h) and the results were comparable to those of film measurements. Within the electro magnet, the isocircle radius increased from 0.39  ±  0.01 mm to 1.37  ±  0.01 mm for the film and from 0.44  ±  0.02 mm to 0.97  ±  0.02 mm for the PG-measurements, respectively. The isocenter distance was essentially dependent on the alignment of the magnet to the isocenter and was between 0.12  ±  0.02 mm and 0.82  ±  0.02 mm. The study demonstrates that evaluation of the PG directly after irradiation is feasible, if only geometrical parameters are of interest. This allows using PG for star shot measurements to evaluate the radiation isocenter accuracy with comparable accuracy as with radiochromic films.

Accelerating clinical development of HIV vaccine strategies: methodological challenges and considerations in constructing an optimised multi-arm phase I/II trial design.

PubMed

Richert, Laura; Doussau, Adélaïde; Lelièvre, Jean-Daniel; Arnold, Vincent; Rieux, Véronique; Bouakane, Amel; Lévy, Yves; Chêne, Geneviève; Thiébaut, Rodolphe

2014-02-26

Many candidate vaccine strategies against human immunodeficiency virus (HIV) infection are under study, but their clinical development is lengthy and iterative. To accelerate HIV vaccine development optimised trial designs are needed. We propose a randomised multi-arm phase I/II design for early stage development of several vaccine strategies, aiming at rapidly discarding those that are unsafe or non-immunogenic. We explored early stage designs to evaluate both the safety and the immunogenicity of four heterologous prime-boost HIV vaccine strategies in parallel. One of the vaccines used as a prime and boost in the different strategies (vaccine 1) has yet to be tested in humans, thus requiring a phase I safety evaluation. However, its toxicity risk is considered minimal based on data from similar vaccines. We newly adapted a randomised phase II trial by integrating an early safety decision rule, emulating that of a phase I study. We evaluated the operating characteristics of the proposed design in simulation studies with either a fixed-sample frequentist or a continuous Bayesian safety decision rule and projected timelines for the trial. We propose a randomised four-arm phase I/II design with two independent binary endpoints for safety and immunogenicity. Immunogenicity evaluation at trial end is based on a single-stage Fleming design per arm, comparing the observed proportion of responders in an immunogenicity screening assay to an unacceptably low proportion, without direct comparisons between arms. Randomisation limits heterogeneity in volunteer characteristics between arms. To avoid exposure of additional participants to an unsafe vaccine during the vaccine boost phase, an early safety decision rule is imposed on the arm starting with vaccine 1 injections. In simulations of the design with either decision rule, the risks of erroneous conclusions were controlled <15%. Flexibility in trial conduct is greater with the continuous Bayesian rule. A 12-month gain in timelines is expected by this optimised design. Other existing designs such as bivariate or seamless phase I/II designs did not offer a clear-cut alternative. By combining phase I and phase II evaluations in a multi-arm trial, the proposed optimised design allows for accelerating early stage clinical development of HIV vaccine strategies.

Direct Visualization of Conformation and Dense Packing of DNA-Based Soft Colloids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Lettinga, Paul M.; Dhont, Jan K. G.; Stiakakis, Emmanuel

2014-12-01

Soft colloids—such as polymer-coated particles, star polymers, block-copolymer micelles, microgels—constitute a broad class of materials where microscopic properties such as deformability and penetrability of the particle play a key role in tailoring their macroscopic properties which is of interest in many technological areas. The ability to access these microscopic properties is not yet demonstrated despite its great importance. Here we introduce novel DNA-coated colloids with star-shaped architecture that allows accessing the above local structural information by directly visualizing their intramolecular monomer density profile and arm's free-end locations with confocal fluorescent microscopy. Compression experiments on a two-dimensional hexagonal lattice formed by these macromolecular assemblies reveal an exceptional resistance to mutual interpenetration of their charged corona at pressures approaching the MPa range. Furthermore, we find that this lattice, in a close packing configuration, is surprisingly tolerant to particle size variation. We anticipate that these stimuli-responsive materials could aid to get deeper insight in a wide range of problems in soft matter, including the study and design of biomimetic lubricated surfaces.

The STAMPEDE trial: paradigm-changing data through innovative trial design.

PubMed

Carthon, Bradley C; Antonarakis, Emmanuel S

2016-09-01

Despite the numerous regulatory approvals for prostate cancer, metastatic prostate cancer remains a huge burden for men worldwide. In an exciting development, James et al . recently published data from the Systemic Therapy in Advanced or Metastatic Prostate Cancer: Evaluation of Drug Efficacy: a multi-stage multi-arm randomised control trial (STAMPEDE). This is an innovative multi-arm multi-stage (MAMS) trial that has utilized one control arm and several comparator arms in order to provide evidence for the inclusion of therapies beyond standard androgen deprivation alone. The patient population included: (I) men with high-risk, non-metastatic, node-negative disease; (II) men with distant-metastatic or node-positive disease; and (III) men with previously-treated prostate cancer by prostatectomy or definitive radiotherapy presenting with relapse. Men were to continue androgen deprivation for at least 2 years. The current data published by this group supports earlier results and provides additional evidence that docetaxel utilized in an up-front fashion provides a survival benefit in men with hormone-sensitive metastatic prostate cancer. Moreover, the initial results from STAMPEDE show how therapies without a demonstrated survival benefit can be efficiently excluded from further study once the likelihood of a benefit is ruled out by a predetermined analysis. In this piece, we will review the STAMPEDE data, contrast it with existing results, and provide our perspectives on how this will affect future trial conduct in the field of prostate cancer.

Planning multi-arm screening studies within the context of a drug development program

PubMed Central

Wason, James M S; Jaki, Thomas; Stallard, Nigel

2013-01-01

Screening trials are small trials used to decide whether an intervention is sufficiently promising to warrant a large confirmatory trial. Previous literature examined the situation where treatments are tested sequentially until one is considered sufficiently promising to take forward to a confirmatory trial. An important consideration for sponsors of clinical trials is how screening trials should be planned to maximize the efficiency of the drug development process. It has been found previously that small screening trials are generally the most efficient. In this paper we consider the design of screening trials in which multiple new treatments are tested simultaneously. We derive analytic formulae for the expected number of patients until a successful treatment is found, and propose methodology to search for the optimal number of treatments, and optimal sample size per treatment. We compare designs in which only the best treatment proceeds to a confirmatory trial and designs in which multiple treatments may proceed to a multi-arm confirmatory trial. We find that inclusion of a large number of treatments in the screening trial is optimal when only one treatment can proceed, and a smaller number of treatments is optimal when more than one can proceed. The designs we investigate are compared on a real-life set of screening designs. Copyright © 2013 John Wiley & Sons, Ltd. PMID:23529936

Novel Tertiary Amino Containing Blinding Composite Membranes via Raft Polymerization and Their Preliminary CO2 Permeation Performance

PubMed Central

Zhu, Lifang; Zhou, Mali; Yang, Shanshan; Shen, Jiangnan

2015-01-01

Facile synthesis of poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) star polymers on the basis of the prepolymer chains, PDMAEMA as the macro chain transfer agent and divinyl benzene (DVB) as the cross-linking reagent by reversible addition-fragmentation chain transfer (RAFT) polymerization was described. The RAFT polymerizations of DMAEMA at 70 °C using four RAFT agents with different R and Z group were investigated. The RAFT agents used in these polymerizations were dibenzyl trithiocarbonate (DBTTC), s-1-dodecyl-s'-(α,α'-dimethyl-α-acetic acid) trithiocarbonate (MTTCD), s,s'-bis (2-hydroxyethyl-2'-dimethylacrylate) trithiocarbonate (BDATC) and s-(2-cyanoprop-2-yl)-s-dodecyltrithiocarbonate (CPTCD). The results indicated that the structure of the end-group of RAFT agents had significant effects on the ability to control polymerization. Compared with the above-mentioned RAFT agents, CPTCD provides better control over the molecular weight and molecular weight distribution. The polydispersity index (PDI) was determined to be within the scope of 1.26 to 1.36. The yields, molecular weight, and distribution of the star polymers can be tuned by changing the molar ratio of DVB/PDMAEMA-CPTCD. The chemical composition and structure of the linear and star polymers were characterized by GPC, FTIR, 1H NMR, XRD analysis. For the pure Chitosan membrane, a great improvement was observed for both CO2 permeation rate and ideal selectivity of the blending composite membrane upon increasing the content of SPDMAEMA-8. At a feed gas pressure of 37.5 cmHg and 30 °C, the blinding composite membrane (Cs: SPDMAEMA-8 = 4:4) has a CO2 permeation rate of 8.54 × 10−4 cm3 (STP) cm−2∙s−1∙cm∙Hg−1 and a N2 permeation rate of 6.76 × 10−5 cm3 (STP) cm−2∙s−1∙cm∙Hg−1, and an ideal CO2/N2 selectivity of 35.2. PMID:25915025

Novel Tertiary Amino Containing Blinding Composite Membranes via Raft Polymerization and Their Preliminary CO2 Permeation Performance.

PubMed

Zhu, Lifang; Zhou, Mali; Yang, Shanshan; Shen, Jiangnan

2015-04-23

Facile synthesis of poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) star polymers on the basis of the prepolymer chains, PDMAEMA as the macro chain transfer agent and divinyl benzene (DVB) as the cross-linking reagent by reversible addition-fragmentation chain transfer (RAFT) polymerization was described. The RAFT polymerizations of DMAEMA at 70 °C using four RAFT agents with different R and Z group were investigated. The RAFT agents used in these polymerizations were dibenzyl trithiocarbonate (DBTTC), s-1-dodecyl-s'-(α,α'-dimethyl-α-acetic acid) trithiocarbonate (MTTCD), s,s'-bis (2-hydroxyethyl-2'-dimethylacrylate) trithiocarbonate (BDATC) and s-(2-cyanoprop-2-yl)-s-dodecyltrithiocarbonate (CPTCD). The results indicated that the structure of the end-group of RAFT agents had significant effects on the ability to control polymerization. Compared with the above-mentioned RAFT agents, CPTCD provides better control over the molecular weight and molecular weight distribution. The polydispersity index (PDI) was determined to be within the scope of 1.26 to 1.36. The yields, molecular weight, and distribution of the star polymers can be tuned by changing the molar ratio of DVB/PDMAEMA-CPTCD. The chemical composition and structure of the linear and star polymers were characterized by GPC, FTIR, 1H NMR, XRD analysis. For the pure Chitosan membrane, a great improvement was observed for both CO₂ permeation rate and ideal selectivity of the blending composite membrane upon increasing the content of SPDMAEMA-8. At a feed gas pressure of 37.5 cmHg and 30 °C, the blinding composite membrane (Cs: SPDMAEMA-8 = 4:4) has a CO₂ permeation rate of 8.54 × 10⁻⁴ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹ and a N₂ permeation rate of 6.76 × 10⁻⁵ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹, and an ideal CO₂/N₂ selectivity of 35.2.

Real-time monitoring of anticancer drug release with highly fluorescent star-conjugated copolymer as a drug carrier.

PubMed

Qiu, Feng; Wang, Dali; Zhu, Qi; Zhu, Lijuan; Tong, Gangsheng; Lu, Yunfeng; Yan, Deyue; Zhu, Xinyuan

2014-04-14

Chemotherapy is one of the major systemic treatments for cancer, in which the drug release kinetics is a key factor for drug delivery. In the present work, a versatile fluorescence-based real-time monitoring system for intracellular drug release has been developed. First, two kinds of star-conjugated copolymers with different connections (e.g., pH-responsive acylhydrazone and stable ether) between a hyperbranched conjugated polymer (HCP) core and many linear poly(ethylene glycol) (PEG) arms were synthesized. Owing to the amphiphilic three-dimensional architecture, the star-conjugated copolymers could self-assemble into multimicelle aggregates from unimolecular micelles with excellent emission performance in the aqueous medium. When doxorubicin (DOX) as a model drug was encapsulated into copolymer micelles, the emission of star-conjugated copolymer and DOX was quenched. In vitro biological studies revealed that fluorescent intensities of both star-conjugated copolymer and DOX were activated when the drug was released from copolymeric micelles, resulting in the enhanced cellular proliferation inhibition against cancer cells. Importantly, pH-responsive feature of the star-conjugated copolymer with acylhydrazone linkage exhibited accelerated DOX release at a mildly acidic environment, because of the fast breakage of acylhydrazone in endosome or lysosome of tumor cells. Such fluorescent star-conjugated copolymers may open up new perspectives to real-time study of drug release kinetics of polymeric drug delivery systems for cancer therapy.

Actively targeted delivery of anticancer drug to tumor cells by redox-responsive star-shaped micelles.

PubMed

Shi, Chunli; Guo, Xing; Qu, Qianqian; Tang, Zhaomin; Wang, Yi; Zhou, Shaobing

2014-10-01

In cancer therapy nanocargos based on star-shaped polymer exhibit unique features such as better stability, smaller size distribution and higher drug capacity in comparison to linear polymeric micelles. In this study, we developed a multifunctional star-shaped micellar system by combination of active targeting ability and redox-responsive behavior. The star-shaped micelles with good stability were self-assembled from four-arm poly(ε-caprolactone)-poly(ethylene glycol) copolymer. The redox-responsive behaviors of these micelles triggered by glutathione were evaluated from the changes of micellar size, morphology and molecular weight. In vitro drug release profiles exhibited that in a stimulated normal physiological environment, the redox-responsive star-shaped micelles could maintain good stability, whereas in a reducing and acid environment similar with that of tumor cells, the encapsulated agent was promptly released. In vitro cellular uptake and subcellular localization of these micelles were further studied with confocal laser scanning microscopy and flow cytometry against the human cervical cancer cell line HeLa. In vivo and ex vivo DOX fluorescence imaging displayed that these FA-functionalized star-shaped micelles possessed much better specificity to target solid tumor. Both the qualitative and quantitative results of the antitumor effect in 4T1 tumor-bearing BALB/c mice demonstrated that these redox-responsive star-shaped micelles have a high therapeutic efficiency to artificial solid tumor. Therefore, the multifunctional star-shaped micelles are a potential platform for targeted anticancer drug delivery. Copyright © 2014 Elsevier Ltd. All rights reserved.

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative Modeling of Entangled Polymer Rheology: Experiments, Tube Models and Slip-Link Simulations

NASA Astrophysics Data System (ADS)

Desai, Priyanka Subhash

Rheology properties are sensitive indicators of molecular structure and dynamics. The relationship between rheology and polymer dynamics is captured in the constitutive model, which, if accurate and robust, would greatly aid molecular design and polymer processing. This dissertation is thus focused on building accurate and quantitative constitutive models that can help predict linear and non-linear viscoelasticity. In this work, we have used a multi-pronged approach based on the tube theory, coarse-grained slip-link simulations, and advanced polymeric synthetic and characterization techniques, to confront some of the outstanding problems in entangled polymer rheology. First, we modified simple tube based constitutive equations in extensional rheology and developed functional forms to test the effect of Kuhn segment alignment on a) tube diameter enlargement and b) monomeric friction reduction between subchains. We, then, used these functional forms to model extensional viscosity data for polystyrene (PS) melts and solutions. We demonstrated that the idea of reduction in segmental friction due to Kuhn alignment is successful in explaining the qualitative difference between melts and solutions in extension as revealed by recent experiments on PS. Second, we compiled literature data and used it to develop a universal tube model parameter set and prescribed their values and uncertainties for 1,4-PBd by comparing linear viscoelastic G' and G" mastercurves for 1,4-PBds of various branching architectures. The high frequency transition region of the mastercurves superposed very well for all the 1,4-PBds irrespective of their molecular weight and architecture, indicating universality in high frequency behavior. Therefore, all three parameters of the tube model were extracted from this high frequency transition region alone. Third, we compared predictions of two versions of the tube model, Hierarchical model and BoB model against linear viscoelastic data of blends of 1,4-PBd star and linear melts. The star was carefully synthesized and characterized. We found massive failures of tube models to predict the terminal relaxation behavior of the star/linear blends. In addition, these blends were also tested against a coarse-grained slip-link model, the "Cluster Fixed Slip-link Model (CFSM)" of Schieber and coworkers. The CFSM with only two parameters gave excellent agreement with all experimental data for the blends.

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, I., E-mail: ingo.hoffmann@tu-berlin.de; Institut Max von Laue-Paul Langevin; Malo de Molina, Paula

2014-01-21

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence onmore » the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.« less

Photoisomers of Azobenzene Star with a Flat Core: Theoretical Insights into Multiple States from DFT and MD Perspective.

PubMed

Koch, Markus; Saphiannikova, Marina; Santer, Svetlana; Guskova, Olga

2017-09-21

This study focuses on comparing physical properties of photoisomers of an azobenzene star with benzene-1,3,5-tricarboxamide core. Three azobenzene arms of the molecule undergo a reversible trans-cis isomerization upon UV-vis light illumination giving rise to multiple states from the planar all-trans one, via two mixed states to the kinked all-cis isomer. Employing density functional theory, we characterize the structural and photophysical properties of each state indicating a role the planar core plays in the coupling between azobenzene chromophores. To characterize the light-triggered switching of solvophilicity/solvophobicity of the star, the difference in solvation free energy is calculated for the transfer of an azobenzene star from its gas phase to implicit or explicit solvents. For the latter case, classical all-atom molecular dynamics simulations of aqueous solutions of azobenzene star are performed employing the polymer consistent force field to shed light on the thermodynamics of explicit hydration as a function of the isomerization state and on the structuring of water around the star. From the analysis of two contributions to the free energy of hydration, the nonpolar van der Waals and the electrostatic terms, it is concluded that isomerization specificity largely determines the polarity of the molecule and the solute-solvent electrostatic interactions. This convertible hydrophilicity/hydrophobicity together with readjustable occupied volume and the surface area accessible to water, affects the self-assembly/disassembly of the azobenzene star with a flat core triggered by light.

Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

PubMed

Hira, Sumit Kumar; Ramesh, Kalyan; Gupta, Uttam; Mitra, Kheyanath; Misra, Nira; Ray, Biswajit; Manna, Partha Pratim

2015-09-16

We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses.

Electrochemical synthesis of multi-armed CuO nanoparticles and their remarkable bactericidal potential against waterborne bacteria

NASA Astrophysics Data System (ADS)

Pandey, Pratibha; Merwyn, S.; Agarwal, G. S.; Tripathi, B. K.; Pant, S. C.

2012-01-01

Copper (II) oxide multi-armed nanoparticles composed of 500-1000 nm long radiating nanospicules with 100-200 nm width near the base and 50-100 nm width at the tapered ends and 25 nm thickness were synthesized by electrochemical deposition in the presence of an oxidant followed by calcination at 150 °C. The nanoparticles were characterized using SEM/EDX for morphology and composition, Raman spectroscopy for compound identification, and broth culture method for antibacterial efficacy. The CuO nanoparticles have shown remarkable bactericidal efficacy against Gram-positive and -negative waterborne disease causing bacteria like Escherichia coli, Salmonella typhi, s taphylococcus aureus and Bacillus subtilis. E. coli has been chosen as representative species for waterborne disease causing bacteria. In antibacterial tests 500 μg/mL nano CuO killed 3 × 108 CFU/mL E. coli bacteria within 4 h of exposure. Moreover, 8.3 × 106 CFU/mL E. coli were killed by 100 and 10 μg/mL nano CuO within 15 min and 4 h of exposure, respectively. Antibacterial activity of nano CuO has been found many-fold compared with commercial bulk CuO. The fate of nanoparticles after antibacterial test has also been studied. The synthesized CuO nanoparticles are expected to have potential antibacterial applications in water purification and in paints and coatings used on frequently touched surfaces and fabrics in hospital settings.

Small-angle X-ray solution scattering study of the multi-aminoacyl-tRNA synthetase complex reveals an elongated and multi-armed particle.

PubMed

Dias, José; Renault, Louis; Pérez, Javier; Mirande, Marc

2013-08-16

In animal cells, nine aminoacyl-tRNA synthetases are associated with the three auxiliary proteins p18, p38, and p43 to form a stable and conserved large multi-aminoacyl-tRNA synthetase complex (MARS), whose molecular mass has been proposed to be between 1.0 and 1.5 MDa. The complex acts as a molecular hub for coordinating protein synthesis and diverse regulatory signal pathways. Electron microscopy studies defined its low resolution molecular envelope as an overall rather compact, asymmetric triangular shape. Here, we have analyzed the composition and homogeneity of the native mammalian MARS isolated from rabbit liver and characterized its overall internal structure, size, and shape at low resolution by hydrodynamic methods and small-angle x-ray scattering in solution. Our data reveal that the MARS exhibits a much more elongated and multi-armed shape than expected from previous reports. The hydrodynamic and structural features of the MARS are large compared with other supramolecular assemblies involved in translation, including ribosome. The large dimensions and non-compact structural organization of MARS favor a large protein surface accessibility for all its components. This may be essential to allow structural rearrangements between the catalytic and cis-acting tRNA binding domains of the synthetases required for binding the bulky tRNA substrates. This non-compact architecture may also contribute to the spatiotemporal controlled release of some of its components, which participate in non-canonical functions after dissociation from the complex.

Hydrogen cyanide polymers: from laboratory to space

NASA Astrophysics Data System (ADS)

Matthews, Clifford N.

1995-02-01

Hydrogen cyanide polymers - heterogeneous solids ranging in color from yellow to orange to red to black - may be among the organic macromolecules most readily formed within the solar system The non-volatile black crust of comet Halley for example, may consist largely of such polymers. It seems likely. too, that HCN polymers are a major constituent of the dark. CN bearing solids identified tentatively by IR spectra in the dust of some other comets. HCN polymerization could also account for some of the yellow-orange-red coloration of Jupiter and Saturn, and perhaps for the orange haze high in Titan's atmosphere. Studies of these polymers show that a yellow-brown powder can be extracted by water and further hydrolyzed to vield α-amino acids. Several instrumental methods used for the separation and identification of these intriguing materials. including pyrolysis mass spectrometry, Fourier transform IR photoacoustic spectroscopy and supercritical fluid extraction chromatography, reveal fragmentation patterns and chemical functionalities consistent with the presence of polymeric peptide precursors - polyamidines - in HCN polymers. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers and other organic products through bolide bombardment or terrestrial synthesis, producing a proteinaceous matrix able to bring about the molecular interactions leading to the emergence or life. Cyanide polymerization could also he a preferred pathway beyond Earth and the solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry.

PubMed

Haler, Jean R N; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-11-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. Graphical Abstract ᅟ.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Haler, Jean R. N.; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-08-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. [Figure not available: see fulltext.

Relating structure and flow of soft colloids

NASA Astrophysics Data System (ADS)

Kundu, S. K.; Gupta, S.; Stellbrink, J.; Willner, L.; Richter, D.

2013-11-01

To relate the complex macroscopic flow of soft colloids to details of its microscopic equilibrium and non-equilibrium structure is still one big challenge in soft matter science. We investigated several well-defined colloidal model systems like star polymers or diblock copolymer micelles by linear/non-linear rheology, static/dynamic light scattering (SLS/DLS) and small angle neutron scattering (SANS). In addition, in-situ SANS experiments during shear (Rheo-SANS) revealed directly shear induced structural changes on a microscopic level. Varying the molecular architecture of the individual colloidal particle as well as particle-particle interactions and covering at the same time a broad concentration range from the very dilute to highly concentrated, glassy regime, we could separate contributions from intra- and inter-particle softness. Both can be precisely "tuned" by varying systematically the functionality, 6 ≤ f≤ 64, for star polymers or aggregation number, 30 ≤ N agg ≤ 1000 for diblock copolymer micelles, as well as the degree of polymerization of the individual polymer arm 100 ≤ D p ≤ 3000. In dilute solutions, the characteristic shear rate at which deformation of the soft colloid is observed can be related to the Zimm time of the polymeric corona. In concentrated solutions, we validated a generalized Stokes-Einstein approach to describe the increase in macroscopic viscosity and mesoscopic self diffusion coefficient on approaching the glassy regime. Both can be explained in terms of an ultra-soft interaction potential. Moreover, non-equilibrium structure factors are obtained by Rheo-SANS. All experimental results are in excellent quantitative agreement with recent theoretical predictions.

Manipulability, force, and compliance analysis for planar continuum manipulators

NASA Technical Reports Server (NTRS)

Gravagne, Ian A.; Walker, Ian D.

2002-01-01

Continuum manipulators, inspired by the natural capabilities of elephant trunks and octopus tentacles, may find niche applications in areas like human-robot interaction, multiarm manipulation, and unknown environment exploration. However, their true capabilities will remain largely inaccessible without proper analytical tools to evaluate their unique properties. Ellipsoids have long served as one of the foremost analytical tools available to the robotics researcher, and the purpose of this paper is to first formulate, and then to examine, three types of ellipsoids for continuum robots: manipulability, force, and compliance.

Causal analysis of ordinal treatments and binary outcomes under truncation by death.

PubMed

Wang, Linbo; Richardson, Thomas S; Zhou, Xiao-Hua

2017-06-01

It is common that in multi-arm randomized trials, the outcome of interest is "truncated by death," meaning that it is only observed or well-defined conditioning on an intermediate outcome. In this case, in addition to pairwise contrasts, the joint inference for all treatment arms is also of interest. Under a monotonicity assumption we present methods for both pairwise and joint causal analyses of ordinal treatments and binary outcomes in presence of truncation by death. We illustrate via examples the appropriateness of our assumptions in different scientific contexts.

Manipulability, force, and compliance analysis for planar continuum manipulators.

PubMed

Gravagne, Ian A; Walker, Ian D

2002-06-01

Continuum manipulators, inspired by the natural capabilities of elephant trunks and octopus tentacles, may find niche applications in areas like human-robot interaction, multiarm manipulation, and unknown environment exploration. However, their true capabilities will remain largely inaccessible without proper analytical tools to evaluate their unique properties. Ellipsoids have long served as one of the foremost analytical tools available to the robotics researcher, and the purpose of this paper is to first formulate, and then to examine, three types of ellipsoids for continuum robots: manipulability, force, and compliance.

A Review of Computational Methods in Materials Science: Examples from Shock-Wave and Polymer Physics

PubMed Central

Steinhauser, Martin O.; Hiermaier, Stefan

2009-01-01

This review discusses several computational methods used on different length and time scales for the simulation of material behavior. First, the importance of physical modeling and its relation to computer simulation on multiscales is discussed. Then, computational methods used on different scales are shortly reviewed, before we focus on the molecular dynamics (MD) method. Here we survey in a tutorial-like fashion some key issues including several MD optimization techniques. Thereafter, computational examples for the capabilities of numerical simulations in materials research are discussed. We focus on recent results of shock wave simulations of a solid which are based on two different modeling approaches and we discuss their respective assets and drawbacks with a view to their application on multiscales. Then, the prospects of computer simulations on the molecular length scale using coarse-grained MD methods are covered by means of examples pertaining to complex topological polymer structures including star-polymers, biomacromolecules such as polyelectrolytes and polymers with intrinsic stiffness. This review ends by highlighting new emerging interdisciplinary applications of computational methods in the field of medical engineering where the application of concepts of polymer physics and of shock waves to biological systems holds a lot of promise for improving medical applications such as extracorporeal shock wave lithotripsy or tumor treatment. PMID:20054467

Hydrogen cyanide polymerization: a preferred cosmochemical pathway.

PubMed

Matthews, C N

1992-01-01

Current research in cosmochemistry shows that crude organic solids of high molecular weight are readily formed in planetary, interplanetary and interstellar environments. Underlying much of this ubiquitous chemistry is a low energy route leading directly to the synthesis of hydrogen cyanide and its polymers. Evidence from laboratory and extraterrestrial investigations suggests that these polymers plus water yield heteropolypeptides, a truly universal process that accounts not only for the past synthesis of protein ancestors on Earth but also for reactions proceeding elsewhere today within our solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies. The existence of this preferred pathway - hydrogen cyanide polymerization - surely increases greatly the probability that carbon-based life is widespread in the universe.

Polymer Nanosheet Containing Star-Like Copolymers: A Novel Scalable Controlled Release System.

PubMed

Cao, Peng-Fei; de Leon, Al; Rong, Lihan; Yin, Ke-Zhen; Abenojar, Eric C; Su, Zhe; Tiu, Brylee David B; Exner, Agata A; Baer, Eric; Advincula, Rigoberto C

2018-04-26

Poly(ε-caprolactone) (PCL)-based nanomaterials, such as nanoparticles and liposomes, have exhibited great potential as controlled release systems, but the difficulties in large-scale fabrication limit their practical applications. Among the various methods being developed to fabricate polymer nanosheets (PNSs) for different applications, such as Langmuir-Blodgett technique and layer-by-layer assembly, are very effort consuming, and only a few PNSs can be obtained. In this paper, poly(ε-caprolactone)-based PNSs with adjustable thickness are obtained in large quantity by simple water exposure of multilayer polymer films, which are fabricated via a layer multiplying coextrusion method. The PNS is also demonstrated as a novel controlled guest release system, in which release kinetics are adjustable by the nanosheet thickness, pH values of the media, and the presence of protecting layers. Theoretical simulations, including Korsmeyer-Peppas model and Finite-element analysis, are also employed to discern the observed guest-release mechanisms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Small-angle X-ray Solution Scattering Study of the Multi-aminoacyl-tRNA Synthetase Complex Reveals an Elongated and Multi-armed particle*

PubMed Central

Dias, José; Renault, Louis; Pérez, Javier; Mirande, Marc

2013-01-01

In animal cells, nine aminoacyl-tRNA synthetases are associated with the three auxiliary proteins p18, p38, and p43 to form a stable and conserved large multi-aminoacyl-tRNA synthetase complex (MARS), whose molecular mass has been proposed to be between 1.0 and 1.5 MDa. The complex acts as a molecular hub for coordinating protein synthesis and diverse regulatory signal pathways. Electron microscopy studies defined its low resolution molecular envelope as an overall rather compact, asymmetric triangular shape. Here, we have analyzed the composition and homogeneity of the native mammalian MARS isolated from rabbit liver and characterized its overall internal structure, size, and shape at low resolution by hydrodynamic methods and small-angle x-ray scattering in solution. Our data reveal that the MARS exhibits a much more elongated and multi-armed shape than expected from previous reports. The hydrodynamic and structural features of the MARS are large compared with other supramolecular assemblies involved in translation, including ribosome. The large dimensions and non-compact structural organization of MARS favor a large protein surface accessibility for all its components. This may be essential to allow structural rearrangements between the catalytic and cis-acting tRNA binding domains of the synthetases required for binding the bulky tRNA substrates. This non-compact architecture may also contribute to the spatiotemporal controlled release of some of its components, which participate in non-canonical functions after dissociation from the complex. PMID:23836901

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhen; Bian, Xin; Yang, Xiu

We construct effective coarse-grained (CG) models for polymeric fluids by employing two coarse-graining strategies. The first one is a forward-coarse-graining procedure by the Mori-Zwanzig (MZ) projection while the other one applies a reverse-coarse-graining procedure, such as the iterative Boltzmann inversion (IBI) and the stochastic parametric optimization (SPO). More specifically, we perform molecular dynamics (MD) simulations of star polymer melts to provide the atomistic fields to be coarse-grained. Each molecule of star polymer with internal degrees of freedom is coarsened into a single CG particle and the effective interactions between CG particles can be either evaluated directly from microscopic dynamics basedmore » on the MZ formalism, or obtained by the reverse methods, i.e., IBI and SPO. The forward procedure has no free parameters to tune and recovers the MD system faithfully. For the reverse procedure, we find that the parameters in CG models are not interchangeable. If the free parameters are properly selected, the reverse CG procedure also yields an effective potential. Moreover, we explain how an aggressive coarse-graining procedure introduces many-body effect, which makes the pairwise potential invalid for the same system at densities away from the training point. From this work, general guidelines for coarse-graining of polymeric fluids can be drawn.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhen; Bian, Xin; Karniadakis, George Em, E-mail: george-karniadakis@brown.edu

We construct effective coarse-grained (CG) models for polymeric fluids by employing two coarse-graining strategies. The first one is a forward-coarse-graining procedure by the Mori-Zwanzig (MZ) projection while the other one applies a reverse-coarse-graining procedure, such as the iterative Boltzmann inversion (IBI) and the stochastic parametric optimization (SPO). More specifically, we perform molecular dynamics (MD) simulations of star polymer melts to provide the atomistic fields to be coarse-grained. Each molecule of a star polymer with internal degrees of freedom is coarsened into a single CG particle and the effective interactions between CG particles can be either evaluated directly from microscopic dynamicsmore » based on the MZ formalism, or obtained by the reverse methods, i.e., IBI and SPO. The forward procedure has no free parameters to tune and recovers the MD system faithfully. For the reverse procedure, we find that the parameters in CG models cannot be selected arbitrarily. If the free parameters are properly defined, the reverse CG procedure also yields an accurate effective potential. Moreover, we explain how an aggressive coarse-graining procedure introduces the many-body effect, which makes the pairwise potential invalid for the same system at densities away from the training point. From this work, general guidelines for coarse-graining of polymeric fluids can be drawn.« less

Myocardial matrix-polyethylene glycol hybrid hydrogels for tissue engineering

NASA Astrophysics Data System (ADS)

Grover, Gregory N.; Rao, Nikhil; Christman, Karen L.

2014-01-01

Similar to other protein-based hydrogels, extracellular matrix (ECM) based hydrogels, derived from decellularized tissues, have a narrow range of mechanical properties and are rapidly degraded. These hydrogels contain natural cellular adhesion sites, form nanofibrous networks similar to native ECM, and are biodegradable. In this study, we expand the properties of these types of materials by incorporating poly(ethylene glycol) (PEG) into the ECM network. We use decellularized myocardial matrix as an example of a tissue specific ECM derived hydrogel. Myocardial matrix-PEG hybrids were synthesized by two different methods, cross-linking the proteins with an amine-reactive PEG-star and photo-induced radical polymerization of two different multi-armed PEG-acrylates. We show that both methods allow for conjugation of PEG to the myocardial matrix by gel electrophoresis and infrared spectroscopy. Scanning electron microscopy demonstrated that the hybrid materials still contain a nanofibrous network similar to unmodified myocardial matrix and that the fiber diameter is changed by the method of PEG incorporation and PEG molecular weight. PEG conjugation also decreased the rate of enzymatic degradation in vitro, and increased material stiffness. Hybrids synthesized with amine-reactive PEG had gelation rates of 30 min, similar to the unmodified myocardial matrix, and incorporation of PEG did not prevent cell adhesion and migration through the hydrogels, thus offering the possibility to have an injectable ECM hydrogel that degrades more slowly in vivo. The photo-polymerized radical systems gelled in 4 min upon irradiation, allowing 3D encapsulation and culture of cells, unlike the soft unmodified myocardial matrix. This work demonstrates that PEG incorporation into ECM-based hydrogels can expand material properties, thereby opening up new possibilities for in vitro and in vivo applications.

KE108-conjugated unimolecular micelles loaded with a novel HDAC inhibitor thailandepsin-A for targeted neuroendocrine cancer therapy.

PubMed

Chen, Guojun; Jaskula-Sztul, Renata; Harrison, April; Dammalapati, Ajitha; Xu, Wenjin; Cheng, Yiqiang; Chen, Herbert; Gong, Shaoqin

2016-08-01

Neuroendocrine (NE) cancers can cause significant patient morbidity. Besides surgery, there are no curative treatments for NE cancers and their metastases, emphasizing the need for the development of other forms of therapy. In this study, multifunctional unimolecular micelles were developed for targeted NE cancer therapy. The unimolecular micelles were formed by multi-arm star amphiphilic block copolymer poly(amidoamine)-poly(valerolactone)-poly(ethylene glycol) conjugated with KE108 peptide and Cy5 dye (abbreviated as PAMAM-PVL-PEG-KE108/Cy5). The unimolecular micelles with a spherical core-shell structure exhibited a uniform size distribution and excellent stability. The hydrophobic drug thailandepsin-A (TDP-A), a recently discovered HDAC inhibitor, was physically encapsulated into the hydrophobic core of the micelles. KE108 peptide, a somatostatin analog possessing high affinity for all five subtypes of somatostatin receptors (SSTR 1-5), commonly overexpressed in NE cancer cells, was used for the first time as an NE cancer targeting ligand. KE108 exhibited superior targeting abilities compared to other common somatostatin analogs, such as octreotide, in NE cancer cell lines. The in vitro assays demonstrated that the TDP-A-loaded, KE108-targeted micelles exhibited the best capabilities in suppressing NE cancer cell growth. Moreover, the in vivo near-infrared fluorescence imaging on NE-tumor-bearing nude mice showed that KE108-conjugated micelles exhibited the greatest tumor accumulation due to their passive targeting and active targeting capabilities. Finally, TDP-A-loaded and KE108-conjugated micelles possessed the best anticancer efficacy without detectable systemic toxicity. Thus, these novel TDP-A-loaded and KE108-conjugated unimolecular micelles offer a promising approach for targeted NE cancer therapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computing the non-Markovian coarse-grained interactions derived from the Mori-Zwanzig formalism in molecular systems: Application to polymer melts

NASA Astrophysics Data System (ADS)

Li, Zhen; Lee, Hee Sun; Darve, Eric; Karniadakis, George Em

2017-01-01

Memory effects are often introduced during coarse-graining of a complex dynamical system. In particular, a generalized Langevin equation (GLE) for the coarse-grained (CG) system arises in the context of Mori-Zwanzig formalism. Upon a pairwise decomposition, GLE can be reformulated into its pairwise version, i.e., non-Markovian dissipative particle dynamics (DPD). GLE models the dynamics of a single coarse particle, while DPD considers the dynamics of many interacting CG particles, with both CG systems governed by non-Markovian interactions. We compare two different methods for the practical implementation of the non-Markovian interactions in GLE and DPD systems. More specifically, a direct evaluation of the non-Markovian (NM) terms is performed in LE-NM and DPD-NM models, which requires the storage of historical information that significantly increases computational complexity. Alternatively, we use a few auxiliary variables in LE-AUX and DPD-AUX models to replace the non-Markovian dynamics with a Markovian dynamics in a higher dimensional space, leading to a much reduced memory footprint and computational cost. In our numerical benchmarks, the GLE and non-Markovian DPD models are constructed from molecular dynamics (MD) simulations of star-polymer melts. Results show that a Markovian dynamics with auxiliary variables successfully generates equivalent non-Markovian dynamics consistent with the reference MD system, while maintaining a tractable computational cost. Also, transient subdiffusion of the star-polymers observed in the MD system can be reproduced by the coarse-grained models. The non-interacting particle models, LE-NM/AUX, are computationally much cheaper than the interacting particle models, DPD-NM/AUX. However, the pairwise models with momentum conservation are more appropriate for correctly reproducing the long-time hydrodynamics characterised by an algebraic decay in the velocity autocorrelation function.

Characterization of Mixed Polypeptide Colloidal Particles by Light Scattering

NASA Astrophysics Data System (ADS)

Shuman, Hannah E.; Gaeckle, Grace K.; Gavin, John; Holland, Nolan B.; Streletzky, Kiril A.

2014-03-01

Temperature-dependent polymer surfactants have been developed by connecting three elastin-like polypeptide (ELP) chains to a charged protein domain (foldon), forming a three-armed star polymer. At low temperatures the polymer is soluble, while at higher temperatures it forms micelles. The behavior of mixtures of the three-armed star ELP (E20-Foldon) and H40-Linear ELP chains was analyzed under different salt and protein concentrations and various foldon to linear ELP ratio using Depolarized Dynamic Light Scattering. It was expected that under certain conditions the pure E20-Foldon would form spherical micelles, which upon adding the linear ELP would change in size and possibly shape. The pure E20-Foldon indeed formed largely spherical micelles with Rh of 10-20nm in solutions with 15-100mM salt and protein concentration between 10 μM and 100 μM. For the mixtures of 50 μM E20-Foldon and varying concentrations of H40-Linear in 25mM of salt, it was discovered that low and high H40-Linear concentration (4 μM and 50 μM) had only one transition. For the mixtures with of 10 and 25 μM of H40-Linear the two distinct transition temperatures were observed by spectrophotometry. The first transition corresponded to significantly elongated diffusive particles of apparent Rh of 30-50nm, while the second transition corresponded to slightly anisotropic diffusive particles with apparent Rh of about 20nm. At all H40-Linear concentrations studied, diffusive particles were seen above the second transition. Their radius and ability to depolarize light increased with the increase of H40-Linear concentration.

Bionano Interaction Study on Antimicrobial Star-Shaped Peptide Polymer Nanoparticles.

PubMed

Lam, Shu J; Wong, Edgar H H; O'Brien-Simpson, Neil M; Pantarat, Namfon; Blencowe, Anton; Reynolds, Eric C; Qiao, Greg G

2016-12-14

'Structurally nanoengineered antimicrobial peptide polymers' (SNAPPs), in the form of star-shaped peptide polymer nanoparticles, have been recently demonstrated as a new class of antimicrobial agents with superior in vitro and in vivo efficacy against Gram-negative pathogens, including multidrug-resistant species. Herein, we present a detailed bionano interaction study on SNAPPs by assessing their antimicrobial activities against several Gram-negative bacteria in complex biological matrices. Simulated body fluid and animal serum were used as test media to reveal factors that influence the antimicrobial efficacy of SNAPPs. With the exception of Acinetobacter baumannii, the presence of divalent cations at physiological concentrations reduced the antimicrobial efficacy of SNAPPs from minimum inhibitory concentrations (MICs) within the nanomolar range (40-300 nM) against Escherichia coli, Pseudomanas aeruginosa, and Klebsiella pneumoniae to 0.6-4.7 μM. By using E. coli as a representative bacterial species, we demonstrated that the reduction in activity was due to a decrease in the ability of SNAPPs to cause outer and inner membrane disruption. This effect could be reversed through coadministration with a chelating agent. Interestingly, the potency of SNAPPs against A. baumannii was retained even under high salt concentrations. The presence of serum proteins was also found to affect the interaction of SNAPPs with bacterial membranes, possibly through intermolecular binding. Collectively, this study highlights the need to consider the possible interactions of (bio)molecules present in vivo with any new antimicrobial agent under development. We also demonstrate that outer membrane disruption/destabilization is an important but hitherto under-recognized target for the antimicrobial action of peptide-based agents, such as antimicrobial peptides (AMPs). Overall, the findings presented herein could aid in the design of more efficient peptide-based antimicrobial agents with uncompromised potency even under physiological conditions.

Multicompartmental Microcapsules from Star Copolymer Micelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Ikjun; Malak, Sidney T.; Xu, Weinan

2013-02-26

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into themore » LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.« less

Dewetting Kinetics in Polymer Grafted Nanoparticle Thin Films: Impact of Architecture and Viscosity on Thermal Stability

NASA Astrophysics Data System (ADS)

Che, Justin; Jawaid, Ali; Grabowski, Christopher; Yi, Yoon-Jae; Vaia, Richard; AFRL Collaboration

Rapid formation of ordered monolayers of polymer grafted nanoparticles (PGN) directly onto solid surfaces has spurred interest in using these materials for additive manufacturing of optical devices and energy storage. Herein, we discuss dewetting of polystyrene grafted Au nanoparticles (PS@Au) with an increased thermal (10-25oC) and energetic (5-15 mN/m) stability relative to linear polymer films of comparable thickness. Analogous to star macromolecules, the enhanced stability is related to the conformations of chains in the grafted canopy. Mechanistically, dewetting of PS@Au is similar to linear PS, however, the thickness transition from spinodal to heterogeneous nucleation is at least 5-6x larger. Time resolved optical microscopy during dewetting at 160oC revealed that the zero shear viscosity for linear PS scaled as η0 Mn3. 3 , consistent with reptation of entangled polymers. In contrast, PS@Au showed η0 Mn2. 2 where Mn reflects the molecular weight of the grafted chains. Overall, PS@Au exhibited significantly slower dewetting rates, consistent with a 100x increase in viscosity relative to the linear chain analogues. Quantification of the relationship between PGN architecture (e.g. nanoparticle size, graft density, polymer molecular weight) and dewetting processes is crucial to optimize the order of these assemblies via post-processing, as well as design the PGN canopy to maximize stability for devices.

A unified teleoperated-autonomous dual-arm robotic system

NASA Technical Reports Server (NTRS)

Hayati, Samad; Lee, Thomas S.; Tso, Kam Sing; Backes, Paul G.; Lloyd, John

1991-01-01

A description is given of complete robot control facility built as part of a NASA telerobotics program to develop a state-of-the-art robot control environment for performing experiments in the repair and assembly of spacelike hardware to gain practical knowledge of such work and to improve the associated technology. The basic architecture of the manipulator control subsystem is presented. The multiarm Robot Control C Library (RCCL), a key software component of the system, is described, along with its implementation on a Sun-4 computer. The system's simulation capability is also described, and the teleoperation and shared control features are explained.

Gold nanostar-polymer hybrids for siRNA delivery: Polymer design towards colloidal stability and in vitro studies on breast cancer cells.

PubMed

Sardo, Carla; Bassi, Barbara; Craparo, Emanuela F; Scialabba, Cinzia; Cabrini, Elisa; Dacarro, Giacomo; D'Agostino, Agnese; Taglietti, Angelo; Giammona, Gaetano; Pallavicini, Piersandro; Cavallaro, Gennara

2017-03-15

To overcome the low bioavailability of siRNA (small interfering RNA) and to improve their transfection efficiency, the use of non-viral delivery carriers is today a feasible approach to transform the discovery of these incredibly potent and versatile drugs into clinical practice. Polymer-modified gold nanoconstructs (AuNCs) are currently viewed as efficient and safe intracellular delivery carriers for siRNA, as they have the possibility to conjugate the ability to stably entrap and deliver siRNAs inside cells with the advantages of gold nanoparticles, which can act as theranostic agents and radiotherapy enhancers through laser-induced hyperthermia. In this study, AuNCs were prepared by coating Gold Nano Stars (GNS) with suitable functionalised polymers, to give new insight on the choice of the coating in order to obtain colloidal stability, satisfying in vitro transfection behaviour and reliability in terms of homogeneous results upon GNS type changing. For this goal, GNS synthesized with three different sizes and shapes were coated with two different polymers: i) α-mercapto-ω-amino polyethylene glycol 3000Da (SH-PEG 3000 -NH 2 ), a hydrophilic linear polymer; ii) PHEA-PEG 2000 -EDA-LA (PPE-LA), an amphiphilic hydroxyethylaspartamide copolymer containing a PEG moiety. Both polymers contain SH or SS groups for anchoring on gold surface and NH 2 groups, which can be protonated in order to obtain a positive surface for successive siRNA layering. The effect of the features of the coating polymers on siRNA layering, and the extent of intracellular uptake and luciferase gene silencing effect were evaluated for each of the obtained coated GNS. The results highlight that amphiphilic biocompatible polymers with multi-grafting function are more suitable for ensuring the colloidal stability and the effectiveness of these colloidal systems, compared to the coating with linear PEG. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and sensing properties of D5h pentagonal silver star nanoparticles.

PubMed

Cathcart, Nicole; Coombs, Neil; Gourevich, Ilya; Kitaev, Vladimir

2016-11-03

In this work, we use silver decahedral nanoparticle (AgDeNP) seeds to synthesize pentagonal silver stars (AgStDeNPs) and study the sensing properties of these nanoparticles. The regrowth process of AgStDeNPs is kinetically-controlled, so the purity of the seed NPs is critical to avoid secondary deposition in the highly non-equilibrium reduction. To control the regrowth process, surface blocking with sodium polyacrylate (PANa) was implemented. PANa moderates rough silver nanostructures typically obtained by reduction with ascorbic acid. To modulate polymer binding to the surface and thus to tune surface blocking, pH served as a key synthetic parameter. Under optimal regrowth conditions, new sliver was deposited on the highest energy sites of the decahedra - the vertices of the rims - to yield pentagonal stars. The universality of this regrowth process was established with several different seed particles. The sharpness and size of the stellated tips are tunable by the amount of added silver. Gold deposition onto AgStDeNPs enables the preparation of diverse structures with enhanced stability. Ease of transformation, e.g. rounding, of star branches opens a promising venue for enhanced SPR sensing. Also, AgStDeNPs enable femtomolar detection of 5,5-dithiobis(2-nitrobenzoic acid) in SERS.

Molecular Dynamics Simulations of Star Polymeric Molecules with Diblock Arms, a Comparative Study.

PubMed

Swope, William C; Carr, Amber C; Parker, Amanda J; Sly, Joseph; Miller, Robert D; Rice, Julia E

2012-10-09

We have performed all atom explicit solvent molecular dynamics simulations of three different star polymeric systems in water, each star molecule consisting of 16 diblock copolymer arms bound to a small adamantane core. The arms of each system consist of an inner "hydrophobic" block (either polylactide, polyvalerolactone, or polyethylene) and an outer hydrophilic block (polyethylene oxide, PEO). These models exhibit unusual structure very close to the core (clearly an artifact of our model) but which we believe becomes "normal" or bulk-like at relatively short distances from this core. We report on a number of temperature-dependent thermodynamic (structural/energetic) properties as well as kinetic properties. Our observations suggest that under physiological conditions, the hydrophobic regions of these systems may be solid and glassy, with only rare and shallow penetration by water, and that a sharp boundary exists between the hydrophobic cores and either the PEO or water. The PEO in these models is seen to be fully water-solvated at low temperatures but tends to phase separate from water as the temperature is increased, reminiscent of a lower critical solution temperature exhibited by PEO-water mixtures. Water penetration concentration and depth is composition and temperature dependent with greater water penetration for the most ester-rich star polymer.

A computational investigation of the thermodynamics and structure in colloid and polymer mixtures

NASA Astrophysics Data System (ADS)

Mahynski, Nathan Alexander

In this dissertation I use computational tools to study the structure and thermodynamics of colloid-polymer mixtures. I show that fluid-fluid phase separation in mixtures of colloids and linear polymers cannot be universally reduced using polymer-based scaling principles since these assume the binodals exist in a single scaling regime, whereas accurate simulations clearly demonstrate otherwise. I show that rethinking these solutions in terms of multiple length scales is necessary to properly explain the thermodynamic stability and structure of these fluid phases, and produce phase diagrams in nearly quantitative agreement with experimental results. I then extend this work to encompass more geometrically complex "star" polymers revealing how the phase behavior for many of these binary mixtures may be mapped onto that of mixtures containing only linear polymers. I further consider the depletion-driven crystallization of athermal colloidal hard spheres induced by polymers. I demonstrate how the partitioning of a finite amount of polymer into the colloidal crystal phase implies that the polymer's architecture can be tailored to interact with the internal void structure of different crystal polymorphs uniquely, thus providing a direct route to thermodynamically stabilizing one arbitrarily chosen structure over another, e.g., the hexagonal close-packed crystal over the face-centered cubic. I then begin to generalize this result by considering the consequences of thermal interactions and complex polymer architectures. These principles lay the groundwork for intelligently engineering co-solute additives in crystallizing colloidal suspensions that can be used to thermodynamically isolate single crystal morphologies. Finally, I examine the competition between self-assembly and phase separation in polymer-grafted nanoparticle systems by comparing and contrasting the validity of two different models for grafted nanoparticles: "nanoparticle amphiphiles" versus "patchy particles." The latter suggests these systems have some utility in forming novel "equilibrium gel" phases, however, I find that considering grafted nanoparticles as amphiphiles provides a qualitatively accurate description of their thermodynamics revealing either first-order phase separation into two isotropic phases or continuous self-assembly. I find no signs of empty liquid formation, suggesting that these nanoparticles do not provide a route to such phases.

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

PubMed

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

2016-05-07

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

Selecting promising treatments in randomized Phase II cancer trials with an active control.

PubMed

Cheung, Ying Kuen

2009-01-01

The primary objective of Phase II cancer trials is to evaluate the potential efficacy of a new regimen in terms of its antitumor activity in a given type of cancer. Due to advances in oncology therapeutics and heterogeneity in the patient population, such evaluation can be interpreted objectively only in the presence of a prospective control group of an active standard treatment. This paper deals with the design problem of Phase II selection trials in which several experimental regimens are compared to an active control, with an objective to identify an experimental arm that is more effective than the control or to declare futility if no such treatment exists. Conducting a multi-arm randomized selection trial is a useful strategy to prioritize experimental treatments for further testing when many candidates are available, but the sample size required in such a trial with an active control could raise feasibility concerns. In this study, we extend the sequential probability ratio test for normal observations to the multi-arm selection setting. The proposed methods, allowing frequent interim monitoring, offer high likelihood of early trial termination, and as such enhance enrollment feasibility. The termination and selection criteria have closed form solutions and are easy to compute with respect to any given set of error constraints. The proposed methods are applied to design a selection trial in which combinations of sorafenib and erlotinib are compared to a control group in patients with non-small-cell lung cancer using a continuous endpoint of change in tumor size. The operating characteristics of the proposed methods are compared to that of a single-stage design via simulations: The sample size requirement is reduced substantially and is feasible at an early stage of drug development.

A dynamic multiarmed bandit-gene expression programming hyper-heuristic for combinatorial optimization problems.

PubMed

Sabar, Nasser R; Ayob, Masri; Kendall, Graham; Qu, Rong

2015-02-01

Hyper-heuristics are search methodologies that aim to provide high-quality solutions across a wide variety of problem domains, rather than developing tailor-made methodologies for each problem instance/domain. A traditional hyper-heuristic framework has two levels, namely, the high level strategy (heuristic selection mechanism and the acceptance criterion) and low level heuristics (a set of problem specific heuristics). Due to the different landscape structures of different problem instances, the high level strategy plays an important role in the design of a hyper-heuristic framework. In this paper, we propose a new high level strategy for a hyper-heuristic framework. The proposed high-level strategy utilizes a dynamic multiarmed bandit-extreme value-based reward as an online heuristic selection mechanism to select the appropriate heuristic to be applied at each iteration. In addition, we propose a gene expression programming framework to automatically generate the acceptance criterion for each problem instance, instead of using human-designed criteria. Two well-known, and very different, combinatorial optimization problems, one static (exam timetabling) and one dynamic (dynamic vehicle routing) are used to demonstrate the generality of the proposed framework. Compared with state-of-the-art hyper-heuristics and other bespoke methods, empirical results demonstrate that the proposed framework is able to generalize well across both domains. We obtain competitive, if not better results, when compared to the best known results obtained from other methods that have been presented in the scientific literature. We also compare our approach against the recently released hyper-heuristic competition test suite. We again demonstrate the generality of our approach when we compare against other methods that have utilized the same six benchmark datasets from this test suite.

A comparative study of coarse-graining methods for polymeric fluids: Mori-Zwanzig vs. iterative Boltzmann inversion vs. stochastic parametric optimization

NASA Astrophysics Data System (ADS)

Li, Zhen; Bian, Xin; Yang, Xiu; Karniadakis, George Em

2016-07-01

We construct effective coarse-grained (CG) models for polymeric fluids by employing two coarse-graining strategies. The first one is a forward-coarse-graining procedure by the Mori-Zwanzig (MZ) projection while the other one applies a reverse-coarse-graining procedure, such as the iterative Boltzmann inversion (IBI) and the stochastic parametric optimization (SPO). More specifically, we perform molecular dynamics (MD) simulations of star polymer melts to provide the atomistic fields to be coarse-grained. Each molecule of a star polymer with internal degrees of freedom is coarsened into a single CG particle and the effective interactions between CG particles can be either evaluated directly from microscopic dynamics based on the MZ formalism, or obtained by the reverse methods, i.e., IBI and SPO. The forward procedure has no free parameters to tune and recovers the MD system faithfully. For the reverse procedure, we find that the parameters in CG models cannot be selected arbitrarily. If the free parameters are properly defined, the reverse CG procedure also yields an accurate effective potential. Moreover, we explain how an aggressive coarse-graining procedure introduces the many-body effect, which makes the pairwise potential invalid for the same system at densities away from the training point. From this work, general guidelines for coarse-graining of polymeric fluids can be drawn.

A comparative study of coarse-graining methods for polymeric fluids: Mori-Zwanzig vs. iterative Boltzmann inversion vs. stochastic parametric optimization.

PubMed

Li, Zhen; Bian, Xin; Yang, Xiu; Karniadakis, George Em

2016-07-28

We construct effective coarse-grained (CG) models for polymeric fluids by employing two coarse-graining strategies. The first one is a forward-coarse-graining procedure by the Mori-Zwanzig (MZ) projection while the other one applies a reverse-coarse-graining procedure, such as the iterative Boltzmann inversion (IBI) and the stochastic parametric optimization (SPO). More specifically, we perform molecular dynamics (MD) simulations of star polymer melts to provide the atomistic fields to be coarse-grained. Each molecule of a star polymer with internal degrees of freedom is coarsened into a single CG particle and the effective interactions between CG particles can be either evaluated directly from microscopic dynamics based on the MZ formalism, or obtained by the reverse methods, i.e., IBI and SPO. The forward procedure has no free parameters to tune and recovers the MD system faithfully. For the reverse procedure, we find that the parameters in CG models cannot be selected arbitrarily. If the free parameters are properly defined, the reverse CG procedure also yields an accurate effective potential. Moreover, we explain how an aggressive coarse-graining procedure introduces the many-body effect, which makes the pairwise potential invalid for the same system at densities away from the training point. From this work, general guidelines for coarse-graining of polymeric fluids can be drawn.

ON THE FORMATION OF AMIDE POLYMERS VIA CARBONYL–AMINO GROUP LINKAGES IN ENERGETICALLY PROCESSED ICES OF ASTROPHYSICAL RELEVANCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Förstel, Marko; Maksyutenko, Pavlo; Jones, Brant M.

2016-04-01

We report on the formation of organic amide polymers via carbonyl–amino group linkages in carbon monoxide and ammonia bearing energetically processed ices of astrophysical relevance. The first group comprises molecules with one carboxyl group and an increasing number of amine moieties starting with formamide (45 u), urea (60 u), and hydrazine carboxamide (75 u). The second group consists of species with two carboxyl (58 u) and up to three amine groups (73 u, 88 u, and 103 u). The formation and polymerization of these linkages from simple inorganic molecules via formamide und urea toward amide polymers is discussed in anmore » astrophysical and astrobiological context. Our results show that long chain molecules, which are closely related to polypeptides, easily form by energetically processing simple, inorganic ices at very low temperatures and can be released into the gas phase by sublimation of the ices in star-forming regions. Our experimental results were obtained by employing reflectron time-of-flight mass spectroscopy, coupled with soft, single photon vacuum ultraviolet photoionization; they are complemented by theoretical calculations.« less

Coordination of multiple robot arms

NASA Technical Reports Server (NTRS)

Barker, L. K.; Soloway, D.

1987-01-01

Kinematic resolved-rate control from one robot arm is extended to the coordinated control of multiple robot arms in the movement of an object. The structure supports the general movement of one axis system (moving reference frame) with respect to another axis system (control reference frame) by one or more robot arms. The grippers of the robot arms do not have to be parallel or at any pre-disposed positions on the object. For multiarm control, the operator chooses the same moving and control reference frames for each of the robot arms. Consequently, each arm then moves as though it were carrying out the commanded motions by itself.

Well Casing Baseline Analysis for the Big Hill Strategic Petroleum Reserve Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moriarty, Dylan Michael; Roberts, Barry L.

This report analyzes data from multi-arm caliper (MAC) surveys taken at the Big Hill SPR site to determine the most likely casing weights within each well. Radial arm data from MAC surveys were used to calculate the approximate wall thickness of each well. Results from this study indicate that (1) most wells at the site have thinner wall thicknesses than expected, (2) most wells experienced an acute increase in diameter near the salt/caprock interface, and (3) there were isolated instances of well sections being the wrong casing weight. All three findings could have a negative impact on well integrity.

Single-photon decision maker

NASA Astrophysics Data System (ADS)

Naruse, Makoto; Berthel, Martin; Drezet, Aurélien; Huant, Serge; Aono, Masashi; Hori, Hirokazu; Kim, Song-Ju

2015-08-01

Decision making is critical in our daily lives and for society in general and is finding evermore practical applications in information and communication technologies. Herein, we demonstrate experimentally that single photons can be used to make decisions in uncertain, dynamically changing environments. Using a nitrogen-vacancy in a nanodiamond as a single-photon source, we demonstrate the decision-making capability by solving the multi-armed bandit problem. This capability is directly and immediately associated with single-photon detection in the proposed architecture, leading to adequate and adaptive autonomous decision making. This study makes it possible to create systems that benefit from the quantum nature of light to perform practical and vital intelligent functions.

Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

PubMed

Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

2015-06-28

Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant kinetic stability that have potential for use as an anti-cancer drug delivery carrier for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

On-sky tests of a polarization grating for visible astronomy

NASA Astrophysics Data System (ADS)

Millar-Blanchaer, Maxwell A.; Moon, Dae-Sik; Graham, James R.; Williams, Michael

2016-08-01

Polarization gratings (PGs) are a type of diffraction grating that take advantage of birefringent liquid crystal polymers to simultaneously act as a polarizing beam splitter and as a spectral dispersive element. Furthermore, PGs are capable of providing high diffraction efficiency (>90%) over a very broad wavelength range. These properties make PGs ideal for spectropolarimetry and/or high throughput, broad wavelength observations for a range of astronomical objects. Here we report on the design and on-sky testing of a prototype spectropolarimeter instrument that employs a PG optimized for operation from 500 nm to 900 nm. The prototype was mounted on a 16-inch telescope at the University of Toronto, where we carried out observations of the polarized twilight sky, a polarized standard star and two spectroscopic standard stars. Using these observations we demonstrate the PG's ability to measure linear polarization fraction and position angle, as well as recover spectra from astronomical objects.

Reversible TAD Chemistry as a Convenient Tool for the Design of (Re)processable PCL-Based Shape-Memory Materials.

PubMed

Defize, Thomas; Riva, Raphaël; Thomassin, Jean-Michel; Alexandre, Michaël; Herck, Niels Van; Prez, Filip Du; Jérôme, Christine

2017-01-01

A chemically cross-linked but remarkably (re)processable shape-memory polymer (SMP) is designed by cross-linking poly(ε-caprolactone) (PCL) stars via the efficient triazolinedione click chemistry, based on the very fast and reversible Alder-ene reaction of 1,2,4-triazoline-3,5-dione (TAD) with indole compounds. Typically, a six-arm star-shaped PCL functionalized by indole moieties at the chain ends is melt-blended with a bisfunctional TAD, directly resulting in a cross-linked PCL-based SMP without the need of post-curing treatment. As demonstrated by the stress relaxation measurement, the labile character of the TAD-indole adducts under stress allows for the solid-state plasticity reprocessing of the permanent shape at will by compression molding of the raw cross-linked material, while keeping excellent shape-memory properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Polymers Having Low Melt Viscosities

NASA Technical Reports Server (NTRS)

Jensen, Brian J.

2005-01-01

High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.

Comparison of the Single Molecule Dynamics of Linear and Circular DNAs in Planar Extensional Flows

NASA Astrophysics Data System (ADS)

Li, Yanfei; Hsiao, Kai-Wen; Brockman, Christopher; Yates, Daniel; McKenna, Gregory; Schroeder, Charles; San Francisco, Michael; Kornfield, Julie; Anderson, Rae

2015-03-01

Chain topology has a profound impact on the flow behaviors of single macromolecules. The absence of free ends separates circular polymers from other chain architectures, i.e., linear, star, and branched. In the present work, we study the single chain dynamics of large circular and linear DNA molecules by comparing the relaxation dynamics, steady state coil-stretch transition, and transient molecular individualism behaviors for the two types of macromolecules. To this end, large circular DNA molecules were biologically synthesized and studied in a microfluidic device that has a cross-slot geometry to develop a stagnation point extensional flow. Although the relaxation time of rings scales in the same way as for the linear analog, the circular polymers show quantitatively different behaviors in the steady state extension and qualitatively different behaviors during a transient stretch. The existence of some commonality between these two topologies is proposed. Texas Tech University John R. Bradford Endowment.

Instabilities in wormlike micelle systems. From shear-banding to elastic turbulence.

PubMed

Fardin, M-A; Lerouge, S

2012-09-01

Shear-banding is ubiquitous in complex fluids. It is related to the organization of the flow into macroscopic bands bearing different viscosities and local shear rates and stacked along the velocity gradient direction. This flow-induced transition towards a heterogeneous flow state has been reported in a variety of systems, including wormlike micellar solutions, telechelic polymers, emulsions, clay suspensions, colloidal gels, star polymers, granular materials, or foams. In the past twenty years, shear-banding flows have been probed by various techniques, such as rheometry, velocimetry and flow birefringence. In wormlike micelle solutions, many of the data collected exhibit unexplained spatio-temporal fluctuations. Different candidates have been identified, the main ones being wall slip, interfacial instability between bands or bulk instability of one of the bands. In this review, we present experimental evidence for a purely elastic instability of the high shear rate band as the main origin for fluctuating shear-banding flows.

Looped star polymers show conformational transition from spherical to flat toroidal shapes.

PubMed

Reiss, Pascal; Fritsche, Miriam; Heermann, Dieter W

2011-11-01

Inspired by the topological organization of the circular Escherichia coli chromosome, which is compacted by separate domains, we study a polymer architecture consisting of a central ring to which either looped or linear side chains are grafted. A shape change from a spherical to a toroidal organization takes place as soon as the inner ring becomes large enough for the attached arms to fit within its circumference. Building up a torus, the system flattens, depending on the effective bending rigidity of the chain induced by entropic repulsion of the attached loops and, to a lesser extent, linear arms. Our results suggest that the natural formation of a toroidal structure with a decreased amount of writhe induced by a specific underlying topology could be one driving force, among others, that nature exploits to ensure proper packaging of the genetic material within a rod-shaped, bacterial envelope.

A general and robust strategy for the synthesis of nearly monodisperse colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Pang, Xinchang; Zhao, Lei; Han, Wei; Xin, Xukai; Lin, Zhiqun

2013-06-01

Colloidal nanocrystals exhibit a wide range of size- and shape-dependent properties and have found application in myriad fields, incuding optics, electronics, mechanics, drug delivery and catalysis, to name but a few. Synthetic protocols that enable the simple and convenient production of colloidal nanocrystals with controlled size, shape and composition are therefore of key general importance. Current strategies include organic solution-phase synthesis, thermolysis of organometallic precursors, sol-gel processes, hydrothermal reactions and biomimetic and dendrimer templating. Often, however, these procedures require stringent experimental conditions, are difficult to generalize, or necessitate tedious multistep reactions and purification. Recently, linear amphiphilic block co-polymer micelles have been used as templates to synthesize functional nanocrystals, but the thermodynamic instability of these micelles limits the scope of this approach. Here, we report a general strategy for crafting a large variety of functional nanocrystals with precisely controlled dimensions, compositions and architectures by using star-like block co-polymers as nanoreactors. This new class of co-polymers forms unimolecular micelles that are structurally stable, therefore overcoming the intrinsic instability of linear block co-polymer micelles. Our approach enables the facile synthesis of organic solvent- and water-soluble nearly monodisperse nanocrystals with desired composition and architecture, including core-shell and hollow nanostructures. We demonstrate the generality of our approach by describing, as examples, the synthesis of various sizes and architectures of metallic, ferroelectric, magnetic, semiconductor and luminescent colloidal nanocrystals.

Multiple patterns of polymer gels in microspheres due to the interplay among phase separation, wetting, and gelation.

PubMed

Yanagisawa, Miho; Nigorikawa, Shinpei; Sakaue, Takahiro; Fujiwara, Kei; Tokita, Masayuki

2014-11-11

We report the spontaneous patterning of polymer microgels by confining a polymer blend within microspheres. A poly(ethylene glycol) (PEG) and gelatin solution was confined inside water-in-oil (W/O) microdroplets coated with a layer of zwitterionic lipids: dioleoylphosphatidylethanolamine (PE) and dioleoylphosphatidylcholine (PC). The droplet confinement affected the kinetics of the phase separation, wetting, and gelation after a temperature quench, which determined the final microgel pattern. The gelatin-rich phase completely wetted to the PE membrane and formed a hollow microcapsule as a stable state in the PE droplets. Gelation during phase separation varied the relation between the droplet size and thickness of the capsule wall. In the case of the PC droplets, phase separation was completed only for the smaller droplets, wherein the microgel partially wetted the PC membrane and had a hemisphere shape. In addition, the temperature decrease below the gelation point increased the interfacial tension between the PEG/gelatin phases and triggered a dewetting transition. Interestingly, the accompanying shape deformation to minimize the interfacial area was only observed for the smaller PC droplets. The critical size decreased as the gelatin concentration increased, indicating the role of the gel elasticity as an inhibitor of the deformation. Furthermore, variously patterned microgels with spherically asymmetric shapes, such as discs and stars, were produced as kinetically trapped states by regulating the incubation time, polymer composition, and droplet size. These findings demonstrate a way to regulate the complex shapes of microgels using the interplay among phase separation, wetting, and gelation of confined polymer blends in microdroplets.

miktoarm polymer: controlled synthesis, characterization, and application as anticancer drug carrier

NASA Astrophysics Data System (ADS)

Lin, Wenjing; Nie, Shuyu; Xiong, Di; Guo, Xindong; Wang, Jufang; Zhang, Lijuan

2014-05-01

Amphiphilic A2(BC)2 miktoarm star polymers [poly(ɛ-caprolactone)]2-[poly(2-(diethylamino)ethyl methacrylate)- b- poly(poly(ethylene glycol) methyl ether methacrylate)]2 [(PCL)2(PDEA- b-PPEGMA)2] were developed by a combination of ring opening polymerization (ROP) and continuous activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The critical micelle concentration (CMC) values were extremely low (0.0024 to 0.0043 mg/mL), depending on the architecture of the polymers. The self-assembled empty and doxorubicin (DOX)-loaded micelles were spherical in morphologies, and the average sizes were about 63 and 110 nm. The release of DOX at pH 5.0 was much faster than that at pH 6.5 and pH 7.4. Moreover, DOX-loaded micelles could effectively inhibit the growth of cancer cells HepG2 with IC50 of 2.0 μg/mL. Intracellular uptake demonstrated that DOX was delivered into the cells effectively after the cells were incubated with DOX-loaded micelles. Therefore, the pH-sensitive (PCL)2(PDEA- b-PPEGMA)2 micelles could be a prospective candidate as anticancer drug carrier for hydrophobic drugs with sustained release behavior.

Dynamics of micelle-nanoparticle systems undergoing shear. A coarse-grained molecular dynamics approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rolfe, Bryan A.; Chun, Jaehun; Joo, Yong L.

2013-09-05

Recent experimental work has shown that polymeric micelles can template nanoparticles via interstitial sites in shear-ordered micelle solutions. In the current study, we report simulation results based on a coarse-grained molecular dynamics (CGMD) model of a solvent/polymer/nanoparticle system. Our results demonstrate the importance of polymer concentration and the micelle corona length in 2D shear-ordering of neat block copolymer solutions. Although our results do not show strong 3D ordering during shear, we find that cessation of shear allows the system to relax into a 3D configuration of greater order than without shear. It is further shown that this post-shear relaxation ismore » strongly dependent on the length of the micelle corona. For the first time, we demonstrate the presence and importance of a flow disturbance surrounding micelles in simple shear flow at moderate Péclet numbers. This disturbance is similar to what is observed around simulated star polymers and ellipsoids. The extent of the flow disturbance increases as expected with a longer micelle corona length. It is further suggested that without proper consideration of these dynamics, a stable nanoparticle configuration would be difficult to obtain.« less

Industrial dual arm robot manipulator for precise assembly of mechanical parts

NASA Astrophysics Data System (ADS)

Park, Chanhun; Kim, Doohyung; Park, Kyoungtaik; Choi, Youngjin

2007-12-01

A new structure of dual arm robot manipulator which consists of two industrial 6-DOF arms and one 2-DOF Torso is introduced. Each industrial 6-DOF arm is able to be used as a stand-alone industrial 6-DOF robot manipulator and as a part of dual arm manipulator at the same time. These structures help the robot maker which is willing to succeed in the emerging dual arm robot market in order to have high competition for the current industrial robot market at same time. Self-collision detection algorithm for multi-arm robot and kinematics algorithms for the developed dual arm robot manipulator which are implemented in our controller are introduced.

Controlling multiple manipulators using RIPS

NASA Technical Reports Server (NTRS)

Wang, Yulun; Jordan, Steve; Mangaser, Amante; Butner, Steve

1989-01-01

A prototype of the RIPS architecture (Robotic Instruction Processing System) was developed. A two arm robot control experiment is underway to characterize the architecture as well as research multi-arm control. This experiment uses two manipulators to cooperatively position an object. The location of the object is specified by the host computer's mouse. Consequently, real time kinematics and dynamics are necessary. The RIPS architecture is specialized so that it can satisfy these real time constraints. The two arm experimental set-up is discussed. A major part of this work is the continued development of a good programming environment for RIPS. The C++ language is employed and favorable results exist in the targeting of this language to the RIPS hardware.

Chiral organosilica particles and their use as inducers of conformational deracemization of liquid crystal phases

NASA Astrophysics Data System (ADS)

Cohen, Orit; Ferris, Andrew J.; Adkins, Raymond; Lemieux, Robert P.; Avnir, David; Gelman, Dmitri; Rosenblatt, Charles

2018-03-01

Chiral organosilica particles of size ∼200 nm were synthesized from an enantio-pure multi-armed chiral D-maltose organosilane precursor in the absence of co-condensation with an achiral monomer. Two distinct experiments were performed to demonstrate the particles' ability to induce conformational deracemization of a host liquid crystal. The first involves an electric field-induced tilt of the liquid crystal director in the deracemized smectic-A phase. The other involves domain wall curvature separating left- and right-handed liquid crystal helical pitch domains imposed by the cells' substrates. The results demonstrate unequivocally that enantio-pure organosilica nanoparticles can be synthesized and can induce chirality in a host.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

Star-shaped polymers of bio-inspired algae core and poly(acrylamide) and poly(acrylic acid) as arms in dissolution of silica/silicate.

PubMed

Chauhan, Kalpana; Patiyal, Priyanka; Chauhan, Ghanshyam S; Sharma, Praveen

2014-06-01

Silica, in natural waters (due to weathering of rocks) decreases system performance in water processing industry due to scaling. In view of that, the present work involves the synthesis of novel green star shaped additives of algae core (a bio-inspired material as diatom maintains silicic acid equilibrium in sea water) as silica polymerization inhibitors. Star shaped materials with bio-inspired core and poly(acrylamide) [poly(AAm)] and poly(acrylic acid) [poly(AAc)] arms were synthesized by economical green approach. The proficiency was evaluated in 'mini lab' scale for the synthesized APAAm (Algae-g-poly(AAm)) and APAAc (Algae-g-poly(AAc)) dendrimers (star shaped) in colloidal silica mitigation/inhibition at 35 °C and 55 °C. Synthesized dendrimers were equally proficient in silica inhibition at 12 h and maintains ≥450 ppm soluble silica. However, APAAm dendrimers of generation 0 confirmed better results (≈300 ppm) in contrast to APAAc dendrimers in silica inhibition at 55 °C. Additionally, dendrimers also worked as a nucleator for heterogeneous polymerization to inhibit silica homo-polymerization. APAAm dendrimer test set showed no silica deposit for more than 10 days of inhibition. EDX characterization results support nucleator mechanism with Si content of 6.97%-10.98% by weight in silica deposits (SiO2-APAAm dendrimer composites). Copyright © 2014 Elsevier Ltd. All rights reserved.

Instrumental research of lithodynamic processes in estuaries of the White Sea

NASA Astrophysics Data System (ADS)

Rimsky-Korsakov, Nikolai; Korotaev, Vladislav; Ivanov, Vadim

2017-04-01

The report provides a comparative analysis of morphological lithodynamic processes in estuaries and river deltas on the basis of 2013-2015 field geophysical and hydrographic surveys held by IO RAS and MSU. Studies performed using side scan sonar (Imagenex YellowFin SSS), bathymetric (FortXXI Scat Echo sounder) and navigation (DGPS/GLONASS Sigma Ashtek receiver) equipment. North Dvina modern delta can be classified as multi-arm delta estuary lagoon performance. Areas of modern river waters occupy a large accumulation of deltaic arms. It formed a young island with elevations of about 1 m. The islands are composed of river alluvium and annually flooded during the flood period. Onega river mouth area is unique due to the specific geological conditions. Short, wellhead site is the cause of the anomalous attenuation of the tidal wave and the limited range of penetration of salt water seashore only to Kokorinskogo threshold. Morphological lithodynamic processes in high tide Mezen estuaries (syzygy - 8.5 m) are caused by tidal currents, river runoff, wind waves and sediment longshore drift. Due to the movement of huge masses of sediment in the Mezen estuary occur intense deformation silty-sand banks, reshaping of the bottom channel trenches and displacement of navigable waterways. Thus, the specificity of the morphological lithodynamic processes in high tidal estuaries is a lack of modern delta, the development of mobile local sediment structures inside the estuary and the formation of a broad mouth bar on the open wellhead coast. In multi-arm deltas an intense process of increasing marine edge of the delta is observed due to wellhead delta arms elongation and the formation of small estuarine bars at the mouths of the underwater channel trenches coming out into the open coast. Simultaneously, the process of filling the river sediments of residual waters within the subaerial delta and the formation of marine coastal bars on the outer perimeter edge of the sea ground delta.

Multi-arm group sequential designs with a simultaneous stopping rule.

PubMed

Urach, S; Posch, M

2016-12-30

Multi-arm group sequential clinical trials are efficient designs to compare multiple treatments to a control. They allow one to test for treatment effects already in interim analyses and can have a lower average sample number than fixed sample designs. Their operating characteristics depend on the stopping rule: We consider simultaneous stopping, where the whole trial is stopped as soon as for any of the arms the null hypothesis of no treatment effect can be rejected, and separate stopping, where only recruitment to arms for which a significant treatment effect could be demonstrated is stopped, but the other arms are continued. For both stopping rules, the family-wise error rate can be controlled by the closed testing procedure applied to group sequential tests of intersection and elementary hypotheses. The group sequential boundaries for the separate stopping rule also control the family-wise error rate if the simultaneous stopping rule is applied. However, we show that for the simultaneous stopping rule, one can apply improved, less conservative stopping boundaries for local tests of elementary hypotheses. We derive corresponding improved Pocock and O'Brien type boundaries as well as optimized boundaries to maximize the power or average sample number and investigate the operating characteristics and small sample properties of the resulting designs. To control the power to reject at least one null hypothesis, the simultaneous stopping rule requires a lower average sample number than the separate stopping rule. This comes at the cost of a lower power to reject all null hypotheses. Some of this loss in power can be regained by applying the improved stopping boundaries for the simultaneous stopping rule. The procedures are illustrated with clinical trials in systemic sclerosis and narcolepsy. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd.

Unimolecular Micelles of Amphiphilic Cyclodextrin-Core Star-Like Copolymers with Covalent pH-Responsive Linkage of Anticancer Prodrugs.

PubMed

Jia, Tao; Huang, Shuo; Yang, Cangjie; Wang, Mingfeng

2017-08-07

Multifunctional stable and stimuli-responsive drug delivery systems are important for efficient cancer treatment due to their advantages such as enhanced cancer-targeting efficiency, improved pharmacokinetics, minimized drug leaching, and reduced undesirable side effects. Here we report a robust and pH-responsive anticancer drug delivery system based on unimolecular micelles of star-like amphiphilic copolymers. The polymers (denoted as CPOFs) were facilely synthesized via one-step atom transfer radical polymerization of functionalizable benzoaldehyde and hydrophilic poly[(oligo ethylene glycol) methyl ether methacrylate] as comonomers from the core of heptakis [2,3,6-tri-o-(2-bromo-2-methyl propionyl]-β-cyclodextrin as the initiator. Doxorubicin (DOX) as an anticancer drug was covalently linked to the benzoaldehyde groups of CPOFs through pH-sensitive Schiff-base bonds. The DOX-conjugated polymers, denoted as CPOF-DOX, formed robust unimolecular micelles with an average diameter of 18 nm in aqueous media. More importantly, these unimolecular micelles showed higher drug loading capacity and more controllable drug release characteristics, compared to our previous unimolecular micelles of β-cyclodextrin-poly(lactic acid)-b-poly[(oligo ethylene glycol) methyl ether methacrylates] that physically encapsulated DOX via hydrophobic interaction. Moreover, the CPOF-DOX unimolecular micelles could be internalized by human cervical cancer HeLa cells in a stepwise way and showed less cytotoxicity compared to carrier-free DOX. We foresee that CPOF-DOX would provide a promising robust and controllable anticancer drug delivery system for future animal study and clinical trials for cancer treatment.

Comparison of the cellular transport mechanism of cationic, star-shaped polymers and liposomes in HaCat cells.

PubMed

Luo, Heng-Cong; Li, Na; Yan, Li; Mai, Kai-Jin; Sun, Kan; Wang, Wei; Lao, Guo-Juan; Yang, Chuan; Zhang, Li-Ming; Ren, Meng

2017-01-01

Several biological barriers must be overcome to achieve efficient nonviral gene delivery. These barriers include target cell uptake, lysosomal degradation, and dissociation from the carrier. In this study, we compared the differences in the uptake mechanism of cationic, star-shaped polymer/MMP-9siRNA complexes (β-CD-(D3)7/MMP-9siRNA complexes: polyplexes) and commercial liposome/MMP-9siRNA complexes (Lipofectamine ® 2000/MMP-9siRNA complexes: liposomes). The uptake pathway and transfection efficiency of the polyplexes and liposomes were determined by fluorescence microscopy, flow cytometry, and reverse transcriptase-polymerase chain reaction. The occurrence of intracellular processing was assessed by confocal laser scanning microscopy. Endosomal acidification inhibitors were used to explore the endosomal escape mechanisms of the polyplexes and lysosomes. We concluded that the polyplexes were internalized by non-caveolae- and non-clathrin-mediated pathways, with no lysosomal trafficking, thereby inducing successful transfection, while the majority of liposomes were internalized by clathrin-dependent endocytosis (CDE), caveolae-mediated endocytosis, and macropinocytosis, and only CDE induced successful transfection. Liposomes might escape more quickly than polyplexes, and the digestion effect of acidic organelles on liposomes was faint compared to the polyplexes, although both complexes escaped from endolysosomes via the proton sponge mechanism. This may be the key aspect that leads to the lower transfection efficiency of the β-CD-(D3)7/MMP-9siRNA complexes. The present study may offer some insights for the rational design of novel delivery systems with increased transfection efficiency but decreased toxicity.

Designing Drug Conjugates Based on Sugar Decorated V-Shape and Star Polymethacrylates: Influence of Composition and Architecture of Polymeric Carrier.

PubMed

Mielańczyk, Anna; Neugebauer, Dorota

2015-12-16

Amphiphilic ethylenediamine (EDA)-functionalized V-shape and star copolymers with centrally placed methyl-α,D-glucopyranoside were designed as nanocarriers. Anticancer doxorubicin (DOX) was conjugated in water via amine groups in copolymers to form ketimine linkers. Variations of arm length and number (40-65 units per arm and 2 vs 3 vs 4 arms), DOX feed amount, and conjugation site content (50-160 units of EDA groups), as responsible for efficiency of drug attachment (10-60 units of conjugated DOX) and its release at various pH (5.0 vs 7.4), were studied to demonstrate potential for drug delivery. Size of conjugate particles (10-195 nm) formed in aqueous solution was strongly dependent on the polymer composition and topology. The broad range of drug amounts (25-95%) were detected by the precipitation method, showing pH sensitivity by some polymeric conjugates with faster DOX release in acidic conditions.

Effect of molecular topology on the transport properties of dendrimers in dilute solution at Θ temperature: A Brownian dynamics study

NASA Astrophysics Data System (ADS)

Bosko, Jaroslaw T.; Ravi Prakash, J.

2008-01-01

Structure and transport properties of dendrimers in dilute solution are studied with the aid of Brownian dynamics simulations. To investigate the effect of molecular topology on the properties, linear chain, star, and dendrimer molecules of comparable molecular weights are studied. A bead-spring chain model with finitely extensible springs and fluctuating hydrodynamic interactions is used to represent polymer molecules under Θ conditions. Structural properties as well as the diffusivity and zero-shear-rate intrinsic viscosity of polymers with varied degrees of branching are analyzed. Results for the free-draining case are compared to and found in very good agreement with the Rouse model predictions. Translational diffusivity is evaluated and the difference between the short-time and long-time behavior due to dynamic correlations is observed. Incorporation of hydrodynamic interactions is found to be sufficient to reproduce the maximum in the intrinsic viscosity versus molecular weight observed experimentally for dendrimers. Results of the nonequilibrium Brownian dynamics simulations of dendrimers and linear chain polymers subjected to a planar shear flow in a wide range of strain rates are also reported. The flow-induced molecular deformation of molecules is found to decrease hydrodynamic interactions and lead to the appearance of shear thickening. Further, branching is found to suppress flow-induced molecular alignment and deformation.

pH-responsive micelles based on (PCL)2(PDEA-b-PPEGMA)2 miktoarm polymer: controlled synthesis, characterization, and application as anticancer drug carrier.

PubMed

Lin, Wenjing; Nie, Shuyu; Xiong, Di; Guo, Xindong; Wang, Jufang; Zhang, Lijuan

2014-01-01

Amphiphilic A2(BC)2 miktoarm star polymers [poly(ϵ-caprolactone)]2-[poly(2-(diethylamino)ethyl methacrylate)-b- poly(poly(ethylene glycol) methyl ether methacrylate)]2 [(PCL)2(PDEA-b-PPEGMA)2] were developed by a combination of ring opening polymerization (ROP) and continuous activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The critical micelle concentration (CMC) values were extremely low (0.0024 to 0.0043 mg/mL), depending on the architecture of the polymers. The self-assembled empty and doxorubicin (DOX)-loaded micelles were spherical in morphologies, and the average sizes were about 63 and 110 nm. The release of DOX at pH 5.0 was much faster than that at pH 6.5 and pH 7.4. Moreover, DOX-loaded micelles could effectively inhibit the growth of cancer cells HepG2 with IC50 of 2.0 μg/mL. Intracellular uptake demonstrated that DOX was delivered into the cells effectively after the cells were incubated with DOX-loaded micelles. Therefore, the pH-sensitive (PCL)2(PDEA-b-PPEGMA)2 micelles could be a prospective candidate as anticancer drug carrier for hydrophobic drugs with sustained release behavior.

Three coordination polymers based on a star-like geometry 4, 4', 4'' -nitrilotribenzoic acid ligand and their framework dependent luminescent properties

NASA Astrophysics Data System (ADS)

Hu, Zhiyong; Zhao, Meng; Su, Jian; Xu, Shasha; Hu, Lei; Liu, Hui; Zhang, Qiong; Zhang, Jun; Wu, Jieying; Tian, Yupeng

2018-02-01

Three novel coordination polymers, [Zn(μ2-HTCA)(Phen)]n (1), {[Cd(μ3-HTCA)(Phen)]·2H2O}n (2), [Mn(μ2-HTCA)(Phen)(H2O)]n (3) were prepared by hydrothermal synthesis from the 4, 4', 4''-nitrilotribenzoicacid (H3TCA) and 1, 10-phenanthroline monohydrate (Phen) with different transition metal salts, which were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray diffraction and thermogravimetric analysis. The photophysical properties of the complexes were investigated by solid-state diffuse reflectance spectra, photoluminescent properties, lifetime and quantum yield. For these complexes, it was found that the band gaps follow the order: 3 ＜ 2 ＜ 1 ＜ 2.80 eV, fluorescence intensity order: 1 ＞ H3TCA ＞ 2 ＞ 3; quantum yield order: H3TCA ＞ 1 ＞ 2 ＞ 3; while the lifetime order: 1 ＞ 2 ＞ H3TCA ＞ 3.

The Curious Case of Fluorination of Conjugated Polymers for Solar Cells.

PubMed

Zhang, Qianqian; Kelly, Mary Allison; Bauer, Nicole; You, Wei

2017-09-19

Organic solar cells (OSCs) have been a rising star in the field of renewable energy since the introduction of the bulk heterojunction (BHJ) in 1992. Recent advances have pushed the efficiencies of OSCs to over 13%, an impressive accomplishment via collaborative efforts in rational materials design and synthesis, careful device engineering, and fundamental understanding of device physics. Throughout these endeavors, several design principles for the conjugated donor polymers used in such solar cells have emerged, including optimizing the conjugated backbone with judicious selection of building blocks, side-chain engineering, and substituents. Among all of the substituents, fluorine is probably the most popular one; improved device characteristics with fluorination have frequently been reported for a wide range of conjugated polymers, in particular, donor-acceptor (D-A)-type polymers. Herein we examine the effect of fluorination on the device performance of solar cells as a function of the position of fluorination (on the acceptor unit or on the donor unit), aiming to outline a clear understanding of the benefits of this curious substituent. As fluorination of the acceptor unit is the most adopted strategy for D-A polymers, we first discuss the effect of fluorination of the acceptor units, highlighting the five most widely utilized acceptor units. While improved device efficiency has been widely observed with fluorinated acceptor units, the underlying reasons vary from case to case and highly depend on the chemical structure of the polymer. Second, the effect of fluorination of the donor unit is addressed. Here we focus on four donor units that have been most studied with fluorination. While device-performance-enhancing effects by fluorination of the donor units have also been observed, it is less clear that fluorine will always benefit the efficiency of the OSC, as there are several cases where the efficiency drops, in particular with "over-fluorination", i.e., when too many fluorine substituents are incorporated. Finally, while this Account focuses on studies in which the polymer is paired with fullerene derivatives as the electron accepting materials, non-fullerene acceptors (NFAs) are quickly becoming key players in the field of OSCs. The effect of fluorination of the polymers on the device performance may be different when NFAs are used as the electron-accepting materials, which remains to be investigated. However, the design of fluorinated polymers may provide guidelines for the design of more efficient NFAs. Indeed, the current highest-performing OSC (∼13%) features fluorination on both the donor polymer and the non-fullerene acceptor.

Modeling steady-state dynamics of macromolecules in exponential-stretching flow using multiscale molecular-dynamics-multiparticle-collision simulations.

PubMed

Ghatage, Dhairyasheel; Chatterji, Apratim

2013-10-01

We introduce a method to obtain steady-state uniaxial exponential-stretching flow of a fluid (akin to extensional flow) in the incompressible limit, which enables us to study the response of suspended macromolecules to the flow by computer simulations. The flow field in this flow is defined by v(x) = εx, where v(x) is the velocity of the fluid and ε is the stretch flow gradient. To eliminate the effect of confining boundaries, we produce the flow in a channel of uniform square cross section with periodic boundary conditions in directions perpendicular to the flow, but simultaneously maintain uniform density of fluid along the length of the tube. In experiments a perfect elongational flow is obtained only along the axis of symmetry in a four-roll geometry or a filament-stretching rheometer. We can reproduce flow conditions very similar to extensional flow near the axis of symmetry by exponential-stretching flow; we do this by adding the right amounts of fluid along the length of the flow in our simulations. The fluid particles added along the length of the tube are the same fluid particles which exit the channel due to the flow; thus mass conservation is maintained in our model by default. We also suggest a scheme for possible realization of exponential-stretching flow in experiments. To establish our method as a useful tool to study various soft matter systems in extensional flow, we embed (i) spherical colloids with excluded volume interactions (modeled by the Weeks-Chandler potential) as well as (ii) a bead-spring model of star polymers in the fluid to study their responses to the exponential-stretched flow and show that the responses of macromolecules in the two flows are very similar. We demonstrate that the variation of number density of the suspended colloids along the direction of flow is in tune with our expectations. We also conclude from our study of the deformation of star polymers with different numbers of arms f that the critical flow gradient ε(c) at which the star undergoes the coil-to-stretch transition is independent of f for f = 2,5,10, and 20.

Bile Acid-Based Drug Delivery Systems for Enhanced Doxorubicin Encapsulation: Comparing Hydrophobic and Ionic Interactions in Drug Loading and Release.

PubMed

Cunningham, Alexander J; Robinson, Mattieu; Banquy, Xavier; Leblond, Jeanne; Zhu, X X

2018-03-05

Doxorubicin (Dox) is a drug of choice in the design of drug delivery systems directed toward breast cancers, but is often limited by loading and control over its release from polymer micelles. Bile acid-based block copolymers present certain advantages over traditional polymer-based systems for drug delivery purposes, since they can enable a higher drug loading via the formation of a reservoir through their aggregation process. In this study, hydrophobic and electrostatic interactions are compared for their influence on Dox loading inside cholic acid based block copolymers. Poly(allyl glycidyl ether) (PAGE) and poly(ethylene glycol) (PEG) were grafted from the cholic acid (CA) core yielding a star-shaped block copolymer with 4 arms (CA-(PAGE- b-PEG) 4 ) and then loaded with Dox via a nanoprecipitation technique. A high Dox loading of 14 wt % was achieved via electrostatic as opposed to hydrophobic interactions with or without oleic acid as a cosurfactant. The electrostatic interactions confer a pH responsiveness to the system. 50% of the loaded Dox was released at pH 5 in comparison to 12% at pH 7.4. The nanoparticles with Dox loaded via hydrophobic interactions did not show such a pH responsiveness. The systems with Dox loaded via electrostatic interactions showed the lowest IC 50 and highest cellular internalization, indicating the pre-eminence of this interaction in Dox loading. The blank formulations are biocompatible and did not show cytotoxicity up to 0.17 mg/mL. The new functionalized star block copolymers based on cholic acid show great potential as drug delivery carriers.

Method and apparatus for hybrid position/force control of multi-arm cooperating robots

NASA Technical Reports Server (NTRS)

Hayati, Samad A. (Inventor)

1989-01-01

Two or more robotic arms having end effectors rigidly attached to an object to be moved are disclosed. A hybrid position/force control system is provided for driving each of the robotic arms. The object to be moved is represented as having a total mass that consists of the actual mass of the object to be moved plus the mass of the moveable arms that are rigidly attached to the moveable object. The arms are driven in a positive way by the hybrid control system to assure that each arm shares in the position/force applied to the object. The burden of actuation is shared by each arm in a non-conflicting way as the arm independently control the position of, and force upon, a designated point on the object.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Chi; Arvapally, Ravi K.; Tekarli, Sammer M.

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

A control approach for robots with flexible links and rigid end-effectors

NASA Technical Reports Server (NTRS)

Barbieri, Enrique; Ozguner, Umit

1989-01-01

Multiarm flexible robots with dexterous end effectors are currently being considered in such tasks as satellite retrieval, servicing and repair where a two phase problem can be identified: Phase 1, robot positioning in space; Phase 2, object retrieval. Some issues in Phase 1 regarding modelling and control strategies for a robotic system comprised of along flexible arm and a rigid three-link end effector are presented. The control objective is to maintain the last (rigid) link stationary in space in the presence of an additive disturbance caused by the flexible energy in the first link after a positioning maneuver has been accomplished. Several configuration strategies can be considered, and optimal decentralized servocompensators can be designed. Preliminary computer simulations are included for a simple proportional controller to illustrate the approach.

Synthesis and Performance of Highly Stable Star-Shaped Polyaniline Electrochromic Materials with Triphenylamine Core

NASA Astrophysics Data System (ADS)

Xiong, Shanxin; Li, Shuaishuai; Zhang, Xiangkai; Wang, Ru; Zhang, Runlan; Wang, Xiaoqin; Wu, Bohua; Gong, Ming; Chu, Jia

2018-02-01

The molecular architecture of conducting polymers has a significant impact on their conjugated structure and electrochemical properties. We have investigated the influence of star-shaped structure on the electrochemical and electrochromic properties of polyaniline (PANI). Star-shaped PANI (SPANI) was prepared by copolymerization of aniline with triphenylamine (TPA) using an emulsion polymerization method. With addition of less than 4.0 mol.% TPA, the resulting SPANI exhibited good solubility in xylene with dodecylbenzenesulfonic acid (DBSA) as doping acid. The structure and thermal stability of the SPANI were characterized using Fourier-transform infrared spectroscopy, Raman spectroscopy, and thermogravimetric analysis, and the electrochemical behavior was analyzed by cyclic voltammetry (CV). The electrochromic properties of SPANI were tested using an electrochemical workstation combined with an ultraviolet-visible (UV-Vis) spectrometer. The results show that, with increasing TPA loading, the thermal stability of SPANI increased. With addition of 4.0 mol.% TPA, the weight loss of SPANI was 36.9% at 700°C, much lower than the value of 71.2% for PANI at the same temperature. The low oxidation potential and large enclosed area of the CV curves indicate that SPANI possesses higher electrochemical activity than PANI. Enhanced electrochromic properties including higher optical contrast and better electrochromic stability of SPANI were also obtained. SPANI with 1.6 mol.% TPA loading exhibited the highest optical contrast of 0.71, higher than the values of 0.58 for PANI, 0.66 for SPANI-0.4%, or 0.63 for SPANI-4.0%. Overdosing of TPA resulted in slow switching speed due to slow ion transport in short branched chains of star-shaped PANI electrochromic material. Long-term stability testing confirmed that all the SPANI-based devices exhibited better stability than the PANI-based device.

Adding Celecoxib With or Without Zoledronic Acid for Hormone-Naïve Prostate Cancer: Long-Term Survival Results From an Adaptive, Multiarm, Multistage, Platform, Randomized Controlled Trial

PubMed Central

Mason, Malcolm D.; Clarke, Noel W.; James, Nicholas D.; Dearnaley, David P.; Spears, Melissa R.; Ritchie, Alastair W.S.; Attard, Gerhardt; Cross, William; Jones, Rob J.; Parker, Christopher C.; Russell, J. Martin; Thalmann, George N.; Schiavone, Francesca; Cassoly, Estelle; Matheson, David; Millman, Robin; Rentsch, Cyrill A.; Barber, Jim; Gilson, Clare; Ibrahim, Azman; Logue, John; Lydon, Anna; Nikapota, Ashok D.; O’Sullivan, Joe M.; Porfiri, Emilio; Protheroe, Andrew; Srihari, Narayanan Nair; Tsang, David; Wagstaff, John; Wallace, Jan; Walmsley, Catherine; Parmar, Mahesh K.B.; Sydes, Matthew R.

2017-01-01

Purpose Systemic Therapy for Advanced or Metastatic Prostate Cancer: Evaluation of Drug Efficacy is a randomized controlled trial using a multiarm, multistage, platform design. It recruits men with high-risk, locally advanced or metastatic prostate cancer who were initiating long-term hormone therapy. We report survival data for two celecoxib (Cel)-containing comparisons, which stopped accrual early at interim analysis on the basis of failure-free survival. Patients and Methods Standard of care (SOC) was hormone therapy continuously (metastatic) or for ≥ 2 years (nonmetastatic); prostate (± pelvic node) radiotherapy was encouraged for men without metastases. Cel 400 mg was administered twice a day for 1 year. Zoledronic acid (ZA) 4 mg was administered for six 3-weekly cycles, then 4-weekly for 2 years. Stratified random assignment allocated patients 2:1:1 to SOC (control), SOC + Cel, or SOC + ZA + Cel. The primary outcome measure was all-cause mortality. Results were analyzed with Cox proportional hazards and flexible parametric models adjusted for stratification factors. Results A total of 1,245 men were randomly assigned (Oct 2005 to April 2011). Groups were balanced: median age, 65 years; 61% metastatic, 14% N+/X M0, 25% N0M0; 94% newly diagnosed; median prostate-specific antigen, 66 ng/mL. Median follow-up was 69 months. Grade 3 to 5 adverse events were seen in 36% SOC-only, 33% SOC + Cel, and 32% SOC + ZA + Cel patients. There were 303 control arm deaths (83% prostate cancer), and median survival was 66 months. Compared with SOC, the adjusted hazard ratio was 0.98 (95% CI, 0.80 to 1.20; P = .847; median survival, 70 months) for SOC + Cel and 0.86 (95% CI, 0.70 to 1.05; P =.130; median survival, 76 months) for SOC + ZA + Cel. Preplanned subgroup analyses in men with metastatic disease showed a hazard ratio of 0.78 (95% CI, 0.62 to 0.98; P = .033) for SOC + ZA + Cel. Conclusion These data show no overall evidence of improved survival with Cel. Preplanned subgroup analyses provide hypotheses for future studies. PMID:28300506

Adding Celecoxib With or Without Zoledronic Acid for Hormone-Naïve Prostate Cancer: Long-Term Survival Results From an Adaptive, Multiarm, Multistage, Platform, Randomized Controlled Trial.

PubMed

Mason, Malcolm D; Clarke, Noel W; James, Nicholas D; Dearnaley, David P; Spears, Melissa R; Ritchie, Alastair W S; Attard, Gerhardt; Cross, William; Jones, Rob J; Parker, Christopher C; Russell, J Martin; Thalmann, George N; Schiavone, Francesca; Cassoly, Estelle; Matheson, David; Millman, Robin; Rentsch, Cyrill A; Barber, Jim; Gilson, Clare; Ibrahim, Azman; Logue, John; Lydon, Anna; Nikapota, Ashok D; O'Sullivan, Joe M; Porfiri, Emilio; Protheroe, Andrew; Srihari, Narayanan Nair; Tsang, David; Wagstaff, John; Wallace, Jan; Walmsley, Catherine; Parmar, Mahesh K B; Sydes, Matthew R

2017-05-10

Purpose Systemic Therapy for Advanced or Metastatic Prostate Cancer: Evaluation of Drug Efficacy is a randomized controlled trial using a multiarm, multistage, platform design. It recruits men with high-risk, locally advanced or metastatic prostate cancer who were initiating long-term hormone therapy. We report survival data for two celecoxib (Cel)-containing comparisons, which stopped accrual early at interim analysis on the basis of failure-free survival. Patients and Methods Standard of care (SOC) was hormone therapy continuously (metastatic) or for ≥ 2 years (nonmetastatic); prostate (± pelvic node) radiotherapy was encouraged for men without metastases. Cel 400 mg was administered twice a day for 1 year. Zoledronic acid (ZA) 4 mg was administered for six 3-weekly cycles, then 4-weekly for 2 years. Stratified random assignment allocated patients 2:1:1 to SOC (control), SOC + Cel, or SOC + ZA + Cel. The primary outcome measure was all-cause mortality. Results were analyzed with Cox proportional hazards and flexible parametric models adjusted for stratification factors. Results A total of 1,245 men were randomly assigned (Oct 2005 to April 2011). Groups were balanced: median age, 65 years; 61% metastatic, 14% N+/X M0, 25% N0M0; 94% newly diagnosed; median prostate-specific antigen, 66 ng/mL. Median follow-up was 69 months. Grade 3 to 5 adverse events were seen in 36% SOC-only, 33% SOC + Cel, and 32% SOC + ZA + Cel patients. There were 303 control arm deaths (83% prostate cancer), and median survival was 66 months. Compared with SOC, the adjusted hazard ratio was 0.98 (95% CI, 0.80 to 1.20; P = .847; median survival, 70 months) for SOC + Cel and 0.86 (95% CI, 0.70 to 1.05; P =.130; median survival, 76 months) for SOC + ZA + Cel. Preplanned subgroup analyses in men with metastatic disease showed a hazard ratio of 0.78 (95% CI, 0.62 to 0.98; P = .033) for SOC + ZA + Cel. Conclusion These data show no overall evidence of improved survival with Cel. Preplanned subgroup analyses provide hypotheses for future studies.

Azide/alkyne-"click"-reactions of encapsulated reagents: toward self-healing materials.

PubMed

Gragert, Maria; Schunack, Marlen; Binder, Wolfgang H

2011-03-02

The successful encapsulation of reactive components for the azide/alkyne-"click"-reaction is reported featuring for the first time the use of a liquid polymer as reactive component. A liquid, azido-telechelic three-arm star poly(isobutylene) (M(n) = 3900 g · mol⁻¹) as well as trivalent alkynes were encapsulated into micron-sized capsules and embedded into a polymer-matrix (high-molecular weight poly(isobutylene), M(n) = 250,000 g · mol⁻¹). Using (Cu(I)Br(PPh₃)₃) as catalyst for the azide/alkyne-"click"-reaction, crosslinking of the two components at 40 °C is observed within 380 min and as fast as 10 min at 80 °C. Significant recovery of the tensile storage modulus was observed in a material containing 10 wt.-% and accordingly 5 wt.-% capsules including the reactive components within 5 d at room temperature, thus proving a new concept for materials with self-healing properties. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of complex macromolecular architectures for advanced microelectronic materials.

PubMed

Hedrick, James L; Magbitang, Teddie; Connor, Eric F; Glauser, Thierry; Volksen, Willi; Hawker, Craig J; Lee, Victor Y; Miller, Robert D

2002-08-02

The distinctive features of well-defined, three-dimensional macromolecules with topologies designed to enhance solubility and amplify end-group functionality facilitated nanophase morphologies in mixtures with organosilicates and ultimately nanoporous organosilicate networks. Novel macromolecular architectures including dendritic and star-shaped polymers and organic nanoparticles were prepared by a modular approach from several libraries of building blocks including various generations of dendritic initiators and dendrons, selectively placed to amplify functionality and/or arm number, coupled with living polymerization techniques. Mixtures of an organosilicate and the macromolecular template were deposited, cured, and the phase separation of the organic component, organized the vitrifying organosilicate into nanostructures. Removal of the sacrificial macromolecular template, also denoted as porogen, by thermolysis, yielded the desired nanoporous organosilicate, and the size scale of phase separation was strongly dependent on the chain topology. These materials were designed for use as interlayer, ultra-low dielectric insulators for on-chip applications with dielectric constant values as low as 1.5. The porogen design, chemistry and role of polymer architecture on hybrid and pore morphology will be emphasized.

Design, synthesis, and characterization of new phosphazene related materials, and study the structure property correlations

NASA Astrophysics Data System (ADS)

Tian, Zhicheng

The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships. Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described. Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique. Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain. Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.). Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.

Three-Dimensional Polypeptide Architectures Through Tandem Catalysis and Click Chemistry

NASA Astrophysics Data System (ADS)

Rhodes, Allison Jane

Rapid renal clearance, liver accumulation, proteolytic degradation and non-specificity are challenges small molecule drugs, peptides, proteins and nucleic acid therapeutics encounter en route to their intended destination within the body. Nanocarriers (i.e. dendritric polymers, vesicles, and micelles) of approximately 100 nm in diameter, shuttle small molecule drugs to their desired location through passive (EPR effect) and active (ligand-mediated) targeting, maximizing therapeutic efficiency. Polypeptide-based polymers are water-soluble, biocompatible, non-toxic and are therefore excellent candidates for nanocarriers. Dendritic polymers, including dendrimers, cylindrical brushes, and star polymers, are the newest class of nanomedicine drug delivery vehicles. The synthesis and characterization of dendritic polymers is challenging, with tedious and costly procedures. Dendritic polymers possess peripheral pendent functional groups that can potentially be used in ligand-mediated drug delivery vehicles and bioimaging applications. More specifically, cylindrical brushes are dendritic polymers where a single linear polymer (primary chain) has polymer chains (secondary chains) grafted to it. Recently, research groups have shown that cylindrical brush polymers are capable of nanoparticle and supramolecular structure self-assembly. The facile preparation of high-density brush copolypeptides by the "grafting from" approach will be discussed. This approach utilizes a novel, tandem catalytic methodology where alloc-alpha-aminoamide groups are installed within the side-chains of the alpha-amino-N-carboxyanhydride (NCA) monomer serving as masked initiators. These groups are inert during cobalt initiated NCA polymerization, and give alloc-alpha-aminoamide substituted polypeptide main-chains. The alloc-alpha-aminoamide groups are activated in situ using nickel to generate initiators for growth of side-chain brush segments. This method proves to be efficient, yielding well-defined, high-density brushes for applications in drug delivery and imaging. Here, we also report a method for the synthesis of soluble, well-defined, azido functionalized polypeptides in a straightforward, 3-step synthesis. Homo and diblock azidopolypeptides were prepared with controlled segment lengths via living polymerization using Co(PMe3)4 initiator. Through copper azide alkyne click chemistry (CuAAC) in organic solvent, azidopolypeptides were regioselectively and quantitatively modified with carboxylic acid (pH-responsive), amino acid and sugar functional groups. Finally, the advances towards well-defined hyperbranched polypeptides through alpha-amino-acid-N-thiocarboxyanhydrides (NTAs) will be discussed. Within the past 10 years, controlled NCA (alpha-amino acid-N-carboxyanhydride) ring-opening polymerization (ROP) has emerged, expanding the application of copolypeptide polymers in various drug delivery and tissue engineering motifs. Modification of NCA monomers to the corresponding alpha-amino-acid-N-thiocarboxyanhydride (NTA) will diversify ROP reactions, leading to more complex polypeptides (such as hyperbranched polymers), in addition to the possibility of performing these polymerizations under ambient conditions, which would greatly expand their potential utility. The project focuses on the preparation of hyperbranched polypeptides with well-defined architectures and controlled branching density in a one-pot reaction. This will be accomplished by taking advantage of the different selectivities of Co(PMe3)4 and depeNi(COD) polymerization initiators, and by exploiting the reactivity difference between NCA and the more stable NTA monomers.

Synthesis and characterization of functionalized methacrylates for coatings and biomedical applications

NASA Astrophysics Data System (ADS)

Shemper, Bianca Sadicoff

The research presented in this dissertation involves the design of polymers for biomaterials and for coatings applications. The development of non-wettable, hard UV-curing, or reactive coatings is discussed. The biomaterials section involves the syntheses of linear and star-like polymers of the functionalized monomer poly(propylene glycol) monomethacrylate (PPGM) via atom transfer radical polymerization (ATRP) (Chapter II). Its copolymerization with a perfluoroalkyl ethyl methacrylate monomer (1H,1H,2H,2H-heptadecafluorodecyl methacrylate) and the syntheses of linear and star-like amphiphilic copolymers containing the fluorinated monomer and poly(ethyleneglycol) methyl ether methacrylate (MPEGMA) are discussed in Chapter III. The four-arm amphiphilic block copolymer obtained showed unique associative properties leading to micellization in selective solvents. Chapter IV includes research involving the design of films with low surface energy by incorporating fluorine into the polymer. The synthesis, characterization and polymerization of a perfluoroalkylether-substituted methacrylic acid (C8F7) are discussed, and the properties of coatings obtained after its photopolymerization on different substrates are evaluated to confirm formation of low-surface energy polymeric coatings. Subsequently, hard coatings based on methyl (alpha-hydroxymethyl)acrylate (MHMA) were prepared via photopolymerization using UV-light. Firstly, mechanistic investigations into the photopolymerization behavior of (alpha-hydroxymethyl)acrylates (RHMA's) are reported (Chapter V). RHMA derivatives were photopolymerized with various multifunctional acrylates and methacrylates and the effect of crosslinker type and degree of functionality on photopolymerization rates and conversions was investigated. Then, in Chapter VI the synthesis of a series of new crosslinkers is described and their photopolymerization kinetics was investigated in bulk. The effect of these novel crosslinkers on the photopolymerization kinetics and coatings properties of MHMA systems is then shown in Chapter VII. This chapter also includes the effect of the presence of synthetic clay in these systems and the preparation of nanocomposite-based films. The final chapter of this dissertation involves the design of reactive coatings for biomedical applications. The syntheses and characterization of novel functionalized methacrylates containing succinimide ester groups susceptible to derivatization with amine-containing species were accomplished. Photopolymerization of these monomers led to formation of hydrogels and derivatization of the hydrogel surfaces with the tripeptide RGD (arginine-glycine-aspartic acid) was successfully achieved.

Origin and evolution of circular waves and spirals in Dictyostelium discoideum territories.

PubMed

Pálsson, E; Cox, E C

1996-02-06

Randomly distributed Dictyostelium discoideum cells form cooperative territories by signaling to each other with cAMP. Cells initiate the process by sending out pulsatile signals, which propagate as waves. With time, circular and spiral patterns form. We show that by adding spatial and temporal noise to the levels of an important regulator of external cAMP levels, the cAMP phosphodiesterase inhibitor, we can explain the natural progression of the system from randomly firing cells to circular waves whose symmetries break to form double- and single- or multi-armed spirals. When phosphodiesterase inhibitor is increased with time, mimicking experimental data, the wavelength of the spirals shortens, and a proportion of them evolve into pairs of connected spirals. We compare these results to recent experiments, finding that the temporal and spatial correspondence between experiment and model is very close.

Stealth properties of poly(ethylene oxide)-based triblock copolymer micelles: a prerequisite for a pH-triggered targeting system.

PubMed

Van Butsele, K; Morille, M; Passirani, C; Legras, P; Benoit, J P; Varshney, S K; Jérôme, R; Jérôme, C

2011-10-01

Evaluation of the biocompatibility of pH-triggered targeting micelles was performed with the goal of studying the effect of a poly(ethylene oxide) (PEO) coating on micelle stealth properties. Upon protonation under acidic conditions, pH-sensitive poly(2-vinylpyridine) (P2VP) blocks were stretched, exhibiting positive charges at the periphery of the micelles as well as being a model targeting unit. The polymer micelles were based on two different macromolecular architectures, an ABC miktoarm star terpolymer and an ABC linear triblock copolymer, which combined three different polymer blocks, i.e. hydrophobic poly(ε-caprolactone), PEO and P2VP. Neutral polymer micelles were formed at physiological pH. These systems were tested for their ability to avoid macrophage uptake, their complement activation and their pharmacological behavior after systemic injection in mice, as a function of their conformation (neutral or protonated). After protonation, complement activation and macrophage uptake were up to twofold higher than for neutral systems. By contrast, when P2VP blocks and the targeting unit were buried by the PEO shell at physiological pH, micelle stealth properties were improved, allowing their future systemic injection with an expected long circulation in blood. Smart systems responsive to pH were thus developed which therefore hold great promise for targeted drug delivery to an acidic tumoral environment. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Crystal-to-Crystal Transition of Ultrasoft Colloids under Shear

NASA Astrophysics Data System (ADS)

Ruiz-Franco, J.; Marakis, J.; Gnan, N.; Kohlbrecher, J.; Gauthier, M.; Lettinga, M. P.; Vlassopoulos, D.; Zaccarelli, E.

2018-02-01

Ultrasoft colloids typically do not spontaneously crystallize, but rather vitrify, at high concentrations. Combining in situ rheo-small-angle-neutron-scattering experiments and numerical simulations we show that shear facilitates crystallization of colloidal star polymers in the vicinity of their glass transition. With increasing shear rate well beyond rheological yielding, a transition is found from an initial bcc-dominated structure to an fcc-dominated one. This crystal-to-crystal transition is not accompanied by intermediate melting but occurs via a sudden reorganization of the crystal structure. Our results provide a new avenue to tailor colloidal crystallization and the crystal-to-crystal transition at the molecular level by coupling softness and shear.

Parametric investigation of scalable tactile sensors

NASA Astrophysics Data System (ADS)

Saadatzi, Mohammad Nasser; Yang, Zhong; Baptist, Joshua R.; Sahasrabuddhe, Ritvij R.; Wijayasinghe, Indika B.; Popa, Dan O.

2017-05-01

In the near future, robots and humans will share the same environment and perform tasks cooperatively. For intuitive, safe, and reliable physical human-robot interaction (pHRI), sensorized robot skins for tactile measurements of contact are necessary. In a previous study, we presented skins consisting of strain gauge arrays encased in silicone encapsulants. Although these structures could measure normal forces applied directly onto the sensing elements, they also exhibited blind spots and response asymmetry to certain loading patterns. This study presents a parametric investigation of piezoresistive polymeric strain gauge that exhibits a symmetric omniaxial response thanks to its novel star-shaped structure. This strain gauge relies on the use of gold micro-patterned star-shaped structures with a thin layer of PEDOT:PSS which is a flexible polymer with piezoresistive properties. In this paper, the sensor is first modeled and comprehensively analyzed in the finite-element simulation environment COMSOL. Simulations include stress-strain loading for a variety of structure parameters such as gauge lengths, widths, and spacing, as well as multiple load locations relative to the gauge. Subsequently, sensors with optimized configurations obtained through simulations were fabricated using cleanroom photolithographic and spin-coating processes, and then experimentally tested. Results show a trend-wise agreement between experiments and simulations.

Formation of gold and silver nanostructures within polyvinylpyrollidone (PVP) gel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan Caixia, E-mail: cxkan@nuaa.edu.c; Wang Changshun; Zhu Jiejun

2010-04-15

Study on reduction of Au(III) and Ag(I) and the formation of Au and Ag nanostructures was performed on the gels of metal precursor and PVP polymer mixture. Some comparing samples were prepared for better understanding the role of reactants on the reduction of metal ions and further growth of nanocrystals. The results suggest that, in addition to its function of generating stable colloids, PVP not only has a reducing effect on metal ions, but also acts as a crystal growth modifier. At low temperatures, the reducing effect of PVP is strong on Ag(I) ions in AgNO{sub 3}, while the reductionmore » of complex Au(III) ions in HAuCl{sub 4} is slow, involving two steps of Au(III)->Au(I)->Au. In the study of temperature disturbance on crystal growth, Au nanoplates of new and well-defined star shape were observed. The differences in the size and shape of nanoparticles are discussed from the colloid chemistry. - Graphical abstract: If a temperature difference was introduced to the gel of Au{sup 3+}(H{sub 2}O)-PVP, large sized Au nanoplates with new and well-defined star shape were observed.« less

Cationic star-shaped polymer as an siRNA carrier for reducing MMP-9 expression in skin fibroblast cells and promoting wound healing in diabetic rats.

PubMed

Li, Na; Luo, Heng-Cong; Yang, Chuan; Deng, Jun-Jie; Ren, Meng; Xie, Xiao-Ying; Lin, Diao-Zhu; Yan, Li; Zhang, Li-Ming

2014-01-01

Excessive expression of matrix metalloproteinase-9 (MMP-9) is deleterious to the cutaneous wound-healing process in the context of diabetes. The aim of the present study was to explore whether a cationic star-shaped polymer consisting of β-cyclodextrin (β-CD) core and poly(amidoamine) dendron arms (β-CD-[D₃]₇) could be used as the gene carrier of small interfering RNA (siRNA) to reduce MMP-9 expression for enhanced diabetic wound healing. The cytotoxicity of β-CD-(D₃)₇ was investigated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay (MMT) method in the rat CRL1213 skin fibroblast cell line. The transfection efficiency of β-CD-(D₃)₇/MMP-9-small interfering RNA (siRNA) complexes was determined by confocal microscopy and flow cytometry. Quantitative real time (RT) polymerase chain reaction was performed to measure the gene expression of MMP-9 after the transfection by β-CD-(D₃)₇/MMP-9-siRNA complexes. The β-CD-(D₃)₇/MMP-9-siRNA complexes were injected on the wounds of streptozocin-induced diabetic rats. Wound closure was measured on days 4 and 7 post-wounding. β-CD-(D₃)₇ exhibited low cytotoxicity in fibroblast cells, and easily formed the complexes with MMP-9-siRNA. The β-CD-(D₃)₇/MMP-9-siRNA complexes were readily taken up by fibroblast cells, resulting in the downregulation of MMP-9 gene expression (P<0.01). Animal experiments revealed that the treatment by β-CD-(D₃)₇/MMP-9-siRNA complexes enhanced wound closure in diabetic rats on day 7 post-wounding (P<0.05). β-CD-(D₃)₇ may be used as an efficient carrier for the delivery of MMP-9-siRNA to reduce MMP-9 expression in skin fibroblast cells and promote wound healing in diabetic rats.

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

NASA Astrophysics Data System (ADS)

Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; von Bojnicic-Kninski, Clemens M.; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A. R.; Breitling, Frank

2016-12-01

Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a ;solid; solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

Patterning highly ordered arrays of complex nanofeatures through EUV directed polarity switching of non chemically amplified photoresist

PubMed Central

Ghosh, Subrata; Satyanarayana, V. S. V.; Pramanick, Bulti; Sharma, Satinder K.; Pradeep, Chullikkattil P.; Morales-Reyes, Israel; Batina, Nikola; Gonsalves, Kenneth E.

2016-01-01

Given the importance of complex nanofeatures in the filed of micro-/nanoelectronics particularly in the area of high-density magnetic recording, photonic crystals, information storage, micro-lens arrays, tissue engineering and catalysis, the present work demonstrates the development of new methodology for patterning complex nanofeatures using a recently developed non-chemically amplified photoresist (n-CARs) poly(4-(methacryloyloxy)phenyl)dimethylsulfoniumtriflate) (polyMAPDST) with the help of extreme ultraviolet lithography (EUVL) as patterning tool. The photosensitivity of polyMAPDST is mainly due to the presence of radiation sensitive trifluoromethanesulfonate unit (triflate group) which undergoes photodegradation upon exposure with EUV photons, and thus brings in polarity change in the polymer structure. Integration of such radiation sensitive unit into polymer network avoids the need of chemical amplification which is otherwise needed for polarity switching in the case of chemically amplified photoresists (CARs). Indeed, we successfully patterned highly ordered wide-raging dense nanofeatures that include nanodots, nanowaves, nanoboats, star-elbow etc. All these developed nanopatterns have been well characterized by FESEM and AFM techniques. Finally, the potential of polyMAPDST has been established by successful transfer of patterns into silicon substrate through adaptation of compatible etch recipes. PMID:26975782

Evaluation of a New Backtrack Free Path Planning Algorithm for Manipulators

NASA Astrophysics Data System (ADS)

Islam, Md. Nazrul; Tamura, Shinsuke; Murata, Tomonari; Yanase, Tatsuro

This paper evaluates a newly proposed backtrack free path planning algorithm (BFA) for manipulators. BFA is an exact algorithm, i.e. it is resolution complete. Different from existing resolution complete algorithms, its computation time and memory space are proportional to the number of arms. Therefore paths can be calculated within practical and predetermined time even for manipulators with many arms, and it becomes possible to plan complicated motions of multi-arm manipulators in fully automated environments. The performance of BFA is evaluated for 2-dimensional environments while changing the number of arms and obstacle placements. Its performance under locus and attitude constraints is also evaluated. Evaluation results show that the computation volume of the algorithm is almost the same as the theoretical one, i.e. it increases linearly with the number of arms even in complicated environments. Moreover BFA achieves the constant performance independent of environments.

Positioning the endoscope in laparoscopic surgery by foot: Influential factors on surgeons' performance in virtual trainer.

PubMed

Abdi, Elahe; Bouri, Mohamed; Burdet, Etienne; Himidan, Sharifa; Bleuler, Hannes

2017-07-01

We have investigated how surgeons can use the foot to position a laparoscopic endoscope, a task that normally requires an extra assistant. Surgeons need to train in order to exploit the possibilities offered by this new technique and safely manipulate the endoscope together with the hands movements. A realistic abdominal cavity has been developed as training simulator to investigate this multi-arm manipulation. In this virtual environment, the surgeon's biological hands are modelled as laparoscopic graspers while the viewpoint is controlled by the dominant foot. 23 surgeons and medical students performed single-handed and bimanual manipulation in this environment. The results show that residents had superior performance compared to both medical students and more experienced surgeons, suggesting that residency is an ideal period for this training. Performing the single-handed task improves the performance in the bimanual task, whereas the converse was not true.

Suppression of turbulence by heterogeneities in a cardiac model with fiber rotation

NASA Astrophysics Data System (ADS)

Zhang, Zhihui; Steinbock, Oliver

2017-09-01

Electrical scroll wave turbulence in human ventricles is associated with ventricular fibrillation and sudden cardiac death. We perform three-dimensional simulations on the basis of the anisotropic Fenton-Karma model and show that macroscopic, insulating heterogeneities (e.g., blood vessels) can cause the spontaneous formation of pinned scroll waves. The wave field of these vortices is periodic, and their frequencies are sufficiently high to push the free, turbulent vortices into the system boundaries where they annihilate. Our study considers cylindrical heterogeneities with radii in the range of 0.1 to 2 cm that extend either in the transmural or a perpendicular direction. Thick cylinders cause the spontaneous formation of multi-armed rotors according to a radius-dependence that is explained in terms of two-dimensional dynamics. For long cylinders, local pinning contacts spread along the heterogeneity by fast and complex self-wrapping.

Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

DOE PAGES

Yang, Chi; Arvapally, Ravi K.; Tekarli, Sammer M.; ...

2015-03-03

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

PIPELINEs: Creating Comparable Clinical Knowledge Efficiently by Linking Trial Platforms

PubMed Central

Shrier, AA; Antonijevic, Z; Beckman, RA; Campbell, RK; Chen, C; Flaherty, KT; Loewy, J; Lacombe, D; Madhavan, S; Selker, HP; Esserman, LJ

2016-01-01

Adaptive, seamless, multisponsor, multitherapy clinical trial designs executed as large scale platforms, could create superior evidence more efficiently than single‐sponsor, single‐drug trials. These trial PIPELINEs also could diminish barriers to trial participation, increase the representation of real‐world populations, and create systematic evidence development for learning throughout a therapeutic life cycle, to continually refine its use. Comparable evidence could arise from multiarm design, shared comparator arms, and standardized endpoints—aiding sponsors in demonstrating the distinct value of their innovative medicines; facilitating providers and patients in selecting the most appropriate treatments; assisting regulators in efficacy and safety determinations; helping payers make coverage and reimbursement decisions; and spurring scientists with translational insights. Reduced trial times and costs could enable more indications, reduced development cycle times, and improved system financial sustainability. Challenges to overcome range from statistical to operational to collaborative governance and data exchange. PMID:27643536

Synthesis and Characterization of Modified Phenylethynyl Terminated Polyimides

NASA Technical Reports Server (NTRS)

Chang, Alice C.

1998-01-01

As an ongoing effort to develop structural adhesives for high performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC (TM) MPEI (Modified Phenylethynyl Terminated Polyimide). These oligomers contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosity as low as 600 poise at 335 C. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strength of approx. 6000 psi and 5200 psi at ambient and 350 F temperatures, respectively. The chemistry and properties of these new MPEIs are presented and compared to an optimized linear PETI, LaRC(Tm) -PETI-5.

Evaluation of a multi-arm multi-stage Bayesian design for phase II drug selection trials - an example in hemato-oncology.

PubMed

Jacob, Louis; Uvarova, Maria; Boulet, Sandrine; Begaj, Inva; Chevret, Sylvie

2016-06-02

Multi-Arm Multi-Stage designs aim at comparing several new treatments to a common reference, in order to select or drop any treatment arm to move forward when such evidence already exists based on interim analyses. We redesigned a Bayesian adaptive design initially proposed for dose-finding, focusing our interest in the comparison of multiple experimental drugs to a control on a binary criterion measure. We redesigned a phase II clinical trial that randomly allocates patients across three (one control and two experimental) treatment arms to assess dropping decision rules. We were interested in dropping any arm due to futility, either based on historical control rate (first rule) or comparison across arms (second rule), and in stopping experimental arm due to its ability to reach a sufficient response rate (third rule), using the difference of response probabilities in Bayes binomial trials between the treated and control as a measure of treatment benefit. Simulations were then conducted to investigate the decision operating characteristics under a variety of plausible scenarios, as a function of the decision thresholds. Our findings suggest that one experimental treatment was less efficient than the control and could have been dropped from the trial based on a sample of approximately 20 instead of 40 patients. In the simulation study, stopping decisions were reached sooner for the first rule than for the second rule, with close mean estimates of response rates and small bias. According to the decision threshold, the mean sample size to detect the required 0.15 absolute benefit ranged from 63 to 70 (rule 3) with false negative rates of less than 2 % (rule 1) up to 6 % (rule 2). In contrast, detecting a 0.15 inferiority in response rates required a sample size ranging on average from 23 to 35 (rules 1 and 2, respectively) with a false positive rate ranging from 3.6 to 0.6 % (rule 3). Adaptive trial design is a good way to improve clinical trials. It allows removing ineffective drugs and reducing the trial sample size, while maintaining unbiased estimates. Decision thresholds can be set according to predefined fixed error decision rates. ClinicalTrials.gov Identifier: NCT01342692 .

Preventing recurrence of endometriosis by means of long-acting progestogen therapy (PRE-EMPT): report of an internal pilot, multi-arm, randomised controlled trial incorporating flexible entry design and adaption of design based on feasibility of recruitment.

PubMed

Middleton, Lee J; Daniels, Jane P; Weckesser, Annalise; Bhattacharya, Siladitya

2017-03-11

Endometriosis is associated with the growth of endometrium in ectopic sites mainly within the pelvis. This results in inflammation and scarring, causing pain and impaired quality of life. Endometriotic lesions can be excised or ablated surgically, but the risk of recurrence is high. A Heath Technology Assessment commissioning call in 2011 sought applications for trials aimed at evaluating long-term effectiveness of postoperative, long-acting, reversible contraceptives (LARCs) in preventing recurrence of endometriosis. A survey of gynaecologists indicated that there was no consensus about which LARC (Levonorgestrel Intrauterine System (LNG-IUS) or depot medroxyprogesterone acetate injection (DMPA)) or comparator (combined oral contraceptive pill (COCP) or no treatment) should be evaluated. Hence, we designed a 'flexible-entry' internal pilot to assess whether a four-arm trial was feasible including a possible design adaption based on pilot findings. In this pilot, women could be randomised to two, three or four treatment options provided that one was a LARC and one was a non-LARC. An assessment of feasibility based on recruitment to these options and a revised substantive trial design was considered by an independent oversight committee. The study ran for 1 year from April 2014 and 77 women were randomised. Only 5 (6%) women accepted randomisation to all groups, with 63 (82%) having a LARC preference and 55 (71%) a non-LARC preference. Four-way and three-way designs were ruled out with a two-way LARC versus COCP design, stratified by prerandomisation choice of LARC and optional subrandomisation to LNG-IUS versus DMPA considered a feasible substantive study. Multi-arm studies are potentially efficient as they can answer multiple questions simultaneously but are difficult to recruit to if there are strong patient or clinician preferences. A flexible approach to randomisation in a pilot phase can be used to assess feasibility of such studies and modify a trial design based on chosen recruitment options, but trialists should consider carefully any practical arrangements should groups need to be dropped during a study. International Standard Randomised Controlled Trial Number, ISRCTN97865475 . Registered on 20 March 2014.

Tunable Pickering Emulsions with Environmentally Responsive Hairy Silica Nanoparticles.

PubMed

Liu, Min; Chen, Xiaoli; Yang, Zongpeng; Xu, Zhou; Hong, Liangzhi; Ngai, To

2016-11-30

Surface modification of the nanoparticles using surface anchoring of amphiphilic polymers offers considerable scope for the design of a wide range of brush-coated hybrid nanoparticles with tunable surface wettability that may serve as new class of efficient Pickering emulsifiers. In the present study, we prepared mixed polymer brush-coated nanoparticles by grafting ABC miktoarm star terpolymers consisting of poly(ethylene glycol), polystyrene, and poly[(3-triisopropyloxysilyl)propyl methacrylate] (μ-PEG-b-PS-b-PIPSMA) on the surface of silica nanoparticles. The wettability of the as-prepared nanoparticles can be precisely tuned by a change of solvent or host-guest complexation. 1 H NMR result confirmed that such wettability change is due to the reorganization of the polymer chain at the grafted layer. We show that this behavior can be used for stabilization and switching between water-in-oil (W/O) and oil-in-water (O/W) emulsions. For hairy particles initially dispersed in oil, W/O emulsions were always obtained with collapsed PEG chains and mobile PS chains at the grafted layer. However, initially dispersing the hairy particles in water resulted in O/W emulsions with collapsed PS chains and mobile PEG chains. When a good solvent for both PS and PEG blocks such as toluene was used, W/O emulsions were always obtained no matter where the hairy particles were dispersed. The wettability of the mixed polymer brush-coated silica particles can also be tuned by host-guest complexation between PEG block and α-CD. More importantly, our result showed that surprisingly the resultant mixed brush-coated hairy nanoparticles can be employed for the one-step production of O/W/O multiple emulsions that are not attainable from conventional Pickering emulsifiers. The functionalized hairy silica nanoparticles at the oil-water interface can be further linked together utilizing poly(acrylic acid) as the reversible linker to form supramolecular colloidosomes, which show pH-dependent release of cargo.

Gels from soft hairy nanoparticles in polymeric matrices

NASA Astrophysics Data System (ADS)

Vlassopoulos, Dimitris

2013-03-01

Hairy particles represent a huge class of soft colloids with tunable interactions and properties. Advances in synthetic chemistry have enabled obtaining well-characterized such systems for specific needs. In this talk we present two model hairy soft particles with diameters of the order of tens of nanometers, star polymers and polymerically grafted spherical particles. In particular, we discuss design strategies for dispersing them in polymeric matrices and eventually creating and breaking gels. Control parameters are the matrix molar mass, the grafting density (or functionality) and the size of the grafts (or arms). The linear viscoelastic properties and slow time evolution of the gels are examined in view of the existing knowledge from colloidal gels consisting of micron-sized particles, and compared. In the case of stars we start from a concentrated glassy suspension in molecular solvent and add homopolymer at increasing concentration, and as a result of the induced osmotic pressure the stars shrink and a depletion gel is formed. For the grafted colloidal particles, they are added at low concentration to a polymer matrix, and it has been shown that under certain conditions the anisotropy of interactions gives rise to network formation. We then focus on the nonlinear rheological response and in particular the effect of shear flow in inducing a solid to liquid transition. Our studies show that the yielding process is gradual and shares many common features with that of flocculated colloidal suspensions, irrespectively of the shape of the building block of the gel. Whereas shear can melt such a gel, it cannot break it into its constituent blocks and hence fully disperse the hairy nanoparticles. On the other hand, the hairy particles are intrinsically hybrid. We show how this important feature is reflected on the heating of the gels. In that case, the mismatch of thermal expansion coefficients of core and shell appears to play a role on the particle response as it imposes and internal strain on the particle, which in turn changes the shell conformation and under some conditions can lead to thermal melting of the gel. These alternative avenues for manipulating the gel-to-liquid transition have potential implications in directing the properties of hairy nanoparticles and their assemblies in viscoelastic matrices. Parts of this work reflect collaboration with D. Truzzolillo (FORTH), J. F. Moll and S. K.Kumar (Columbia). R. H. Colby (Penn State), M. Gauthier (Waterloo) and B. C. Benicewicz (Univ. South Carolina).

Azo polymeric micelles designed for colon-targeted dimethyl fumarate delivery for colon cancer therapy.

PubMed

Ma, Zhen-Gang; Ma, Rui; Xiao, Xiao-Lin; Zhang, Yong-Hui; Zhang, Xin-Zi; Hu, Nan; Gao, Jin-Lai; Zheng, Yu-Feng; Dong, De-Li; Sun, Zhi-Jie

2016-10-15

Colon-targeted drug delivery and circumventing drug resistance are extremely important for colon cancer chemotherapy. Our previous work found that dimethyl fumarate (DMF), the approved drug by the FDA for the treatment of multiple sclerosis, exhibited anti-tumor activity on colon cancer cells. Based on the pharmacological properties of DMF and azo bond in olsalazine chemical structure, we designed azo polymeric micelles for colon-targeted dimethyl fumarate delivery for colon cancer therapy. We synthesized the star-shape amphiphilic polymer with azo bond and fabricated the DMF-loaded azo polymeric micelles. The four-arm polymer star-PCL-azo-mPEG (sPCEG-azo) (constituted by star-shape PCL (polycaprolactone) and mPEG (methoxypolyethylene glycols)-olsalazine) showed self-assembly ability. The average diameter and polydispersity index of the DMF-loaded sPCEG-azo polymeric micelles were 153.6nm and 0.195, respectively. In vitro drug release study showed that the cumulative release of DMF from the DMF-loaded sPCEG-azo polymeric micelles was no more than 20% in rat gastric fluid within 10h, whereas in the rat colonic fluids, the cumulative release of DMF reached 60% in the initial 2h and 100% within 10h, indicating that the DMF-loaded sPCEG-azo polymeric micelles had excellent colon-targeted property. The DMF-loaded sPCEG-azo polymeric micelles had no significant cytotoxicity on colon cancer cells in phosphate buffered solution (PBS) and rat gastric fluid. In rat colonic fluid, the micelles showed significant cytotoxic effect on colon cancer cells. The blank sPCEG-azo polymeric micelles (without DMF) showed no cytotoxic effect on colon cancer cells in rat colonic fluids. In conclusion, the DMF-loaded sPCEG-azo polymeric micelles show colon-targeted DMF release and anti-tumor activity, providing a novel approach potential for colon cancer therapy. Colon-targeted drug delivery and circumventing drug resistance are extremely important for colon cancer chemotherapy. Our previous work found that dimethyl fumarate (DMF), the approved drug by the FDA for the treatment of multiple sclerosis, exhibited anti-tumor activities on colon cancer cells (Br J Pharmacol. 2015 172(15):3929-43.). Based on the pharmacological properties of DMF and azo bond in olsalazine chemical structure, we designed azo polymeric micelles for colon-targeted dimethyl fumarate delivery for colon cancer therapy. We found that the DMF-loaded sPCEG-azo polymeric micelles showed colon-targeted DMF release and anti-tumor activities, providing a novel approach potential for colon cancer therapy. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms.

PubMed

Kotwica, Kamil; Kostyuchenko, Anastasia S; Data, Przemyslaw; Marszalek, Tomasz; Skorka, Lukasz; Jaroch, Tomasz; Kacka, Sylwia; Zagorska, Malgorzata; Nowakowski, Robert; Monkman, Andrew P; Fisyuk, Alexander S; Pisula, Wojciech; Pron, Adam

2016-08-08

Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg (opt)) as well as electrochemical (Eg (electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg (opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Holographic three-dimensional telepresence using large-area photorefractive polymer.

PubMed

Blanche, P-A; Bablumian, A; Voorakaranam, R; Christenson, C; Lin, W; Gu, T; Flores, D; Wang, P; Hsieh, W-Y; Kathaperumal, M; Rachwal, B; Siddiqui, O; Thomas, J; Norwood, R A; Yamamoto, M; Peyghambarian, N

2010-11-04

Holography is a technique that is used to display objects or scenes in three dimensions. Such three-dimensional (3D) images, or holograms, can be seen with the unassisted eye and are very similar to how humans see the actual environment surrounding them. The concept of 3D telepresence, a real-time dynamic hologram depicting a scene occurring in a different location, has attracted considerable public interest since it was depicted in the original Star Wars film in 1977. However, the lack of sufficient computational power to produce realistic computer-generated holograms and the absence of large-area and dynamically updatable holographic recording media have prevented realization of the concept. Here we use a holographic stereographic technique and a photorefractive polymer material as the recording medium to demonstrate a holographic display that can refresh images every two seconds. A 50 Hz nanosecond pulsed laser is used to write the holographic pixels. Multicoloured holographic 3D images are produced by using angular multiplexing, and the full parallax display employs spatial multiplexing. 3D telepresence is demonstrated by taking multiple images from one location and transmitting the information via Ethernet to another location where the hologram is printed with the quasi-real-time dynamic 3D display. Further improvements could bring applications in telemedicine, prototyping, advertising, updatable 3D maps and entertainment.

Hydrazone linkages in pH responsive drug delivery systems.

PubMed

Sonawane, Sandeep J; Kalhapure, Rahul S; Govender, Thirumala

2017-03-01

Stimuli-responsive polymeric drug delivery systems using various triggers to release the drug at the sites have become a major focus area. Among various stimuli-responsive materials, pH-responsiveness has been studied extensively. The materials used for fabricating pH-responsive drug delivery systems include a specific chemical functionality in their structure that can respond to changes in the pH of the surrounding environment. Various chemical functionalities, for example, acetal, amine, ortho ester, amine and hydrazone, have been used to design materials that are capable of releasing their payload at the acidic pH conditions of the tumor or infection sites. Hydrazone linkages are significant synthons for numerous transformations and have gained importance in pharmaceutical sciences due to their various biological and clinical applications. These linkages have been employed in various drug delivery vehicles, such as linear polymers, star shaped polymers, dendrimers, micelles, liposomes and inorganic nanoparticles, for pH-responsive drug delivery. This review paper focuses on the synthesis and characterization methods of hydrazone bond containing materials and their applications in pH-responsive drug delivery systems. It provides detailed suggestions as guidelines to materials and formulation scientists for designing biocompatible pH-responsive materials with hydrazone linkages and identifying future studies. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Molecular Architecture on Polymer Melt Surface Dynamics

NASA Astrophysics Data System (ADS)

Foster, Mark

The dynamics of the thermally stimulated surface height fluctuations in a polymer melt dictate wetting, adhesion, and tribology at that surface. These surface fluctuations can be profoundly altered by tethering of the chains. One type of tethering is the tethering of one part of a molecule to another part of the same molecule. This tethering is found in both long chain branched polymers and in macrocycles. We have studied the surface fluctuations with X-ray Photon Correlation Spectroscopy for melts of well-defined, anionically polymerized polystyrenes of various architectures, including linear, 6 arm star, pom-pom, comb and cyclic architectures. For linear chains, the variation of surface relaxation time with in-plane scattering vector can be fit using a hydrodynamic continuum theory (HCT) of thermally stimulated capillary waves that knows nothing of the chain architecture. Assuming the theory is applicable, apparent viscosities of the films may then be inferred from the XPCS data. For unentangled linear chains, the viscosity inferred from XPCS data in this manner is the same as that measured by conventional bulk rheometry. The HCT does a reasonable job of describing the variation of relaxation time with scattering vector for long branched chains also, but only if a viscosity much larger than that of the bulk is assumed. The discrepancy between the viscosity inferred from surface relaxation times using the HCT and that derived from conventional rheometry grows larger as the bulk Tg is approached and is different for each long chain branched architecture. However, for densely branched combs and cyclic chains different behaviors are found. Acknowledgement: Thanks to NSF (CBET 0730692) and the Advanced Photon Source, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, under Contract No. W-31-109-ENG-38.

Signal amplification strategy for biomarkers: Structural origins of epitaxial-growth twinned nanocrystals and D-π-A type polymers.

PubMed

Liu, He; Gu, Yue; Dong, Tao; Yan, Liuqing; Yan, Xiaoyi; Zhang, Tingting; Lu, Nannan; Xu, Zhiqian; Xu, Haixin; Zhang, Zhiquan; Bian, Ting

2018-06-30

The combination of nanoparticles and biomarkers yields functional nanostructured biointerface, which is playing a notable role in biotechnology development. Due to the 5-fold twined structure in the Au-Pt star-shaped decahedra not only allowed it to act as efficient scaffold for immobilization of antibody, but it also exhibits superior electrocatalytic activity toward H 2 O 2 reduction, the nanocrystal as the efficient signal transduction label is first employed to construct an electrochemical immunosensor. Donor-π-Acceptor (D-π-A) linking fashion generates a dipolar push-pull system and assures superior intramolecular charge transfer. It is considered as a suitable π-conjugated backbone for conducting polymer on biointerface application. Under a D-π-A architecture which imidazole as the π-bridge and amino phenyl/phenyl groups as peripheral electron-donating/withdrawing functional groups, 4-(2,4,5-triphenyl-1H-imidazol-1-yl) aniline (TPIDA) is designed and synthesized for good biocompatibility and high conductivity. In this proposal, we attempt to integrate the above-mentioned two features from nanobiotechnology and organic bioelectronics. Then, a novel nonenzymatic sandwich-type immunosensor is performed by Au-Pt core-shell with surface-engineered twinning as a label and π-conjugated D-π-A polymers as the signal amplification platform. Human IgG (HIgG) as the model target protein can be detected with a wide linear range from 0.1 pg mL -1 to 100 ng mL -1 . The detection limit is down to 0.06 pg mL -1 (S/N = 3). Moreover, as a practical application, the prepared biosensor is used to monitor HIgG level in human serum with desirable results obtained. Copyright © 2018 Elsevier B.V. All rights reserved.

Coordinated trajectory planning of dual-arm space robot using constrained particle swarm optimization

NASA Astrophysics Data System (ADS)

Wang, Mingming; Luo, Jianjun; Yuan, Jianping; Walter, Ulrich

2018-05-01

Application of the multi-arm space robot will be more effective than single arm especially when the target is tumbling. This paper investigates the application of particle swarm optimization (PSO) strategy to coordinated trajectory planning of the dual-arm space robot in free-floating mode. In order to overcome the dynamics singularities issue, the direct kinematics equations in conjunction with constrained PSO are employed for coordinated trajectory planning of dual-arm space robot. The joint trajectories are parametrized with Bézier curve to simplify the calculation. Constrained PSO scheme with adaptive inertia weight is implemented to find the optimal solution of joint trajectories while specific objectives and imposed constraints are satisfied. The proposed method is not sensitive to the singularity issue due to the application of forward kinematic equations. Simulation results are presented for coordinated trajectory planning of two kinematically redundant manipulators mounted on a free-floating spacecraft and demonstrate the effectiveness of the proposed method.

Comparison of joint space versus task force load distribution optimization for a multiarm manipulator system

NASA Technical Reports Server (NTRS)

Soloway, Donald I.; Alberts, Thomas E.

1989-01-01

It is often proposed that the redundancy in choosing a force distribution for multiple arms grasping a single object should be handled by minimizing a quadratic performance index. The performance index may be formulated in terms of joint torques or in terms of the Cartesian space force/torque applied to the body by the grippers. The former seeks to minimize power consumption while the latter minimizes body stresses. Because the cost functions are related to each other by a joint angle dependent transformation on the weight matrix, it might be argued that either method tends to reduce power consumption, but clearly the joint space minimization is optimal. A comparison of these two options is presented with consideration given to computational cost and power consumption. Simulation results using a two arm robot system are presented to show the savings realized by employing the joint space optimization. These savings are offset by additional complexity, computation time and in some cases processor power consumption.

A Systematic Review of the Effects of Behavioral Counseling on Sexual Risk Behaviors and HIV/STI Prevalence in Low- and Middle-Income Countries.

PubMed

Zajac, Kristyn; Kennedy, Caitlin E; Fonner, Virginia A; Armstrong, Kevin S; O'Reilly, Kevin R; Sweat, Michael D

2015-07-01

The purpose of this study was to assess the effectiveness of behavioral counseling interventions in reducing sexual risk behaviors and HIV/STI prevalence in low- and middle-income countries. A systematic review of papers published between 1990 and 2011 was conducted, identifying studies that utilized either a multi-arm or pre-post design and presented post-intervention data. Standardized methods of searching and data abstraction were used, and 30 studies met inclusion criteria. Results are summarized by intervention groups: (a) people living with HIV; (b) people who use drugs and alcohol; (c) serodiscordant couples; (d) key populations for HIV prevention; and (e) people at low to moderate HIV risk. Evidence for the effectiveness of behavioral counseling was mixed, with more rigorously designed studies often showing modest or no effects. Recommendations about the use of behavioral counseling in developing countries are made based on study results and in light of the field's movement towards combination prevention programs.

Interlocking Mechanism between Molecular Gears Attached to Surfaces.

PubMed

Zhao, Rundong; Zhao, Yan-Ling; Qi, Fei; Hermann, Klaus E; Zhang, Rui-Qin; Van Hove, Michel A

2018-03-27

While molecular machines play an increasingly significant role in nanoscience research and applications, there remains a shortage of investigations and understanding of the molecular gear (cogwheel), which is an indispensable and fundamental component to drive a larger correlated molecular machine system. Employing ab initio calculations, we investigate model systems consisting of molecules adsorbed on metal or graphene surfaces, ranging from very simple triple-arm gears such as PF 3 and NH 3 to larger multiarm gears based on carbon rings. We explore in detail the transmission of slow rotational motion from one gear to the next by these relatively simple molecules, so as to isolate and reveal the mechanisms of the relevant intermolecular interactions. Several characteristics of molecular gears are discussed, in particular the flexibility of the arms and the slipping and skipping between interlocking arms of adjacent gears, which differ from familiar macroscopic rigid gears. The underlying theoretical concepts suggest strongly that other analogous structures may also exhibit similar behavior which may inspire future exploration in designing large correlated molecular machines.

Coevolutionary Free Lunches

NASA Technical Reports Server (NTRS)

Wolpert, David H.; Macready, William G.

2005-01-01

Recent work on the mathematical foundations of optimization has begun to uncover its rich structure. In particular, the "No Free Lunch" (NFL) theorems state that any two algorithms are equivalent when their performance is averaged across all possible problems. This highlights the need for exploiting problem-specific knowledge to achieve better than random performance. In this paper we present a general framework covering more search scenarios. In addition to the optimization scenarios addressed in the NFL results, this framework covers multi-armed bandit problems and evolution of multiple co-evolving players. As a particular instance of the latter, it covers "self-play" problems. In these problems the set of players work together to produce a champion, who then engages one or more antagonists in a subsequent multi-player game. In contrast to the traditional optimization case where the NFL results hold, we show that in self-play there are free lunches: in coevolution some algorithms have better performance than other algorithms, averaged across all possible problems. We consider the implications of these results to biology where there is no champion.

Multi-arm multilateral haptics-based immersive tele-robotic system (HITS) for improvised explosive device disposal

NASA Astrophysics Data System (ADS)

Erickson, David; Lacheray, Hervé; Lai, Gilbert; Haddadi, Amir

2014-06-01

This paper presents the latest advancements of the Haptics-based Immersive Tele-robotic System (HITS) project, a next generation Improvised Explosive Device (IED) disposal (IEDD) robotic interface containing an immersive telepresence environment for a remotely-controlled three-articulated-robotic-arm system. While the haptic feedback enhances the operator's perception of the remote environment, a third teleoperated dexterous arm, equipped with multiple vision sensors and cameras, provides stereo vision with proper visual cues, and a 3D photo-realistic model of the potential IED. This decentralized system combines various capabilities including stable and scaled motion, singularity avoidance, cross-coupled hybrid control, active collision detection and avoidance, compliance control and constrained motion to provide a safe and intuitive control environment for the operators. Experimental results and validation of the current system are presented through various essential IEDD tasks. This project demonstrates that a two-armed anthropomorphic Explosive Ordnance Disposal (EOD) robot interface can achieve complex neutralization techniques against realistic IEDs without the operator approaching at any time.

Anticancer activity of drug conjugates in head and neck cancer cells.

PubMed

Majumdar, Debatosh; Rahman, Mohammad Aminur; Chen, Zhuo Georgia; Shin, Dong M

2016-06-01

Sexually transmitted oral cancer/head and neck cancer is increasing rapidly. Human papilloma virus (HPV) is playing a role in the pathogenesis of a subset of squamous cell carcinoma of head and neck (SCCHN). Paclitaxel is a widely used anticancer drug for breast, ovarian, testicular, cervical, non-small cell lung, head and neck cancer. However, it is water insoluble and orally inactive. We report the synthesis of water soluble nanosize conjugates of paclitaxel, branched PEG, and EGFR-targeting peptide by employing native chemical ligation. We performed a native chemical ligation between the N-hydroxy succinimide (NHS) ester of paclitaxel succinate and cysteine at pH 6.5 to give the cysteine-conjugated paclitaxel derivative. The thiol functionality of cysteine was activated and subsequently conjugated to multiarm thiol-PEG to obtain the paclitaxel branched PEG conjugate. Finally, we conjugated an EGFR-targeting peptide to obtain conjugates of paclitaxel, branched PEG, and EGFR-targeting peptide. These conjugates show anticancer activity against squamous cell carcinoma of head and neck cells (SCCHN, Tu212).

Infomax Strategies for an Optimal Balance Between Exploration and Exploitation

NASA Astrophysics Data System (ADS)

Reddy, Gautam; Celani, Antonio; Vergassola, Massimo

2016-06-01

Proper balance between exploitation and exploration is what makes good decisions that achieve high reward, like payoff or evolutionary fitness. The Infomax principle postulates that maximization of information directs the function of diverse systems, from living systems to artificial neural networks. While specific applications turn out to be successful, the validity of information as a proxy for reward remains unclear. Here, we consider the multi-armed bandit decision problem, which features arms (slot-machines) of unknown probabilities of success and a player trying to maximize cumulative payoff by choosing the sequence of arms to play. We show that an Infomax strategy (Info-p) which optimally gathers information on the highest probability of success among the arms, saturates known optimal bounds and compares favorably to existing policies. Conversely, gathering information on the identity of the best arm in the bandit leads to a strategy that is vastly suboptimal in terms of payoff. The nature of the quantity selected for Infomax acquisition is then crucial for effective tradeoffs between exploration and exploitation.

From simple to complex prebiotic chemistry in a carbon-rich universe

NASA Astrophysics Data System (ADS)

Lage, C.; Janot-Pacheco, E.; Domiciano de Souza, A.; Suárez, O.; Bendjoya, P.; Gadotti, D. A.

2012-09-01

It is well known that the main components of important biomolecules are quite common not only in the Solar System, but also in other planetary systems and in the Galactic ISM. The ubiquitous presence of C in the Universe and the unique carbon chemical properties and carbon bonding thermodynamics supports the spontaneous self-replication of monomers into larger polymers, yielding the formation of large molecules. The detection of an ever increasing number of organic molecules in the interstellar medium (ISM) by radio-telescopes and chemical analysis of meteorites boosted astrochemical theories on radiation-induced chemistry, supported by laboratory experiments. In this scenario of exogenous origin of carbon compounds, polyaromatic hydrocarbons (PAHs) may represent a resilient way of accumulating carbon as a robust cosmic reservoir. Consisting of a family of compounds with fused aromatic rings, the abundances of its larger members (50-100 carbon atoms) were estimated to be on top scores just after H2 and CO. PAHs have been detected in the ISM, in star-forming regions, ~14% of low-mass premainsequence stars, and, remarkably, in some 54% of intermediate mass stars. They have also been detected by SPITZER in distant galaxies up to z = 3. PAHs were promptly photolysed into a family of radicals if exposed to UV and oxygen-bearing molecules in laboratory. The presence of oxygenbearing molecules was shown in the laboratory to bring aromatic rings into an unstable chemistry leading to the production of e.g. alcohols, ketones and ether radicals. It has already been observed that carbon-and oxygen-rich stellar envelopes give rise to richer carbon chemistry. It appears very tempting to think that key prebiotic fragments should appear along planetary formation as C-O reaction byproducts such as methanol (CH3OH), formaldehyde (H2CO) and also simpler hydrocarbons as methyl acetylene (CH3CCH). Under an Astrobiology perspective it is plausible to map PAHs and oxygen compounds together in the same target - envelopes of young stars - with the ALMA facility. We intend to do it in the frame of a CNRS funded international collaboration between Brazilian groups, OCA and ESO.

Strong poly(ethylene oxide) based gel adhesives via oxime cross-linking.

PubMed

Ghosh, Smita; Cabral, Jaydee D; Hanton, Lyall R; Moratti, Stephen C

2016-01-01

There is a demand for materials to replace or augment the use of sutures and staples in surgical procedures. Currently available commercial surgical adhesives provide either high bond strength with biological toxicity or polymer and protein-based products that are biologically acceptable (though with potential sensitizing potential) but have much reduced bond strength. It is desirable to provide novel biocompatible and biodegradable surgical adhesives/sealants capable of high strength with minimal immune or inflammatory response. In this work, we report the end group derivatization of 8-arm star PEOs with aldehyde and amine end groups. Gels were prepared employing the Schiff-base chemistry between the aldehydes and the amines. Gel setting times, swelling behavior and rheological characterization were carried out for these gels. The mechanical-viscoelastic properties were found to be directly proportional to the crosslinking density of the gels, the 10K PEO gel was stiffer in comparison to the 20K PEO gel. The adhesive properties of these gels were tested using porcine skin and showed excellent adhesion properties. Cytotoxicity studies were carried out for the individual gel components using two different methods: (a) Crystal Violet Staining assay (CVS assay) and (b) impedance and cell index measurement by the xCELLigence system at concentrations >5%. Gels prepared by mixing 20% w/w solutions were also tested for cytotoxicity. The results revealed that the individual gel components as well as the prepared gels and their leachables were non-cytotoxic at these concentrations. This work presents a new type of glue that is aimed at surgery applications using a water soluble star shaped polymer. It show excellent adhesion to skin and is tough and easy to use. We show that it is very biocompatible based on tests on live human cells, and could therefore in principle be used for internal surgery. Comparison with other reported and commercial glues shows that it is stronger than most, and does not swell in water to the same degree as many other water based bioadhesives. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Flexible trial design in practice - stopping arms for lack-of-benefit and adding research arms mid-trial in STAMPEDE: a multi-arm multi-stage randomized controlled trial

PubMed Central

2012-01-01

Background Systemic Therapy for Advanced or Metastatic Prostate cancer: Evaluation of Drug Efficacy (STAMPEDE) is a randomized controlled trial that follows a novel multi-arm, multi-stage (MAMS) design. We describe methodological and practical issues arising with (1) stopping recruitment to research arms following a pre-planned intermediate analysis and (2) adding a new research arm during the trial. Methods STAMPEDE recruits men who have locally advanced or metastatic prostate cancer who are starting standard long-term hormone therapy. Originally there were five research and one control arms, each undergoing a pilot stage (focus: safety, feasibility), three intermediate ‘activity’ stages (focus: failure-free survival), and a final ‘efficacy’ stage (focus: overall survival). Lack-of-sufficient-activity guidelines support the pairwise interim comparisons of each research arm against the control arm; these pre-defined activity cut-off becomes increasingly stringent over the stages. Accrual of further patients continues to the control arm and to those research arms showing activity and an acceptable safety profile. The design facilitates adding new research arms should sufficiently interesting agents emerge. These new arms are compared only to contemporaneously recruited control arm patients using the same intermediate guidelines in a time-delayed manner. The addition of new research arms is subject to adequate recruitment rates to support the overall trial aims. Results (1) Stopping Existing Therapy: After the second intermediate activity analysis, recruitment was discontinued to two research arms for lack-of-sufficient activity. Detailed preparations meant that changes were implemented swiftly at 100 international centers and recruitment continued seamlessly into Activity Stage III with 3 remaining research arms and the control arm. Further regulatory and ethical approvals were not required because this was already included in the initial trial design. (2) Adding New Therapy: An application to add a new research arm was approved by the funder, (who also organized peer review), industrial partner and regulatory and ethical bodies. This was all done in advance of any decision to stop current therapies. Conclusions The STAMPEDE experience shows that recruitment to a MAMS trial and mid-flow changes its design are achievable with good planning. This benefits patients and the scientific community as research treatments are evaluated in a more efficient and cost-effective manner. Trial registration ISRCTN78818544, NCT00268476 First patient into trial: 17 October 2005 First patient into abiraterone comparison: 15 November 2011 PMID:22978443

Flexible trial design in practice - stopping arms for lack-of-benefit and adding research arms mid-trial in STAMPEDE: a multi-arm multi-stage randomized controlled trial.

PubMed

Sydes, Matthew R; Parmar, Mahesh K B; Mason, Malcolm D; Clarke, Noel W; Amos, Claire; Anderson, John; de Bono, Johann; Dearnaley, David P; Dwyer, John; Green, Charlene; Jovic, Gordana; Ritchie, Alastair W S; Russell, J Martin; Sanders, Karen; Thalmann, George; James, Nicholas D

2012-09-15

Systemic Therapy for Advanced or Metastatic Prostate cancer: Evaluation of Drug Efficacy (STAMPEDE) is a randomized controlled trial that follows a novel multi-arm, multi-stage (MAMS) design. We describe methodological and practical issues arising with (1) stopping recruitment to research arms following a pre-planned intermediate analysis and (2) adding a new research arm during the trial. STAMPEDE recruits men who have locally advanced or metastatic prostate cancer who are starting standard long-term hormone therapy. Originally there were five research and one control arms, each undergoing a pilot stage (focus: safety, feasibility), three intermediate 'activity' stages (focus: failure-free survival), and a final 'efficacy' stage (focus: overall survival). Lack-of-sufficient-activity guidelines support the pairwise interim comparisons of each research arm against the control arm; these pre-defined activity cut-off becomes increasingly stringent over the stages. Accrual of further patients continues to the control arm and to those research arms showing activity and an acceptable safety profile. The design facilitates adding new research arms should sufficiently interesting agents emerge. These new arms are compared only to contemporaneously recruited control arm patients using the same intermediate guidelines in a time-delayed manner. The addition of new research arms is subject to adequate recruitment rates to support the overall trial aims. (1) Stopping Existing Therapy: After the second intermediate activity analysis, recruitment was discontinued to two research arms for lack-of-sufficient activity. Detailed preparations meant that changes were implemented swiftly at 100 international centers and recruitment continued seamlessly into Activity Stage III with 3 remaining research arms and the control arm. Further regulatory and ethical approvals were not required because this was already included in the initial trial design.(2) Adding New Therapy: An application to add a new research arm was approved by the funder, (who also organized peer review), industrial partner and regulatory and ethical bodies. This was all done in advance of any decision to stop current therapies. The STAMPEDE experience shows that recruitment to a MAMS trial and mid-flow changes its design are achievable with good planning. This benefits patients and the scientific community as research treatments are evaluated in a more efficient and cost-effective manner. ISRCTN78818544, NCT00268476. First patient into trial: 17 October 2005. First patient into abiraterone comparison: 15 November 2011.

Biodegradable and adjustable sol-gel glass based hybrid scaffolds from multi-armed oligomeric building blocks.

PubMed

Kascholke, Christian; Hendrikx, Stephan; Flath, Tobias; Kuzmenka, Dzmitry; Dörfler, Hans-Martin; Schumann, Dirk; Gressenbuch, Mathias; Schulze, F Peter; Schulz-Siegmund, Michaela; Hacker, Michael C

2017-11-01

Biodegradability is a crucial characteristic to improve the clinical potential of sol-gel-derived glass materials. To this end, a set of degradable organic/inorganic class II hybrids from a tetraethoxysilane(TEOS)-derived silica sol and oligovalent cross-linker oligomers containing oligo(d,l-lactide) domains was developed and characterized. A series of 18 oligomers (Mn: 1100-3200Da) with different degrees of ethoxylation and varying length of oligoester units was established and chemical composition was determined. Applicability of an established indirect rapid prototyping method enabled fabrication of a total of 85 different hybrid scaffold formulations from 3-isocyanatopropyltriethoxysilane-functionalized macromers. In vitro degradation was analyzed over 12months and a continuous linear weight loss (0.2-0.5wt%/d) combined with only moderate material swelling was detected which was controlled by oligo(lactide) content and matrix hydrophilicity. Compressive strength (2-30MPa) and compressive modulus (44-716MPa) were determined and total content, oligo(ethylene oxide) content, oligo(lactide) content and molecular weight of the oligomeric cross-linkers as well as material porosity were identified as the main factors determining hybrid mechanics. Cytocompatibility was assessed by cell culture experiments with human adipose tissue-derived stem cells (hASC). Cell migration into the entire scaffold pore network was indicated and continuous proliferation over 14days was found. ALP activity linearly increased over 2weeks indicating osteogenic differentiation. The presented glass-based hybrid concept with precisely adjustable material properties holds promise for regenerative purposes. Adaption of degradation kinetics toward physiological relevance is still an unmet challenge of (bio-)glass engineering. We therefore present a glass-derived hybrid material with adjustable degradation. A flexible design concept based on degradable multi-armed oligomers was combined with an established indirect rapid prototyping method to produce a systematic set of porous sol-gel-derived class II hybrid scaffolds. Mechanical properties in the range of cancellous bone were narrowly controlled by hybrid composition. The oligoester introduction resulted in significantly increased compressive moduli. Cytocompatible hybrids degraded in physiologically relevant time frames and a promising linear and controllable weight loss profile was found. To our knowledge, our degradation study represents the most extensive long-term investigation of sol-gel-derived class II hybrids. Due to the broad adjustability of material properties, our concept offers potential for engineering of biodegradable hybrid materials for versatile applications. Copyright © 2017. Published by Elsevier Ltd.

Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger.

PubMed

Phillips, Daniel J; Congdon, Thomas R; Gibson, Matthew I

2016-03-07

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity - a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-terminated poly(vinyl alcohol) was synthesised by RAFT polymerization. Upon addition of Fe 3+ , larger supramolecular star polymers form by assembly with two or three catechols. This increase in molecular weight effectively 'switches on' the IRI activity and is the first example of external control over the function of AFP mimetics. This provides a simple but elegant solution to the challenge of external control of AFP-mimetic function.

Star-shaped poly(oligoethylene glycol) copolymer-based gels: Thermo-responsive behaviour and bioapplicability for risedronate intranasal delivery.

PubMed

Soliman, Mahmoud E; Elmowafy, Enas; Casettari, Luca; Alexander, Cameron

2018-05-30

The aim of this work was to obtain an intranasal delivery system with improved mechanical and mucoadhesive properties that could provide prolonged retention time for the delivery of risedronate (RS). For this, novel in situ forming gels comprising thermo-responsive star-shaped polymers, utilizing either polyethylene glycol methyl ether (PEGMA-ME 188, Mn 188) or polyethylene glycol ethyl ether (PEGMA-EE 246, Mn 246), with polyethylene glycol methyl ether (PEGMA-ME 475, Mn 475), were synthesized and characterized. RS was trapped in the selected gel-forming solutions at a concentration of 0.2% w/v. The pH, rheological properties, in vitro drug release, ex vivo permeation as well as mucoadhesion were also examined. MTT assays were conducted to verify nasal tolerability of the developed formulations. Initial in vivo studies were carried out to evaluate anti-osteoporotic activity in a glucocorticoid induced osteoporosis model in rats. The results showed successful development of thermo-sensitive formulations with favorable mechanical properties at 37 °C, which formed non-irritant, mucoadhesive porous networks, facilitating nasal RS delivery. Moreover, sustained release of RS, augmented permeability and marked anti-osteoporotic efficacy as compared to intranasal (IN) and intravenous (IV) RS solutions were realized. The combined results show that the in situ gels should have promising application as nasal drug delivery systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Oligomer Molecules for Efficient Organic Photovoltaics.

PubMed

Lin, Yuze; Zhan, Xiaowei

2016-02-16

Solar cells, a renewable, clean energy technology that efficiently converts sunlight into electricity, are a promising long-term solution for energy and environmental problems caused by a mass of production and the use of fossil fuels. Solution-processed organic solar cells (OSCs) have attracted much attention in the past few years because of several advantages, including easy fabrication, low cost, lightweight, and flexibility. Now, OSCs exhibit power conversion efficiencies (PCEs) of over 10%. In the early stage of OSCs, vapor-deposited organic dye materials were first used in bilayer heterojunction devices in the 1980s, and then, solution-processed polymers were introduced in bulk heterojunction (BHJ) devices. Relative to polymers, vapor-deposited small molecules offer potential advantages, such as a defined molecular structure, definite molecular weight, easy purification, mass-scale production, and good batch-to-batch reproducibility. However, the limited solubility and high crystallinity of vapor-deposited small molecules are unfavorable for use in solution-processed BHJ OSCs. Conversely, polymers have good solution-processing and film-forming properties and are easily processed into flexible devices, whereas their polydispersity of molecular weights and difficulty in purification results in batch to batch variation, which may hamper performance reproducibility and commercialization. Oligomer molecules (OMs) are monodisperse big molecules with intermediate molecular weights (generally in the thousands), and their sizes are between those of small molecules (generally with molecular weights <1000) and polymers (generally with molecular weights >10000). OMs not only overcome shortcomings of both vapor-deposited small molecules and solution-processed polymers, but also combine their advantages, such as defined molecular structure, definite molecular weight, easy purification, mass-scale production, good batch-to-batch reproducibility, good solution processability, and film-forming properties. Therefore, OMs are a good choice for solution-processed reproducible OSCs toward scalable commercialized applications. Considerable efforts have been dedicated to developing new OM electron donors and electron acceptors for OSCs. So far, the highest PCEs of solution-processed OSCs based on OM donors and acceptors are 9-10% and 6-7%, respectively. OM materials have become promising alternatives to polymer and/or fullerene materials for efficient and stable OSCs. In this Account, we present a brief survey of the recent developments in solution-processable OM electron donors and acceptors and their application in OSCs. Rational design of OMs with star- and linear-shaped structures based on triphenylamine, benzodithiophene, and indacenodithiophene units and their impacts on device performance are discussed. Structure-property relationships are also proposed. Furthermore, the remaining challenges and the key research directions in the near future are also addressed. In the next years, an interdisciplinary approach involving novel OM materials, especially electron acceptor materials, accurate morphology optimization, and advanced device technologies will probably bring high-efficiency and stable OSCs to final commercialization.

Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions

PubMed Central

Ledin, Petr A.; Xu, Weinan; Friscourt, Frédéric; Boons, Geert-Jan; Tsukruk, Vladimir V.

2016-01-01

Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic–inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly functionalized via strain-promoted azide–alkyne cycloaddition (SPAAC) to synthesize a series of nearly monodisperse branched core–shell nanoparticles with hydrophobic POSS cores and hydrophilic arms. We established that SPAAC is a robust method for POSS core octafunctionalization with the reaction rate constant of 1.9 × 10−2 M−1 s−1. Functionalization with poly(ethylene glycol) (PEG) azide, fluorescein azide, and unprotected lactose azide gave conjugates which represent different classes of compounds: polymer conjugates, fluorescent dots, and bioconjugates. These resulting hybrid compounds were preliminarily tested for their ability to self-assemble in solution and at the air–water interface. We observed the formation of robust smooth Langmuir monolayers with diverse morphologies. We found that polar lactose moieties are completely submerged into the subphase whereas the relatively hydrophobic fluorescein arms had extended conformation at the interface, and PEG arms were partially submerged. Finally, we observed the formation of stable micelles with sizes between 70 and 160 nm in aqueous solutions with size and morphology of the structures dependent on the molecular weight and the type of the peripheral hydrophilic moieties. PMID:26131712

Interaction chromatography for characterization and large-scale fractionation of chemically heterogeneous copolymers

NASA Astrophysics Data System (ADS)

Han, Junwon

The remarkable development of polymer synthesis techniques to make complex polymers with controlled chain architectures has inevitably demanded the advancement of polymer characterization tools to analyze the molecular dispersity in polymeric materials beyond size exclusion chromatography (SEC). In particular, man-made synthetic copolymers that consist of more than one monomer type are disperse mixtures of polymer chains that have distributions in terms of both chemical heterogeneity and chain length (molar mass). While the molecular weight distribution has been quite reliably estimated by the SEC, it is still challenging to properly characterize the chemical composition distribution in the copolymers. Here, I have developed and applied adsorption-based interaction chromatography (IC) techniques as a promising tool to characterize and fractionate polystyrene-based block, random and branched copolymers in terms of their chemical heterogeneity. The first part of this thesis is focused on the adsorption-desorption based purification of PS-b-PMMA diblock copolymers using nanoporous silica. The liquid chromatography analysis and large scale purification are discussed for the PS-b-PMMA block copolymers that have been synthesized by sequential anionic polymerization. SEC and IC are compared to critically analyze the contents of PS homopolymers in the as-synthesized block copolymers. In addition, I have developed an IC technique to provide faster and more reliable information on the chemical heterogeneity in the as-synthesized block copolymers. Finally, a large scale (multi-gram) separation technique is developed to obtain "homopolymer-free" block copolymers via a simple chromatographic filtration technique. By taking advantage of the large specific surface area of nanoporous silica (≈300m 2/g), large scale purification of neat PS-b-PMMA has successfully been achieved by controlling adsorption and desorption of the block copolymers on the silica gel surface using a gravity column. The second part of this thesis is focused on the liquid chromatography analysis and fractionation of RAFT-polymerized PS-b -PMMA diblock copolymers and AFM studies. In this study, PS- b-PMMA block copolymers were synthesized by a RAFT free radical polymerization process---the PMMA block with a phenyldithiobenzoate end group was synthesized first. The contents of unreacted PS and PMMA homopolymers in as-synthesized PS-b-PMMA block copolymers were quantitatively analyzed by solvent gradient interaction chromatography (SGIC) technique employing bare silica and C18-bonded silica columns, respectively. In addition, by 2-dimensional large-scale IC fractionation method, atomic force microscopy (AFM) study of these fractionated samples revealed various morphologies with respect to the chemical composition of each fraction. The third part of this thesis is to analyze random copolymers with tunable monomer sequence distributions using interaction chromatography. Here, IC was used for characterizing the composition and monomer sequence distribution in statistical copolymers of poly(styrene-co-4-bromostyrene) (PBrxS). The PBrS copolymers were synthesized by the bromination of monodisperse polystyrenes; the degree of bromination (x) and the sequence distribution were adjusted by varying the bromination time and the solvent quality, respectively. Both normal-phase (bare silica) and reversed-phase (C18-bonded silica) columns were used at different combinations of solvents and non-solvents to monitor the content of the 4-bromostyrene units in the copolymer and their average monomer sequence distribution. The fourth part of this thesis is to analyze and fractionate highly branched polymers such as dendronized polymers and star-shaped homo and copolymers. I have developed an interaction chromatography technique to separate polymers with nonlinear chain architecture. Specifically, the IC technique has been used to separate dendronized polymers and PS-based highly branched copolymers and to ultimately obtain well-defined dendronized or branched copolymers with a low polydispersity. The effects of excess arm-polymers on (1) the micellar self-assembly of dendronized polymers and (2) the regularity of the pore morphology in the low-k applications by the sol-gel process have been studied.

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

NASA Astrophysics Data System (ADS)

McLeod, David Charles

Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular compositions, architectures, and thermal stabilities of the resulting ?-hydroxy ether-functionalized homopolymers were evaluated using NMR and FTIR spectroscopy, size exclusion chromatography, and thermal gravimetric analysis. Aziridines and thiiranes (saturated, three-membered heterocycles containing either a single nitrogen or sulfur atom, respectively) are also susceptible to nucleophilic ring-opening reactions, and functional materials derived from aziridine- or thiirane-containing polymers could potentially have many interesting properties as a result of their high amine or thiol content, such as the ability to form pH- or redox-responsive structures. The synthesis of polymers containing aziridines that are activated towards nucleophilic ring-opening by C-aryl and/or N-sulfonyl substituents is unprecedented in the literature. Efficient methods for synthesizing styrenic monomers that contain these highly-reactive functionalities, namely 2-(4-vinylphenyl)aziridine (VPA) and its sulfonyl-activated derivative, N-mesyl-2-(4-vinylphenyl)aziridine (NMVPA), were developed utilizing 4VPO as a starting material. VPA was polymerized under LCC ATRP and RAFT conditions, but these methods were ineffective at producing well-defined polymers due to side reactions between the aziridine groups and the polymerization mediating compounds. Nitroxide-mediated radical polymerization (NMRP) produced well-defined polyVPA at low to moderate conversions of monomer, but cross-linking side reactions were evident at higher monomer conversions. Nearly all undesirable side reactions were prevented by attaching a mesyl group to the aziridine nitrogen atom, and well-defined polyNMVPA was realized under RAFT and NMRP conditions. Under ATRP conditions, reactions between the aziridine groups and catalyst still occurred, so the polymerization of NMVPA was not controlled using this technique. The synthesis of thiirane-containing styrenic polymers from either 2-(4-vinylphenyl)thiirane (VPT) or 2-((4-vinylphenoxy)methyl)thiirane (VPOMT), which were produced in a facile manner from 4VPO or 4VPGE, respectively, was attempted under conventional radical polymerization and RAFT polymerization conditions. Rapid desulfurization or ring-opening polymerization of VPT occurred when elevated temperatures or UV radiation was applied to reactions containing this monomer. The more-stable VPOMT monomer was successfully polymerized at elevated temperatures using thermally-labile azo-type initiators, and, under RAFT conditions, polymers of VPOMT increased in molecular weight as higher conversions of monomer were reached; however, the polymers produced under RAFT conditions were ill-defined and eventually underwent macrogelation, due to cross-linking side reactions of the thiirane moieties.

Other Targets in the Search for Life--from Saturn's Titan to Planetary Systems around other Stars

NASA Astrophysics Data System (ADS)

Lunine, J. I.

2001-12-01

In addition to the ``standard" targets in the search for life beyond Earth--namely Mars, Europa, and putative extra-solar terrestrial planets--there are others that are key to informing us as to the origin and persistence of life in the cosmos. Saturn's moon Titan, with its dense nitrogen atmosphere rich in methane, may hold important clues to how abiotic organic chemistry evolves toward biochemistry. In particular, while the stratospheric processing of methane and nitrogen by ultraviolet photons and cosmic rays generates a free radical chemistry that is by itself uninteresting from the point of view of biosynthesis, the products of this chemistry come to rest as liquids and solids on the surface of Titan. There, they are protected from upper atmospheric sources of energy, but localized surface processes, including those associated with impact heating, might drive the chemistry in interesting directions with respect to polymer structures, chirality, and other signatures of advanced organic chemistry. The first step in assessing these possibilities will come in three years with the Cassini-Huygens mission. Beyond our solar system, giant planets in orbit around other stars are not directly targets of the search for life elsewhere (their natural satellites being unpromising targets in terms of detectability), but their presence implies important things about the habitability of Earth-like planets that might orbit the same stars. Giant planets affect the orbital stability and impact history of terrestrial planets, as well as the delivery of water and biogenic compounds to the surfaces of putative ``other Earths". Further, giant planets provide fertile ground for testing detection and characterization techniques. Thus, to maximize the chances of success in answering the fundamental questions of astrobiology, we must broaden both our minds and the targets we choose to explore. Some of the work described herein was supported by the Jet Propulsion Laboratory's DDF, and by the NASA Origins Program.

Momentum conserving Brownian dynamics propagator for complex soft matter fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padding, J. T.; Briels, W. J.

2014-12-28

We present a Galilean invariant, momentum conserving first order Brownian dynamics scheme for coarse-grained simulations of highly frictional soft matter systems. Friction forces are taken to be with respect to moving background material. The motion of the background material is described by locally averaged velocities in the neighborhood of the dissolved coarse coordinates. The velocity variables are updated by a momentum conserving scheme. The properties of the stochastic updates are derived through the Chapman-Kolmogorov and Fokker-Planck equations for the evolution of the probability distribution of coarse-grained position and velocity variables, by requiring the equilibrium distribution to be a stationary solution.more » We test our new scheme on concentrated star polymer solutions and find that the transverse current and velocity time auto-correlation functions behave as expected from hydrodynamics. In particular, the velocity auto-correlation functions display a long time tail in complete agreement with hydrodynamics.« less

Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger†

PubMed Central

Phillips, Daniel J.; Congdon, Thomas R.; Gibson, Matthew I.

2016-01-01

Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-terminated poly(vinyl alcohol) was synthesised by RAFT polymerization. Upon addition of Fe3+, larger supramolecular star polymers form by assembly with two or three catechols. This increase in molecular weight effectively ‘switches on’ the IRI activity and is the first example of external control over the function of AFP mimetics. This provides a simple but elegant solution to the challenge of external control of AFP-mimetic function. PMID:28003855

Instability of counter-rotating stellar disks

NASA Astrophysics Data System (ADS)

Hohlfeld, R. G.; Lovelace, R. V. E.

2015-09-01

We use an N-body simulation, constructed using GADGET-2, to investigate an accretion flow onto an astrophysical disk that is in the opposite sense to the disk's rotation. In order to separate dynamics intrinsic to the counter-rotating flow from the impact of the flow onto the disk, we consider an initial condition in which the counter-rotating flow is in an annular region immediately exterior the main portion of the astrophysical disk. Such counter-rotating flows are seen in systems such as NGC 4826 (known as the "Evil Eye Galaxy"). Interaction between the rotating and counter-rotating components is due to two-stream instability in the boundary region. A multi-armed spiral density wave is excited in the astrophysical disk and a density distribution with high azimuthal mode number is excited in the counter-rotating flow. Density fluctuations in the counter-rotating flow aggregate into larger clumps and some of the material in the counter-rotating flow is scattered to large radii. Accretion flow processes such as this are increasingly seen to be of importance in the evolution of multi-component galactic disks.

Action Centered Contextual Bandits.

PubMed

Greenewald, Kristjan; Tewari, Ambuj; Klasnja, Predrag; Murphy, Susan

2017-12-01

Contextual bandits have become popular as they offer a middle ground between very simple approaches based on multi-armed bandits and very complex approaches using the full power of reinforcement learning. They have demonstrated success in web applications and have a rich body of associated theoretical guarantees. Linear models are well understood theoretically and preferred by practitioners because they are not only easily interpretable but also simple to implement and debug. Furthermore, if the linear model is true, we get very strong performance guarantees. Unfortunately, in emerging applications in mobile health, the time-invariant linear model assumption is untenable. We provide an extension of the linear model for contextual bandits that has two parts: baseline reward and treatment effect. We allow the former to be complex but keep the latter simple. We argue that this model is plausible for mobile health applications. At the same time, it leads to algorithms with strong performance guarantees as in the linear model setting, while still allowing for complex nonlinear baseline modeling. Our theory is supported by experiments on data gathered in a recently concluded mobile health study.

Coevolutionary Free Lunches

NASA Technical Reports Server (NTRS)

Wolpert, David H.; Macready, William G.

2005-01-01

Recent work on the foundations of optimization has begun to uncover its underlying rich structure. In particular, the "No Free Lunch" (NFL) theorems [WM97] state that any two algorithms are equivalent when their performance is averaged across all possible problems. This highlights the need for exploiting problem-specific knowledge to achieve better than random performance. In this paper we present a general framework covering most search scenarios. In addition to the optimization scenarios addressed in the NFL results, this framework covers multi-armed bandit problems and evolution of multiple co-evolving agents. As a particular instance of the latter, it covers "self-play" problems. In these problems the agents work together to produce a champion, who then engages one or more antagonists in a subsequent multi-player game In contrast to the traditional optimization case where the NFL results hold, we show that in self-play there are free lunches: in coevolution some algorithms have better performance than other algorithms, averaged across all possible problems. However in the typical coevolutionary scenarios encountered in biology, where there is no champion, NFL still holds.

Understanding Melt-Memory of Commercial Polyolefins

NASA Astrophysics Data System (ADS)

Alamo, Rufina

Self-nucleation (SN) or controlling self-generated seeds in a polymer melt is an avenue to increase the rate of solidification of semicrystalline polymers of commercial relevance. Self-nuclei are remains in the melt of the segmental self-assembly to form polymer crystallites providing a path to enhance primary crystal nucleation. SN has been extensively studied in homopolymers such as iPP. Recently, a strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. The melt memory is associated with clusters or seeds that remain in the melt from the copolymer's sequence length partitioning. Cooling from progressively lower self-seeded melt temperatures, ethylene copolymers with a broad inter-chain comonomer composition (1 - 15 mol%) display first the expected accelerated crystallization, followed by a decrease in the rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. This unusual inversion of the crystallization rate was postulated to arise from the onset of liquid-liquid phase separation (LLPS) between comonomer-rich and comonomer-poor components of the broad copolymer. The UCST type phase diagram of these commercial copolymers has been documented via SANS using a blend of components, some deuterated, to reproduce the broad distribution. Furthermore, the components that contribute to LLPS have been identified by the crystallization behavior of molar mass fractions. The influence of long chain branching on the topology of copolymer melts has been analyzed using model 3-arm stars hydrogenated polybutadienes. The effect of melt viscosity on strength of melt memory is also evident when SN data of random ethylene copolymers are compared with those of propylene-ethylene copolymers. The strong dependence of melt viscosity on melt memory, and a critical threshold crystallinity level to observe the effect of melt memory on crystallization rate, support the kinetic nature of the SN phenomenon. Support from NSF, DMR-1105129 and DMR-1607786 is gratefully acknowledged.

A chemical EOR benchmark study of different reservoir simulators

NASA Astrophysics Data System (ADS)

Goudarzi, Ali; Delshad, Mojdeh; Sepehrnoori, Kamy

2016-09-01

Interest in chemical EOR processes has intensified in recent years due to the advancements in chemical formulations and injection techniques. Injecting Polymer (P), surfactant/polymer (SP), and alkaline/surfactant/polymer (ASP) are techniques for improving sweep and displacement efficiencies with the aim of improving oil production in both secondary and tertiary floods. There has been great interest in chemical flooding recently for different challenging situations. These include high temperature reservoirs, formations with extreme salinity and hardness, naturally fractured carbonates, and sandstone reservoirs with heavy and viscous crude oils. More oil reservoirs are reaching maturity where secondary polymer floods and tertiary surfactant methods have become increasingly important. This significance has added to the industry's interest in using reservoir simulators as tools for reservoir evaluation and management to minimize costs and increase the process efficiency. Reservoir simulators with special features are needed to represent coupled chemical and physical processes present in chemical EOR processes. The simulators need to be first validated against well controlled lab and pilot scale experiments to reliably predict the full field implementations. The available data from laboratory scale include 1) phase behavior and rheological data; and 2) results of secondary and tertiary coreflood experiments for P, SP, and ASP floods under reservoir conditions, i.e. chemical retentions, pressure drop, and oil recovery. Data collected from corefloods are used as benchmark tests comparing numerical reservoir simulators with chemical EOR modeling capabilities such as STARS of CMG, ECLIPSE-100 of Schlumberger, REVEAL of Petroleum Experts. The research UTCHEM simulator from The University of Texas at Austin is also included since it has been the benchmark for chemical flooding simulation for over 25 years. The results of this benchmark comparison will be utilized to improve chemical design for field-scale studies using commercial simulators. The benchmark tests illustrate the potential of commercial simulators for chemical flooding projects and provide a comprehensive table of strengths and limitations of each simulator for a given chemical EOR process. Mechanistic simulations of chemical EOR processes will provide predictive capability and can aid in optimization of the field injection projects. The objective of this paper is not to compare the computational efficiency and solution algorithms; it only focuses on the process modeling comparison.

Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

2016-12-01

We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

What is the optimal systemic treatment of men with metastatic, hormone-naive prostate cancer? A STOPCAP systematic review and network meta-analysis.

PubMed

Vale, C L; Fisher, D J; White, I R; Carpenter, J R; Burdett, S; Clarke, N W; Fizazi, K; Gravis, G; James, N D; Mason, M D; Parmar, M K B; Rydzewska, L H; Sweeney, C J; Spears, M R; Sydes, M R; Tierney, J F

2018-05-01

Our prior Systemic Treatment Options for Cancer of the Prostate systematic reviews showed improved survival for men with metastatic hormone-naive prostate cancer when abiraterone acetate plus prednisolone/prednisone (AAP) or docetaxel (Doc), but not zoledronic acid (ZA), were added to androgen-deprivation therapy (ADT). Trial evidence also suggests a benefit of combining celecoxib (Cel) with ZA and ADT. To establish the optimal treatments, a network meta-analysis (NMA) was carried out based on aggregate data (AD) from all available studies. Overall survival (OS) and failure-free survival data from completed Systemic Treatment Options for Cancer of the Prostate reviews of Doc, ZA and AAP and from recent trials of ZA and Cel contributed to this comprehensive AD-NMA. The primary outcome was OS. Correlations between treatment comparisons within one multi-arm, multi-stage trial were estimated from control-arm event counts. Network consistency and a common heterogeneity variance were assumed. We identified 10 completed trials which had closed to recruitment, and one trial in which recruitment was ongoing, as eligible for inclusion. Results are based on six trials including 6204 men (97% of men randomised in all completed trials). Network estimates of effects on OS were consistent with reported comparisons with ADT alone for AAP [hazard ration (HR) = 0.61, 95% confidence interval (CI) 0.53-0.71], Doc (HR = 0.77, 95% CI 0.68-0.87), ZA + Cel (HR = 0.78, 95% CI 0.62-0.97), ZA + Doc (HR = 0.79, 95% CI 0.66-0.94), Cel (HR = 0.94 95% CI 0.75-1.17) and ZA (HR = 0.90 95% CI 0.79-1.03). The effect of ZA + Cel is consistent with the additive effects of the individual treatments. Results suggest that AAP has the highest probability of being the most effective treatment both for OS (94% probability) and failure-free survival (100% probability). Doc was the second-best treatment of OS (35% probability). Uniquely, we have included all available results and appropriately accounted for inclusion of multi-arm, multi-stage trials in this AD-NMA. Our results support the use of AAP or Doc with ADT in men with metastatic hormone-naive prostate cancer. AAP appears to be the most effective treatment, but it is not clear to what extent and whether this is due to a true increased benefit with AAP or the variable features of the individual trials. To fully account for patient variability across trials, changes in prognosis or treatment effects over time and the potential impact of treatment on progression, a network meta-analysis based on individual participant data is in development.

Evaluation of a New Prototype Geodetic Astrolabe for Measuring Deflections of the Vertical

NASA Astrophysics Data System (ADS)

Slater, J. A.; Thompson, N.; Angell, L. E.; Belenkii, M. S.; Bruns, D. G.; Johnson, D. O.

2009-12-01

During the last three years, the National Geospatial-Intelligence Agency (NGA), with assistance from the U.S. Naval Observatory (USNO), sponsored the development of a new electronic geodetic astrolabe for measuring deflections of the vertical (DoV). NGA’s current operational astrolabes, built in 1995, have a number of undesirable features including the need for a pool of liquid mercury as a reflecting surface. The new state-of-the-art prototype instrument, completed by Trex Enterprises in early 2009, was designed to meet a 0.2 arcsec accuracy requirement. It reduces the weight, eliminates the mercury, and dramatically reduces observation times. The new astrolabe consists of a 101 mm aperture telescope with a 1.5° field of view and an inclinometer mounted inside a 92-cm high, 30-cm diameter tube, an external GPS receiver for timing, and a laptop computer that controls and monitors the instrument and performs the computations. Star images are recorded by an astronomical-grade camera with a 2,048 x 2,048 pixel CCD sensor that is externally triggered by time pulses from the GPS receiver. The prototype was designed for nighttime observation of visible stars equal to or brighter than magnitude 10.0. The inclinometer is a system of two orthogonal pendula that define the local gravitational vertical, each consisting of a brass plumb bob suspended from an aluminized polymer ribbon set between two electrodes. An internal reference collimator is rigidly tied to the inclinometer and projects an array of reference points of light onto the CCD sensor. After the astrolabe is coarsely leveled to within 20 arcsec, voice coil actuators automatically adjust and maintain the inclinometer vertical to within 0.02 arcsec. Independent images are collected at 6 second intervals using a 200 msec exposure time. The CCD coordinates are determined for each star and a collimator reference point on each image. Stars are identified by referencing a customized star catalog produced by USNO. A plate model is fitted to the topocentric coordinates of the stars, and then used to solve for the astronomical latitude and longitude of the vertical reference point on the CCD. The average of 100-150 individual image solutions (10-15 minutes) defines the astronomical position for the observation session. In order to remove an azimuthal orientation bias, the astrolabe is rotated 180°, a new observation session solution is produced for that orientation and then averaged with the first solution to get the final astronomical position of the site. By combining these coordinates with GPS-derived geodetic latitude and longitude, one obtains the DoV. Initial testing of the prototype at a known astronomic position has been completed. The tests evaluated the session-to-session and day-to-day repeatability of the solutions, the number of observations required for a solution, the accuracy with respect to the known position, and the operational robustness of the hardware and software. Based on the field tests, Trex will make improvements to the prototype hardware and software and then produce operational units for use by NGA.

Synthesis, characterization, and evaluation of paclitaxel loaded in six-arm star-shaped poly(lactic-co-glycolic acid)

PubMed Central

Chen, Yongxia; Yang, Ziying; Liu, Chao; Wang, Cuiwei; Zhao, Shunxin; Yang, Jing; Sun, Hongfan; Zhang, Zhengpu; Kong, Deling; Song, Cunxian

2013-01-01

Background Star-shaped polymers provide more terminal groups, and are promising for application in drug-delivery systems. Methods A new series of six-arm star-shaped poly(lactic-co-glycolic acid) (6-s-PLGA) was synthesized by ring-opening polymerization. The structure and properties of the 6-s-PLGA were characterized by carbon-13 nuclear magnetic resonance spectroscopy, infrared spectroscopy, gel permeation chromatography, and differential scanning calorimetry. Then, paclitaxel-loaded six-arm star-shaped poly(lactic-co-glycolic acid) nanoparticles (6-s-PLGA-PTX-NPs) were prepared under the conditions optimized by the orthogonal testing. High-performance liquid chromatography was used to analyze the nanoparticles’ encapsulation efficiency and drug-loading capacity, dynamic light scattering was used to determine their size and size distribution, and transmission electron microscopy was used to evaluate their morphology. The release performance of the 6-s-PLGA-PTX-NPs in vitro and the cytostatic effect of 6-s-PLGA-PTX-NPs were investigated in comparison with paclitaxel-loaded linear poly(lactic-co-glycolic acid) nanoparticles (L-PLGA-PTX-NPs). Results The results of carbon-13 nuclear magnetic resonance spectroscopy and infrared spectroscopy suggest that the polymerization was successfully initiated by inositol and confirm the structure of 6-s-PLGA. The molecular weights of a series of 6-s-PLGAs had a ratio corresponding to the molar ratio of raw materials to initiator. Differential scanning calorimetry revealed that the 6-s-PLGA had a low glass transition temperature of 40°C–50°C. The 6-s-PLGA-PTX-NPs were monodispersed with an average diameter of 240.4±6.9 nm in water, which was further confirmed by transmission electron microscopy. The encapsulation efficiency of the 6-s-PLGA-PTX-NPs was higher than that of the L-PLGA-PTX-NPs. In terms of the in vitro release of nanoparticles, paclitaxel (PTX) was released more slowly and more steadily from 6-s-PLGA than from linear poly(lactic-co-glycolic acid). In the cytostatic study, the 6-s-PLGA-PTX-NPs and L-PLGA-PTX-NPs were found to have a similar antiproliferative effect, which indicates durable efficacy due to the slower release of the PTX when loaded in 6-s-PLGA. Conclusion The results suggest that 6-s-PLGA may be promising for application in PTX delivery to enhance sustained antiproliferative therapy. PMID:24235829

Mussel-inspired histidine-based transient network metal coordination hydrogels

PubMed Central

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

Nitroxide-Based Macromolecular Contrast Agents with Unprecedented Transverse Relaxivity and Stability for Magnetic Resonance Imaging of Tumors

PubMed Central

2017-01-01

Metal-free magnetic resonance imaging (MRI) agents could overcome the established toxicity associated with metal-based agents in some patient populations and enable new modes of functional MRI in vivo. Herein, we report nitroxide-functionalized brush-arm star polymer organic radical contrast agents (BASP-ORCAs) that overcome the low contrast and poor in vivo stability associated with nitroxide-based MRI contrast agents. As a consequence of their unique nanoarchitectures, BASP-ORCAs possess per-nitroxide transverse relaxivities up to ∼44-fold greater than common nitroxides, exceptional stability in highly reducing environments, and low toxicity. These features combine to provide for accumulation of a sufficient concentration of BASP-ORCA in murine subcutaneous tumors up to 20 h following systemic administration such that MRI contrast on par with metal-based agents is observed. BASP-ORCAs are, to our knowledge, the first nitroxide MRI contrast agents capable of tumor imaging over long time periods using clinical high-field 1H MRI techniques. PMID:28776023

Phases and Dynamics of Self-Assembled DNA Programmed Nanocubes

NASA Astrophysics Data System (ADS)

Knorowski, Christopher; Travesset, Alex

2013-03-01

Systems of Nanoparticles grafted with complementary DNA strands have been shown to self-assemble into an array of superlattices. In this talk, we extend our previous model, which successfully predicted equilibrium phases and dynamics of assembly for spherical Nanoparticles without fitting parameters, to the case of nanocubes. We show that the phase diagram consists of bcc and sc lattices, depending on DNA length. The bcc lattices are either rotator and orientational glass or cubatic. For temperatures above the DNA melting temperature, the system is equivalent to f-star polymer systems, and consist of bcc, also with rotator, orientational glass or cubatic orientational order as well as sc. We also provide a characterization of the dynamics, including the role of topological defects in crystal nucleation and growth. This work is funded by DOE through the Ames Lab under Contract DE-AC02-07CH11358. Most simulations are performed on the Exalted GPU cluster, which is funded by a grant from Iowa State University and Nvidia Corp.

System for star catalog equalization to enhance attitude determination

NASA Technical Reports Server (NTRS)

Liu, Yong (Inventor); Wu, Yeong-Wei Andy (Inventor); Li, Rongsheng (Inventor)

2001-01-01

An apparatus for star catalog equalization to enhance attitude determination includes a star tracker, a star catalog and a controller. The star tracker is used to sense the positions of stars and generate signals corresponding to the positions of the stars as seen in its field of view. The star catalog contains star location data that is stored using a primary and multiple secondary arrays sorted by both declination (DEC) and right ascension (RA), respectively. The star location data stored in the star catalog is predetermined by calculating a plurality of desired star locations, associating one of a plurality of stars with each of the plurality of desired star locations based upon a neighborhood association angle to generate an associated plurality of star locations: If an artificial star gap occurs during association, then the neighborhood association angle for reassociation is increased. The controller uses the star catalog to determine which stars to select to provide star measurement residuals for correcting gyroscope bias and spacecraft attitude.

A Bayesian adaptive design for biomarker trials with linked treatments.

PubMed

Wason, James M S; Abraham, Jean E; Baird, Richard D; Gournaris, Ioannis; Vallier, Anne-Laure; Brenton, James D; Earl, Helena M; Mander, Adrian P

2015-09-01

Response to treatments is highly heterogeneous in cancer. Increased availability of biomarkers and targeted treatments has led to the need for trial designs that efficiently test new treatments in biomarker-stratified patient subgroups. We propose a novel Bayesian adaptive randomisation (BAR) design for use in multi-arm phase II trials where biomarkers exist that are potentially predictive of a linked treatment's effect. The design is motivated in part by two phase II trials that are currently in development. The design starts by randomising patients to the control treatment or to experimental treatments that the biomarker profile suggests should be active. At interim analyses, data from treated patients are used to update the allocation probabilities. If the linked treatments are effective, the allocation remains high; if ineffective, the allocation changes over the course of the trial to unlinked treatments that are more effective. Our proposed design has high power to detect treatment effects if the pairings of treatment with biomarker are correct, but also performs well when alternative pairings are true. The design is consistently more powerful than parallel-groups stratified trials. This BAR design is a powerful approach to use when there are pairings of biomarkers with treatments available for testing simultaneously.

Bayesian adaptive phase II screening design for combination trials.

PubMed

Cai, Chunyan; Yuan, Ying; Johnson, Valen E

2013-01-01

Trials of combination therapies for the treatment of cancer are playing an increasingly important role in the battle against this disease. To more efficiently handle the large number of combination therapies that must be tested, we propose a novel Bayesian phase II adaptive screening design to simultaneously select among possible treatment combinations involving multiple agents. Our design is based on formulating the selection procedure as a Bayesian hypothesis testing problem in which the superiority of each treatment combination is equated to a single hypothesis. During the trial conduct, we use the current values of the posterior probabilities of all hypotheses to adaptively allocate patients to treatment combinations. Simulation studies show that the proposed design substantially outperforms the conventional multiarm balanced factorial trial design. The proposed design yields a significantly higher probability for selecting the best treatment while allocating substantially more patients to efficacious treatments. The proposed design is most appropriate for the trials combining multiple agents and screening out the efficacious combination to be further investigated. The proposed Bayesian adaptive phase II screening design substantially outperformed the conventional complete factorial design. Our design allocates more patients to better treatments while providing higher power to identify the best treatment at the end of the trial.

The involvement of model-based but not model-free learning signals during observational reward learning in the absence of choice.

PubMed

Dunne, Simon; D'Souza, Arun; O'Doherty, John P

2016-06-01

A major open question is whether computational strategies thought to be used during experiential learning, specifically model-based and model-free reinforcement learning, also support observational learning. Furthermore, the question of how observational learning occurs when observers must learn about the value of options from observing outcomes in the absence of choice has not been addressed. In the present study we used a multi-armed bandit task that encouraged human participants to employ both experiential and observational learning while they underwent functional magnetic resonance imaging (fMRI). We found evidence for the presence of model-based learning signals during both observational and experiential learning in the intraparietal sulcus. However, unlike during experiential learning, model-free learning signals in the ventral striatum were not detectable during this form of observational learning. These results provide insight into the flexibility of the model-based learning system, implicating this system in learning during observation as well as from direct experience, and further suggest that the model-free reinforcement learning system may be less flexible with regard to its involvement in observational learning. Copyright © 2016 the American Physiological Society.

The Effect of Varied Initial Conditions on the Evolution of Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Michael, Scott A.; Durisen, R. H.; Boley, A. C.

2006-12-01

We present a series of three-dimensional hydrodynamics simulations of gravitationally unstable protoplanetary disks with globally constant cooling times. The purpose of these simulations is to study the effects of varying the initial surface density profile, equation of state, and cooling time. All non-fragmenting disks exhibit the same phases of evolution described by Mejía et al. (2005) axisymmetric cooling, a burst in a well-defined multi-armed mode, and a transition to an asymptotic behavior in which heating and cooling are roughly balanced over much of the disk. The burst tends to be weaker for initial surface density profiles that fall more steeply with r. Regardless of initial surface density profile, the outer disk redistributes its mass to follow an approximate Σ ∝ r-5/2 power law. Comparison of different equations of state show that, for a given cooling time, a disk with γ = 7/5 is more likely to fragment than one with γ = 5/3. By varying the cooling time with both equations of state, we are able to confirm the tcoolΩ < 8.25 and 5.14 fragmentation criterion for γ = 7/5 and 5/3, respectively, as found by Rice et al. (2005).

SiRNA Crosslinked Nanoparticles for the Treatment of Inflammation-induced Liver Injury.

PubMed

Tang, Yaqin; Zeng, Ziying; He, Xiao; Wang, Tingting; Ning, Xinghai; Feng, Xuli

2017-02-01

RNA interference mediated by small interfering RNA (siRNA) provides a powerful tool for gene regulation, and has a broad potential as a promising therapeutic strategy. However, therapeutics based on siRNA have had limited clinical success due to their undesirable pharmacokinetic properties. This study presents pH-sensitive nanoparticles-based siRNA delivery systems (PNSDS), which are positive-charge-free nanocarriers, composed of siRNA chemically crosslinked with multi-armed poly(ethylene glycol) carriers via acid-labile acetal linkers. The unique siRNA crosslinked structure of PNSDS allows it to have minimal cytotoxicity, high siRNA loading efficiency, and a stimulus-responsive property that enables the selective intracellular release of siRNA in response to pH conditions. This study demonstrates that PNSDS can deliver tumor necrosis factor alpha (TNF-α) siRNA into macrophages and induce the efficient down regulation of the targeted gene in complete cell culture media. Moreover, PNSDS with mannose targeting moieties can selectively accumulate in mice liver, induce specific inhibition of macrophage TNF-α expression in vivo, and consequently protect mice from inflammation-induced liver damages. Therefore, this novel siRNA delivering platform would greatly improve the therapeutic potential of RNAi based therapies.

Selective automation and skill transfer in medical robotics: a demonstration on surgical knot-tying.

PubMed

Knoll, Alois; Mayer, Hermann; Staub, Christoph; Bauernschmitt, Robert

2012-12-01

Transferring non-trivial human manipulation skills to robot systems is a challenging task. There have been a number of attempts to design research systems for skill transfer, but the level of the complexity of the actual skills transferable to the robot was rather limited, and delicate operations requiring a high dexterity and long action sequences with many sub-operations were impossible to transfer. A novel approach to human-machine skill transfer for multi-arm robot systems is presented. The methodology capitalizes on the metaphor of 'scaffolded learning', which has gained widespread acceptance in psychology. The main idea is to formalize the superior knowledge of a teacher in a certain way to generate support for a trainee. In our case, the scaffolding is constituted by abstract patterns, which facilitate the structuring and segmentation of information during 'learning by demonstration'. The actual skill generalization is then based on simulating fluid dynamics. The approach has been successfully evaluated in the medical domain for the delicate task of automated knot-tying for suturing with standard surgical instruments and a realistic minimally invasive robotic surgery system. Copyright © 2012 John Wiley & Sons, Ltd.

Combinations of 148 navigation stars and the star tracker

NASA Technical Reports Server (NTRS)

Duncan, R.

1980-01-01

The angular separation of all star combinations for 148 nav star on the onboard software for space transportation system-3 flight and following missions is presented as well as the separation of each pair that satisfies the viewing constraints of using both star trackers simultaneously. Tables show (1) shuttle star catalog 1980 star position in M 1950 coordinates; (2) two star combination of 148 nav stars; and (3) summary of two star-combinations of the star tracker 5 deg filter. These 148 stars present 10,875 combinations. For the star tracker filters of plus or minus 5 deg, there are 875 combinations. Formalhaut (nav star 26) has the best number of combinations, which is 33.

Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

NASA Astrophysics Data System (ADS)

Theodorakis, P. E.; Avgeropoulos, A.; Freire, J. J.; Kosmas, M.; Vlahos, C.

2007-11-01

The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.

Modeling and self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution

NASA Astrophysics Data System (ADS)

Wu, Xiaohan; Li, Suming; Coumes, Fanny; Darcos, Vincent; Lai Kee Him, Joséphine; Bron, Patrick

2013-09-01

A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications.A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications. Electronic supplementary information (ESI) available: 1H-NMR, DOSY, FTIR, and GPC measurements, methods and results of the copolymers in PEG-PLA-PEG synthesis. See DOI: 10.1039/c3nr02899b

False star detection and isolation during star tracking based on improved chi-square tests.

PubMed

Zhang, Hao; Niu, Yanxiong; Lu, Jiazhen; Yang, Yanqiang; Su, Guohua

2017-08-01

The star sensor is a precise attitude measurement device for a spacecraft. Star tracking is the main and key working mode for a star sensor. However, during star tracking, false stars become an inevitable interference for star sensor applications, which may result in declined measurement accuracy. A false star detection and isolation algorithm in star tracking based on improved chi-square tests is proposed in this paper. Two estimations are established based on a Kalman filter and a priori information, respectively. The false star detection is operated through adopting the global state chi-square test in a Kalman filter. The false star isolation is achieved using a local state chi-square test. Semi-physical experiments under different trajectories with various false stars are designed for verification. Experiment results show that various false stars can be detected and isolated from navigation stars during star tracking, and the attitude measurement accuracy is hardly influenced by false stars. The proposed algorithm is proved to have an excellent performance in terms of speed, stability, and robustness.

Design and application of star map simulation system for star sensors

NASA Astrophysics Data System (ADS)

Wu, Feng; Shen, Weimin; Zhu, Xifang; Chen, Yuheng; Xu, Qinquan

2013-12-01

Modern star sensors are powerful to measure attitude automatically which assure a perfect performance of spacecrafts. They achieve very accurate attitudes by applying algorithms to process star maps obtained by the star camera mounted on them. Therefore, star maps play an important role in designing star cameras and developing procession algorithms. Furthermore, star maps supply significant supports to exam the performance of star sensors completely before their launch. However, it is not always convenient to supply abundant star maps by taking pictures of the sky. Thus, star map simulation with the aid of computer attracts a lot of interests by virtue of its low price and good convenience. A method to simulate star maps by programming and extending the function of the optical design program ZEMAX is proposed. The star map simulation system is established. Firstly, based on analyzing the working procedures of star sensors to measure attitudes and the basic method to design optical system by ZEMAX, the principle of simulating star sensor imaging is given out in detail. The theory about adding false stars and noises, and outputting maps is discussed and the corresponding approaches are proposed. Then, by external programming, the star map simulation program is designed and produced. Its user interference and operation are introduced. Applications of star map simulation method in evaluating optical system, star image extraction algorithm and star identification algorithm, and calibrating system errors are presented completely. It was proved that the proposed simulation method provides magnificent supports to the study on star sensors, and improves the performance of star sensors efficiently.

The multiplicity of T Tauri stars in the star forming regions Taurus-Auriga and Ophiuchus-Scorpius: A 2.2 micron speckle imaging survey

NASA Technical Reports Server (NTRS)

Ghez, A. M.; Neugebauer, G.; Matthews, K.

1993-01-01

We present the results of a magnitude limited (K less than = 8.5 mag) speckle imaging survey of 69 T Tauri stars in the star forming regions Taurus-Auriga and Ophiuchus-Scorpius. Thirty-three companion stars were found with separations ranging from 0.07 sec to 2.5 sec, nine are new detections. This survey reveals a distinction between the classical T Tauri stars (CTTS) and the weak-lined T Tauri stars (WTTS) based on the binary star frequency as a function of separation: the WTTS binary star distribution is enhanced at the closer separations (less than 50 AU) relative to the CTTS binary star distribution. We suggest that the nearby companion stars shorten the accretion time scale in multiple star systems, thereby accounting for the presence of WTTS that are coeval with many CTTS. The binary star frequency in the projected linear separation range 16 to 252 AU for T Tauri stars (60 (+/- 17)%) is a factor of 4 greater than that of the solar-type main-sequence stars (16(+/- 3)%). Given the limited separation range of this survey, the rate at which binaries are detected suggests that most, if not all, T Tauri stars have companions. We propose that the observed overabundance of companions of T Tauri stars is an evolutionary effect, in which triple and higher order T Tauri stars are disrupted by close encounters with another star or system of stars.

An Introduction to the Sun and Stars

NASA Astrophysics Data System (ADS)

Green, Simon F.; Jones, Mark H.

2015-02-01

Introduction; 1. Seeing the Sun; 2. The working Sun; 3. Measuring stars; 4. Comparing stars; 5. The formation of stars; 6. The main sequence life of stars; 7. The life of stars beyond the main sequence; 8. The death of stars; 9. The remnants of stars; Conclusion; Answers and comments; Appendices; Glossary; Further reading; Acknowledgements; Figure references; Index.

A Brightness-Referenced Star Identification Algorithm for APS Star Trackers

PubMed Central

Zhang, Peng; Zhao, Qile; Liu, Jingnan; Liu, Ning

2014-01-01

Star trackers are currently the most accurate spacecraft attitude sensors. As a result, they are widely used in remote sensing satellites. Since traditional charge-coupled device (CCD)-based star trackers have a limited sensitivity range and dynamic range, the matching process for a star tracker is typically not very sensitive to star brightness. For active pixel sensor (APS) star trackers, the intensity of an imaged star is valuable information that can be used in star identification process. In this paper an improved brightness referenced star identification algorithm is presented. This algorithm utilizes the k-vector search theory and adds imaged stars' intensities to narrow the search scope and therefore increase the efficiency of the matching process. Based on different imaging conditions (slew, bright bodies, etc.) the developed matching algorithm operates in one of two identification modes: a three-star mode, and a four-star mode. If the reference bright stars (the stars brighter than three magnitude) show up, the algorithm runs the three-star mode and efficiency is further improved. The proposed method was compared with other two distinctive methods the pyramid and geometric voting methods. All three methods were tested with simulation data and actual in orbit data from the APS star tracker of ZY-3. Using a catalog composed of 1500 stars, the results show that without false stars the efficiency of this new method is 4∼5 times that of the pyramid method and 35∼37 times that of the geometric method. PMID:25299950

A brightness-referenced star identification algorithm for APS star trackers.

PubMed

Zhang, Peng; Zhao, Qile; Liu, Jingnan; Liu, Ning

2014-10-08

Star trackers are currently the most accurate spacecraft attitude sensors. As a result, they are widely used in remote sensing satellites. Since traditional charge-coupled device (CCD)-based star trackers have a limited sensitivity range and dynamic range, the matching process for a star tracker is typically not very sensitive to star brightness. For active pixel sensor (APS) star trackers, the intensity of an imaged star is valuable information that can be used in star identification process. In this paper an improved brightness referenced star identification algorithm is presented. This algorithm utilizes the k-vector search theory and adds imaged stars' intensities to narrow the search scope and therefore increase the efficiency of the matching process. Based on different imaging conditions (slew, bright bodies, etc.) the developed matching algorithm operates in one of two identification modes: a three-star mode, and a four-star mode. If the reference bright stars (the stars brighter than three magnitude) show up, the algorithm runs the three-star mode and efficiency is further improved. The proposed method was compared with other two distinctive methods the pyramid and geometric voting methods. All three methods were tested with simulation data and actual in orbit data from the APS star tracker of ZY-3. Using a catalog composed of 1500 stars, the results show that without false stars the efficiency of this new method is 4~5 times that of the pyramid method and 35~37 times that of the geometric method.

Toward the first stars: hints from the CEMP-no stars

NASA Astrophysics Data System (ADS)

Choplin, A.

2017-12-01

CEMP-no stars are iron-deficient, carbon-rich stars, with no or little s- and r-elements. Because of their very low iron content, they are often considered to be closely linked to the first stars. Their origin is still a matter of debate. Understanding their formation could provide very valuable information on the first stars, early nucleosynthesis, early galactic chemical evolution and first supernovae. The most explored formation scenario for CEMP-no stars suggests that CEMP-no stars formed from the ejecta (wind and/or supernova) of a massive source star, that lived before the CEMP-no star. Here we discuss models of fast rotating massive source stars with and without triggering a late mixing event just before the end of the life of the source star. We find that without this late mixing event, the bulk of observed CEMP-no stars cannot be reproduced by our models. On the opposite, the bulk is reproductible if adding the late mixing event in the source star models.

A novel star extraction method based on modified water flow model

NASA Astrophysics Data System (ADS)

Zhang, Hao; Niu, Yanxiong; Lu, Jiazhen; Ouyang, Zibiao; Yang, Yanqiang

2017-11-01

Star extraction is the essential procedure for attitude measurement of star sensor. The great challenge for star extraction is to segment star area exactly from various noise and background. In this paper, a novel star extraction method based on Modified Water Flow Model(MWFM) is proposed. The star image is regarded as a 3D terrain. The morphology is adopted for noise elimination and Tentative Star Area(TSA) selection. Star area can be extracted through adaptive water flowing within TSAs. This method can achieve accurate star extraction with improved efficiency under complex conditions such as loud noise and uneven backgrounds. Several groups of different types of star images are processed using proposed method. Comparisons with existing methods are conducted. Experimental results show that MWFM performs excellently under different imaging conditions. The star extraction rate is better than 95%. The star centroid accuracy is better than 0.075 pixels. The time-consumption is also significantly reduced.

A new method for determining which stars are near a star sensor field-of-view

NASA Technical Reports Server (NTRS)

Yates, Russell E., Jr.; Vedder, John D.

1991-01-01

A new method is described for determining which stars in a navigation star catalog are near a star sensor field of view (FOV). This method assumes that an estimate of spacecraft inertial attitude is known. Vector component ranges for the star sensor FOV are computed, so that stars whose vector components lie within these ranges are near the star sensor FOV. This method requires no presorting of the navigation star catalog, and is more efficient than tradition methods.

The Maximum Mass of Rotating Strange Stars

NASA Astrophysics Data System (ADS)

Szkudlarek, M.; Gondek-Rosiń; ska, D.; Villain, L.; Ansorg, M.

2012-12-01

Strange quark stars are considered as a possible alternative to neutron stars as compact objects (e.g. Weber 2003). A hot compact star (a proto-neutron star or a strange star) born in a supernova explosion or a remnant of neutron stars binary merger are expected to rotate differentially and be important sources of gravitational waves. We present results of the first relativistic calculations of differentially rotating strange quark stars for broad ranges of degree of differential rotation and maximum densities. Using a highly accurate, relativistic code we show that rotation may cause a significant increase of maximum allowed mass of strange stars, much larger than in the case of neutron stars with the same degree of differential rotation. Depending on the maximum allowed mass a massive neutron star (strange star) can be temporarily stabilized by differential rotation or collapse to a black hole.

Fifteen DO, PG 1159 and related white dwarf stars in the SDSS, including two DO stars with ultra-high excitation ion lines

NASA Astrophysics Data System (ADS)

Krzesiński, J.; Nitta, A.; Kleinman, S. J.; Harris, H. C.; Liebert, J.; Schmidt, G.; Lamb, D. Q.; Brinkmann, J.

2004-04-01

We report on observations of 15 spectroscopically-identified DO stars from the Sloan Digital Sky Survey (SDSS) database, 13 of which are new discoveries. There are four PG 1159 type stars, two DO stars showing ultra-high excitation ion features (CVI, NVII, OVII, OVIII, NeIX, NeX) likely formed in stellar winds, 6 normal DO stars, one DBO and DBAO star, and one DAO star, which may also be magnetic. Since roughly 60 DO stars were known up to now, this new finding substantially increases the number of known DO white dwarf stars and we expect to at least double the current number of known DO stars by the end of the SDSS. We present each spectrum and provide catalog information (magnitudes, proper motion, coordinates) for each star.

Registration of eight six-rowed feed barley germplasm lines resistant to both Russian wheat aphid and greenbug

USDA-ARS?s Scientific Manuscript database

STARS 1006B (Reg. No. GP- , PI 659760), STARS 1007B (Reg. No. GP- , PI 659761), STARS 1008B (Reg. No. GP- , PI 659762), STARS 1009B (Reg. No. GP- , PI 659763), STARS 1010B (Reg. No. GP- , PI 659764), STARS 1011B (Reg. No. GP- , PI 659765), STARS 1012B (Reg. No. GP- , PI 659766), and STARS 1013B (Reg...

A deep near-infrared spectroscopic survey of the Scutum-Crux arm for Wolf-Rayet stars

NASA Astrophysics Data System (ADS)

Rosslowe, C. K.; Crowther, Paul A.

2018-01-01

We present a New Technology Telescope/Son-of-Isaac spectroscopic survey of infrared selected Wolf-Rayet (WR) candidates in the Scutum-Crux spiral arm (298° ≤ l ≤ 340°, |b| ≤ 0.5°. We obtained near-IR spectra of 127 candidates, revealing 17 WR stars - a ∼13 per cent success rate - of which 16 are newly identified here. The majority of the new WR stars are classified as narrow-lined WN5-7 stars, with two broad-lined WN4-6 stars and three WC6-8 stars. The new stars, with distances estimated from previous absolute magnitude calibrations, have no obvious association with the Scutum-Crux arm. Refined near-infrared (YHJK) classification criteria based on over a hundred Galactic and Magellanic Cloud WR stars, providing diagnostics for hydrogen in WN stars, plus the identification of WO stars and intermediate WN/C stars. Finally, we find that only a quarter of WR stars in the survey region are associated with star clusters and/or H II regions, with similar statistics found for luminous blue variables (LBVs) in the Milky Way. The relative isolation of evolved massive stars is discussed, together with the significance of the co-location of LBVs and WR stars in young star clusters.

Far-infrared properties of flare stars and dM stars

NASA Technical Reports Server (NTRS)

Mullan, D. J.; Stencel, R. E.; Backman, D. E.

1989-01-01

Results are reported from a search of the IRAS data base for flare stars and for a control sample of dM stars. At 12 microns, 70-80 percent of both samples have been detected. The K-12 colors of flare stars are significantly different from those of dM stars: for a given K magnitude, a flare star is about 70 percent brighter at 12 microns than a dM star. At 100 microns, 27 percent of the flare stars which are sources at 12 microns have been detected, while none of the comparable dM stars has been detected. Implications for microflaring are discussed.

OPTICAL SPECTROSCOPY OF X-RAY-SELECTED YOUNG STARS IN THE CARINA NEBULA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaidya, Kaushar; Chen, Wen-Ping; Lee, Hsu-Tai

We present low-resolution optical spectra for 29 X-ray sources identified as either massive star candidates or low-mass pre-main-sequence (PMS) star candidates in the clusters Trumpler 16 and Trumpler 14 of the Carina Nebula. Spectra of two more objects (one with an X-ray counterpart, and one with no X-ray counterpart), not originally our targets, but found close (∼3″) to two of our targets, are presented as well. Twenty early-type stars, including an O8 star, seven B1–B2 stars, two B3 stars, a B5 star, and nine emission-line stars, are identified. Eleven T Tauri stars, including eight classical T Tauri stars (CTTSs) and threemore » weak-lined T Tauri stars, are identified. The early-type stars in our sample are more reddened compared to the previously known OB stars of the region. The Chandra hardness ratios of our T Tauri stars are found to be consistent with the Chandra hardness ratios of T Tauri stars of the Orion Nebula Cluster. Most early-type stars are found to be nonvariable in X-ray emission, except the B2 star J104518.81–594217.9, the B3 star J104507.84–594134.0, and the Ae star J104424.76–594555.0, which are possible X-ray variables. J104452.20–594155.1, a CTTS, is among the brightest and the hardest X-ray sources in our sample, appears to be a variable, and shows a strong X-ray flare. The mean optical and near-infrared photometric variability in the V and K{sub s} bands, of all sources, is found to be ∼0.04 and 0.05 mag, respectively. The T Tauri stars show significantly larger mean variation, ∼0.1 mag, in the K{sub s} band. The addition of one O star and seven B1–B2 stars reported here contributes to an 11% increase of the known OB population in the observed field. The 11 T Tauri stars are the first ever confirmed low-mass PMS stars in the Carina Nebula region.« less

Neutron Star Discovered Where a Black Hole Was Expected

NASA Astrophysics Data System (ADS)

2005-11-01

A very massive star collapsed to form a neutron star and not a black hole as expected, according to new results from NASA's Chandra X-ray Observatory. This discovery shows that nature has a harder time making black holes than previously thought. Scientists found this neutron star -- a dense whirling ball of neutrons about 12 miles in diameter -- in an extremely young star cluster. Astronomers were able to use well-determined properties of other stars in the cluster to deduce that the progenitor of this neutron star was at least 40 times the mass of the Sun. ESO Optical Image of Westerlund 1 ESO Optical Image of Westerlund 1 "Our discovery shows that some of the most massive stars do not collapse to form black holes as predicted, but instead form neutron stars," said Michael Muno, a UCLA postdoctoral Hubble Fellow and lead author of a paper to be published in The Astrophysical Journal Letters. When very massive stars make neutron stars and not black holes, they will have a greater influence on the composition of future generations of stars. When the star collapses to form the neutron star, more than 95% of its mass, much of which is metal-rich material from its core, is returned to the space around it. "This means that enormous amounts of heavy elements are put back into circulation and can form other stars and planets," said J. Simon Clark of the Open University in the United Kingdom. Animation: Dissolve from Optical to X-ray Image of Westerlund 1 Animation: Dissolve from Optical to X-ray Image of Westerlund 1 Astronomers do not completely understand how massive a star must be to form a black hole rather than a neutron star. The most reliable method for estimating the mass of the progenitor star is to show that the neutron star or black hole is a member of a cluster of stars, all of which are close to the same age. Because more massive stars evolve faster than less massive ones, the mass of a star can be estimated from if its evolutionary stage is known. Neutron stars and black holes are the end stages in the evolution of a star, so their progenitors must have been among the most massive stars in the cluster. Muno and colleagues discovered a pulsing neutron star in a cluster of stars known as Westerlund 1. This cluster contains a hundred thousand or more stars in a region only 30 light years across, which suggests that all the stars were born in a single episode of star formation. Based on optical properties such as brightness and color some of the normal stars in the cluster are known to have masses of about 40 suns. Since the progenitor of the neutron star has already exploded as a supernova, its mass must have been more than 40 solar masses. 2MASS Infrared Image of Westerlund 1 2MASS Infrared Image of Westerlund 1 Introductory astronomy courses sometimes teach that stars with more than 25 solar masses become black holes -- a concept that until recently had no observational evidence to test it. However, some theories allow such massive stars to avoid becoming black holes. For example, theoretical calculations by Alexander Heger of the University of Chicago and colleagues indicate that extremely massive stars blow off mass so effectively during their lives that they leave neutron stars when they go supernovae. Assuming that the neutron star in Westerlund 1 is one of these, it raises the question of where the black holes observed in the Milky Way and other galaxies come from. Other factors, such as the chemical composition of the star, how rapidly it is rotating, or the strength of its magnetic field might dictate whether a massive star leaves behind a neutron star or a black hole. The theory for stars of normal chemical composition leaves a small window of initial masses - between about 25 and somewhat less than 40 solar masses - for the formation of black holes from the evolution of single massive stars. The identification of additional neutron stars or the discovery of black holes in young star clusters should further constrain the masses and properties of neutron star and black hole progenitors. The work described by Muno was based on two Chandra observations on May 22 and June 18, 2005. NASA's Marshall Space Flight Center, Huntsville, Ala., manages the Chandra program for the agency's Science Mission Directorate. The Smithsonian Astrophysical Observatory controls science and flight operations from the Chandra X-ray Center in Cambridge, Mass. Additional information and images are available at: http://chandra.harvard.edu and http://chandra.nasa.gov

Stargazing: an integrative conceptual review, theoretical reconciliation, and extension for star employee research.

PubMed

Call, Matthew L; Nyberg, Anthony J; Thatcher, Sherry M B

2015-05-01

Stars--employees with disproportionately high and prolonged (a) performance, (b) visibility, and (c) relevant social capital--have garnered attention in economics, sociology, and management. However, star research is often isolated within these research disciplines. Thus, 3 distinct star research streams are evolving, each disconnected from the others and each bringing siloed theoretical perspectives, terms, and assumptions. A conceptual review of these perspectives reveals a focus on the expost effects that stars exert in organizations with little explanation of who a star is and how one becomes a star. To synthesize the stars literature across these 3 disciplines, we apply psychological theories, specifically motivation theories, to create an integrative framework for stars research. Thus, we present a unified stars definition and extend theory on the making, managing, and mobility of stars. We extend research about how and why employees may be motivated to become stars, how best to manage stars and their relationships with colleagues, and how to motivate star retention. We then outline directions for future research. (c) 2015 APA, all rights reserved.

Wolf-Rayet stars as starting points or as endpoints of the evolution of massive stars?

NASA Technical Reports Server (NTRS)

Lamers, H. J. G. L. M.; Maeder, A.; Schmutz, W.; Cassinelli, J. P.

1991-01-01

The paper investigates the evidence for the two interpretations of Wolf-Rayet stars suggested in the literature: (1) massive premain-sequence stars with disks and (2) massive stars which have lost most of their H-rich layers in a stellar wind is investigated. The abundance determinations which are done in two different ways and which lead to different conclusions are discussed. The composition is solar, which would suggest interpretation (1), or the CNO abundances are strongly anomalous, which would suggest interpretation (2). Results from evolutionary calculations, stellar statistics, the existence of Ofpe/WN9 transition stars and W-R stars with evolved companions show overwhelming evidence that W-R stars are not premain-sequence stars but that they are in a late stage of evolution. Moreover, the fact that W-R stars are usually in clear regions of space, whereas massive premain-sequence stars are embedded in ultracompact H II regions also shows that W-R stars are not young premain-sequence stars.

Observations of southern emission-line stars

NASA Technical Reports Server (NTRS)

Henize, K. G.

1976-01-01

A catalog of 1929 stars showing H-alpha emission on photographic plates is presented which covers the entire southern sky south of declination -25 deg to a red limiting magnitude of about 11.0. The catalog provides previous designations of known emission-line stars equatorial (1900) and galactic coordinates, visual and photographic magnitudes, H-alpha emission parameters, spectral types, and notes on unusual spectral features. The objects listed include 16 M stars, 25 S stars, 37 carbon stars, 20 symbiotic stars, 40 confirmed or suspected T Tauri stars, 16 novae, 14 planetary nebulae, 11 P Cygni stars, 9 Bep stars, 87 confirmed or suspected Wolf-Rayet stars, and 26 'peculiar' stars. Two new T associations are discovered, one in Lupus and one in Chamaeleon. Objects with variations in continuum or H-alpha intensity are noted, and the distribution by spectral type is analyzed. It is found that the sky distribution of these emission-line stars shows significant concentrations in the region of the small Sagittarius cloud and in the Carina region.

Binary neutron stars with arbitrary spins in numerical relativity

NASA Astrophysics Data System (ADS)

Tacik, Nick; Foucart, Francois; Pfeiffer, Harald P.; Haas, Roland; Ossokine, Serguei; Kaplan, Jeff; Muhlberger, Curran; Duez, Matt D.; Kidder, Lawrence E.; Scheel, Mark A.; Szilágyi, Béla

2015-12-01

We present a code to construct initial data for binary neutron star systems in which the stars are rotating. Our code, based on a formalism developed by Tichy, allows for arbitrary rotation axes of the neutron stars and is able to achieve rotation rates near rotational breakup. We compute the neutron star angular momentum through quasilocal angular momentum integrals. When constructing irrotational binary neutron stars, we find a very small residual dimensionless spin of ˜2 ×10-4 . Evolutions of rotating neutron star binaries show that the magnitude of the stars' angular momentum is conserved, and that the spin and orbit precession of the stars is well described by post-Newtonian approximation. We demonstrate that orbital eccentricity of the binary neutron stars can be controlled to ˜0.1 % . The neutron stars show quasinormal mode oscillations at an amplitude which increases with the rotation rate of the stars.

On the origin of high-velocity runaway stars

NASA Astrophysics Data System (ADS)

Gvaramadze, Vasilii V.; Gualandris, Alessia; Portegies Zwart, Simon

2009-06-01

We explore the hypothesis that some high-velocity runaway stars attain their peculiar velocities in the course of exchange encounters between hard massive binaries and a very massive star (either an ordinary 50-100Msolar star or a more massive one, formed through runaway mergers of ordinary stars in the core of a young massive star cluster). In this process, one of the binary components becomes gravitationally bound to the very massive star, while the second one is ejected, sometimes with a high speed. We performed three-body scattering experiments and found that early B-type stars (the progenitors of the majority of neutron stars) can be ejected with velocities of >~200-400kms-1 (typical of pulsars), while 3-4Msolar stars can attain velocities of >~300-400kms-1 (typical of the bound population of halo late B-type stars). We also found that the ejected stars can occasionally attain velocities exceeding the Milky Ways's escape velocity.

Identification of stars in a J1744.0 star catalogue Yixiangkaocheng

NASA Astrophysics Data System (ADS)

Ahn, S.-H.

2012-05-01

The stars in the Chinese star catalogue, Yixiangkaocheng, which were edited by the Jesuit astronomer Kögler in AD 1744 and published in AD 1756, are identified with their counterparts in the Hipparcos catalogue. The equinox of the catalogue is confirmed to be J1744.0. By considering the precession of equinox, proper motions and nutation, the star closest to the location of each star in Yixiangkaocheng, having a proper magnitude, is selected as the corresponding identified star. I identified 2848 stars and 13 nebulosities out of 3083 objects in Yixiangkaocheng, and so the identification rate reached 92.80 per cent. I find that the magnitude classification system in Yixiangkaocheng agrees with the modern magnitude system. The catalogue includes dim stars, whose visual magnitudes are larger than 7, but most of these stars have Flamsteed designations. I find that the stars whose declination is lower than -30° have relatively larger offsets and different systematic behaviour from other stars. This indicates that there might be two different sources of stars in Yixiangkaocheng. In particular, I find that μ1 Sco and γ1 Sgr approximately mark the boundary between two different source catalogues. The observer's location, as estimated from these facts, agrees with the latitude of Greenwich where Flamsteed made his observations. The positional offsets between the Yixiangkaocheng stars and the Hipparcos stars are 0.6 arcmin, which implies that the source catalogue of stars with δ > -30° must have come from telescopic observations. Nebulosities in Yixiangkaocheng are identified with a few double stars, o Cet (the variable star, Mira), the Andromeda galaxy, ω Cen and NGC6231. These entities are associated with listings in Halley's Catalogue of the Southern Stars of AD 1679 as well as Flamsteed's catalogue of AD 1690.

AN ELEMENTAL ASSAY OF VERY, EXTREMELY, AND ULTRA-METAL-POOR STARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, T.; Christlieb, N.; Hansen, C. J.

2015-07-10

We present a high-resolution elemental-abundance analysis for a sample of 23 very metal-poor ([Fe/H] < −2.0) stars, 12 of which are extremely metal-poor ([Fe/H] < −3.0), and 4 of which are ultra-metal-poor ([Fe/H] < −4.0). These stars were targeted to explore differences in the abundance ratios for elements that constrain the possible astrophysical sites of element production, including Li, C, N, O, the α-elements, the iron-peak elements, and a number of neutron-capture elements. This sample substantially increases the number of known carbon-enhanced metal-poor (CEMP) and nitrogen-enhanced metal-poor (NEMP) stars—our program stars include eight that are considered “normal” metal-poor stars, sixmore » CEMP-no stars, five CEMP-s stars, two CEMP-r stars, and two CEMP-r/s stars. One of the CEMP-r stars and one of the CEMP-r/s stars are possible NEMP stars. We detect lithium for three of the six CEMP-no stars, all of which are Li depleted with respect to the Spite plateau. The majority of the CEMP stars have [C/N] > 0. The stars with [C/N] < 0 suggest a larger degree of mixing; the few CEMP-no stars that exhibit this signature are only found at [Fe/H] < −3.4, a metallicity below which we also find the CEMP-no stars with large enhancements in Na, Mg, and Al. We confirm the existence of two plateaus in the absolute carbon abundances of CEMP stars, as suggested by Spite et al. We also present evidence for a “floor” in the absolute Ba abundances of CEMP-no stars at A(Ba) ∼ −2.0.« less

THE PREVALENCE AND IMPACT OF WOLF–RAYET STARS IN EMERGING MASSIVE STAR CLUSTERS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sokal, Kimberly R.; Johnson, Kelsey E.; Indebetouw, Rémy

We investigate Wolf–Rayet (WR) stars as a source of feedback contributing to the removal of natal material in the early evolution of massive star clusters. Despite previous work suggesting that massive star clusters clear out their natal material before the massive stars evolve into the WR phase, WR stars have been detected in several emerging massive star clusters. These detections suggest that the timescale for clusters to emerge can be at least as long as the time required to produce WR stars (a few million years), and could also indicate that WR stars may be providing the tipping point inmore » the combined feedback processes that drive a massive star cluster to emerge. We explore the potential overlap between the emerging phase and the WR phase with an observational survey to search for WR stars in emerging massive star clusters hosting WR stars. We select candidate emerging massive star clusters from known radio continuum sources with thermal emission and obtain optical spectra with the 4 m Mayall Telescope at Kitt Peak National Observatory and the 6.5 m MMT.{sup 4} We identify 21 sources with significantly detected WR signatures, which we term “emerging WR clusters.” WR features are detected in ∼50% of the radio-selected sample, and thus we find that WR stars are commonly present in currently emerging massive star clusters. The observed extinctions and ages suggest that clusters without WR detections remain embedded for longer periods of time, and may indicate that WR stars can aid, and therefore accelerate, the emergence process.« less

System and method for calibrating inter-star-tracker misalignments in a stellar inertial attitude determination system

NASA Technical Reports Server (NTRS)

Li, Rongsheng (Inventor); Wu, Yeong-Wei Andy (Inventor); Hein, Douglas H. (Inventor)

2004-01-01

A method and apparatus for determining star tracker misalignments is disclosed. The method comprises the steps of defining a defining a reference frame for the star tracker assembly according to a boresight of the primary star tracker and a boresight of a second star tracker wherein the boresight of the primary star tracker and a plane spanned by the boresight of the primary star tracker and the boresight of the second star tracker at least partially define a datum for the reference frame for the star tracker assembly; and determining the misalignment of the at least one star tracker as a rotation of the defined reference frame.

Energy star compliant voice over internet protocol (VoIP) telecommunications network including energy star compliant VoIP devices

DOEpatents

Kouchri, Farrokh Mohammadzadeh

2012-11-06

A Voice over Internet Protocol (VoIP) communications system, a method of managing a communications network in such a system and a program product therefore. The system/network includes an ENERGY STAR (E-star) aware softswitch and E-star compliant communications devices at system endpoints. The E-star aware softswitch allows E-star compliant communications devices to enter and remain in power saving mode. The E-star aware softswitch spools messages and forwards only selected messages (e.g., calls) to the devices in power saving mode. When the E-star compliant communications devices exit power saving mode, the E-star aware softswitch forwards spooled messages.

The Search for New Luminous Blue Variable Stars: Near-Infrared Spectroscopy of Stars With 24 micron Shells

NASA Astrophysics Data System (ADS)

Stringfellow, Guy; Gvaramadze, Vasilii

2010-02-01

Luminous Blue Variable (LBV) stars represent an extremely rare class of very luminous and massive stars. Only about a dozen confirmed Galactic LBV stars are known to date, which precludes us from determining a solid evolutionary connection between LBV and other intermediate (e.g. Ofpe/WN9, WNL) phases in the life of very massive stars. The known LBV stars each have their own unique properties, so new discoveries add insight into the properties and evolutionary status of LBVs and massive stars; even one new discovery of objects of this type could provide break-through results in the understanding of the intermediate stages of massive star evolution. We have culled a prime sample of possible LBV candidates from the Spitzer 24 (micron) archival data. All have circumstellar nebulae, rings, and shells (typical of LBVs and related stars) surrounding reddened central stars. Spectroscopic followup of about two dozen optically visible central stars associated with the shells from this sample showed that they are either candidate LBVs, late WN-type Wolf-Rayet stars or blue supergiants. We propose infrared spectroscopic observations of the central stars for a large fraction (23 stars) of our northern sample to determine their nature and discover additional LBV candidates. These stars have no plausible optical counterparts, so infrared spectra are needed. This program requires two nights of Hale time using TripleSpec.

A robust star identification algorithm with star shortlisting

NASA Astrophysics Data System (ADS)

Mehta, Deval Samirbhai; Chen, Shoushun; Low, Kay Soon

2018-05-01

A star tracker provides the most accurate attitude solution in terms of arc seconds compared to the other existing attitude sensors. When no prior attitude information is available, it operates in "Lost-In-Space (LIS)" mode. Star pattern recognition, also known as star identification algorithm, forms the most crucial part of a star tracker in the LIS mode. Recognition reliability and speed are the two most important parameters of a star pattern recognition technique. In this paper, a novel star identification algorithm with star ID shortlisting is proposed. Firstly, the star IDs are shortlisted based on worst-case patch mismatch, and later stars are identified in the image by an initial match confirmed with a running sequential angular match technique. The proposed idea is tested on 16,200 simulated star images having magnitude uncertainty, noise stars, positional deviation, and varying size of the field of view. The proposed idea is also benchmarked with the state-of-the-art star pattern recognition techniques. Finally, the real-time performance of the proposed technique is tested on the 3104 real star images captured by a star tracker SST-20S currently mounted on a satellite. The proposed technique can achieve an identification accuracy of 98% and takes only 8.2 ms for identification on real images. Simulation and real-time results depict that the proposed technique is highly robust and achieves a high speed of identification suitable for actual space applications.

Are some CEMP-s stars the daughters of spinstars?

NASA Astrophysics Data System (ADS)

Choplin, Arthur; Hirschi, Raphael; Meynet, Georges; Ekström, Sylvia

2017-11-01

Carbon-enhanced metal-poor (CEMP)-s stars are long-lived low-mass stars with a very low iron content as well as overabundances of carbon and s-elements. Their peculiar chemical pattern is often explained by pollution from an asymptotic giant branch (AGB) star companion. Recent observations have shown that most CEMP-s stars are in binary systems, providing support to the AGB companion scenario. A few CEMP-s stars, however, appear to be single. We inspect four apparently single CEMP-s stars and discuss the possibility that they formed from the ejecta of a previous-generation massive star, referred to as the "source" star. In order to investigate this scenario, we computed low-metallicity massive-star models with and without rotation and including complete s-process nucleosynthesis. We find that non-rotating source stars cannot explain the observed abundance of any of the four CEMP-s stars. Three out of the four CEMP-s stars can be explained by a 25M⊙ source star with vini 500 km s-1 (spinstar). The fourth CEMP-s star has a high Pb abundance that cannot be explained by any of the models we computed. Since spinstars and AGB predict different ranges of [O/Fe] and [ls/hs], these ratios could be an interesting way to further test these two scenarios.

CHEMICAL ABUNDANCES OF MEMBER STARS IN THE OPEN CLUSTER NGC 2632 (PRAESEPE)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, X. L.; Chen, Y. Q.; Zhao, G.

2015-11-15

Based on high-resolution, high signal-to-noise ratio spectra, we present abundances of 17 elements (Fe, O, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Co, Ni, Y, Zr, Ba, La) for six stars (one Am star, one F dwarf star, and four GK giant stars) and radial velocities for 18 proper-motion selected member stars in the open cluster NGC 2632. In the Am star, s-process elements Y and Ba are clearly overabundant, which may be considered as an indicator of a peculiar Am star. The average [Fe/H] is 0.16 ± 0.06 from four GK giant member stars, which is similarmore » to that of solar-type stars in the literature. As compared with dwarf stars, significant overabundances are found for Na, Mg, and Ba elements in our giant stars, which can be explained by the evolutionary effect. We also detect a star-to-star scatter of [Na/Fe] ratios among four giants which locate approximately at the same position in the CMD. Finally, we perform an analysis on the possible connection between the abundance and spatial structure of NGC 2632, but we find no inhomogeneous abundance among different clumps of stars in this cluster based on our limited sample.« less

End of the Line for a Star like Ours

ERIC Educational Resources Information Center

Riddle, Bob

2010-01-01

Stars of different masses have varying life spans, with the more massive stars "burning out" more quickly than stars of lower masses. How or what they do when they burn out also varies, depending on the mass of the star. All stars are called "main sequence stars" as they continue fusing hydrogen and staying in a state of equilibrium--a balance…

How bright planets became dim stars: planetary speculations in John Herschel's double star astronomy

NASA Astrophysics Data System (ADS)

Case, S.

2014-03-01

Previous research on the origins of double star astronomy in the early nineteenth century emphasized the role mathematical methods and instrumentation played in motivating early observations of these objects. The work of the British astronomer John Herschel, however, shows that questions regarding the physical nature of double stars were also important. In particular, an analysis of John Herschel's early work on double stars illustrates the way in which speculations regarding these objects were shaped by assumptions of the properties of stars themselves. For Herschel, a major consideration in double star astronomy was distinguishing between types of double stars. Optical doubles were useful in determining parallax while binary doubles were not. In practice, classification of a specific double star pair into one of these categories was based on the assumption that stars were of approximately the same luminosity and thus differences in relative brightness between stars were caused by difference in distances. Such assumptions, though ultimately abandoned, would lead Herschel in the 1830s to advance the possibility that the dim companion stars in certain double star pairs were not stars at all but in fact planets.

How bright planets became dim stars: planetary speculations in John Herschel's double star astronomy.

PubMed

Case, Stephen

2014-03-01

Previous research on the origins of double star astronomy in the early nineteenth century emphasized the role mathematical methods and instrumentation played in motivating early observations of these objects. The work of the British astronomer John Herschel, however, shows that questions regarding the physical nature of double stars were also important. In particular, an analysis of John Herschel's early work on double stars illustrates the way in which speculations regarding these objects were shaped by assumptions of the properties of stars themselves. For Herschel, a major consideration in double star astronomy was distinguishing between types of double stars. Optical doubles were useful in determining parallax while binary doubles were not. In practice, classification of a specific double star pair into one of these categories was based on the assumption that stars were of approximately the same luminosity and thus differences in relative brightness between stars were caused by difference in distances. Such assumptions, though ultimately abandoned, would lead Herschel in the 1830s to advance the possibility that the dim companion stars in certain double star pairs were not stars at all but in fact planets. Copyright © 2014 Elsevier Ltd. All rights reserved.

Massive Star Formation Viewed through Extragalactic-Tinted Glasses

NASA Astrophysics Data System (ADS)

Willis, Sarah; Marengo, M.; Smith, H. A.; Allen, L.

2014-01-01

Massive Galactic star forming regions are the local analogs to the luminous star forming regions that dominate the emission from star forming galaxies. Their proximity to us enables the characterization of the full range of stellar masses that form in these more massive environments, improving our understanding of star formation tracers used in extragalactic studies. We have surveyed a sample of massive star forming regions with a range of morphologies and luminosities to probe the star formation activity in a variety of environments. We have used Spitzer IRAC and deep ground based J, H, Ks observations to characterize the Young Stellar Object (YSO) content of 6 massive star forming regions. These YSOs provide insight into the rate and efficiency of star formation within these regions, and enable comparison with nearby, low mass star forming regions as well as extreme cases of Galactic star formation including ‘mini-starburst’ regions. In addition, we have conducted an in-depth analysis of NGC 6334 to investigate how the star formation activity varies within an individual star forming region, using Herschel data in the far-infrared to probe the earliest stages of the ongoing star formation activity.

Managing the star performer.

PubMed

Hills, Laura

2013-01-01

Our culture seems to be endlessly fascinated with its stars in entertainment, athletics, politics, and business, and holds fast to the idea that extraordinary talent accounts for an individual's extraordinary performance. At first glance, managing a star performer in your medical practice may seem like it would be an easy task. However, there's much more to managing a star performer than many practice managers realize. The concern is how to keep the star performer happy and functioning at a high level without detriment to the rest of the medical practice team. This article offers tips for practice managers who manage star performers. It explores ways to keep the star performer motivated, while at the same time helping the star performer to meld into the existing medical practice team. This article suggests strategies for redefining the star performer's role, for holding the star performer accountable for his or her behavior, and for coaching the star performer. Finally, this article offers practical tips for keeping the star performer during trying times, for identifying and cultivating new star performers, and for managing medical practice prima donnas.

Massive Stars

NASA Astrophysics Data System (ADS)

Livio, Mario; Villaver, Eva

2009-11-01

Participants; Preface Mario Livio and Eva Villaver; 1. High-mass star formation by gravitational collapse of massive cores M. R. Krumholz; 2. Observations of massive star formation N. A. Patel; 3. Massive star formation in the Galactic center D. F. Figer; 4. An X-ray tour of massive star-forming regions with Chandra L. K. Townsley; 5. Massive stars: feedback effects in the local universe M. S. Oey and C. J. Clarke; 6. The initial mass function in clusters B. G. Elmegreen; 7. Massive stars and star clusters in the Antennae galaxies B. C. Whitmore; 8. On the binarity of Eta Carinae T. R. Gull; 9. Parameters and winds of hot massive stars R. P. Kudritzki and M. A. Urbaneja; 10. Unraveling the Galaxy to find the first stars J. Tumlinson; 11. Optically observable zero-age main-sequence O stars N. R. Walborn; 12. Metallicity-dependent Wolf-Raynet winds P. A. Crowther; 13. Eruptive mass loss in very massive stars and Population III stars N. Smith; 14. From progenitor to afterlife R. A. Chevalier; 15. Pair-production supernovae: theory and observation E. Scannapieco; 16. Cosmic infrared background and Population III: an overview A. Kashlinsky.

A hydrodynamical model of the circumstellar bubble created by two massive stars

NASA Astrophysics Data System (ADS)

van Marle, A. J.; Meliani, Z.; Marcowith, A.

2012-05-01

Context. Numerical models of the wind-blown bubble of massive stars usually only account for the wind of a single star. However, since massive stars are usually formed in clusters, it would be more realistic to follow the evolution of a bubble created by several stars. Aims: We develop a two-dimensional (2D) model of the circumstellar bubble created by two massive stars, a 40 M⊙ star and a 25 M⊙ star, and follow its evolution. The stars are separated by approximately 16 pc and surrounded by a cold medium with a density of 20 particles per cm3. Methods: We use the MPI-AMRVAC hydrodynamics code to solve the conservation equations of hydrodynamics on a 2D cylindrical grid using time-dependent models for the wind parameters of the two stars. At the end of the stellar evolution (4.5 and 7.0 million years for the 40 and 25 M⊙ stars, respectively), we simulate the supernova explosion of each star. Results: Each star initially creates its own bubble. However, as the bubbles expand they merge, creating a combined, aspherical bubble. The combined bubble evolves over time, influenced by the stellar winds and supernova explosions. Conclusions: The evolution of a wind-blown bubble created by two stars deviates from that of the bubbles around single stars. In particular, once one of the stars has exploded, the bubble is too large for the wind of the remaining star to maintain and the outer shell starts to disintegrate. The lack of thermal pressure inside the bubble also changes the behavior of circumstellar features close to the remaining star. The supernovae are contained inside the bubble, which reflects part of the energy back into the circumstellar medium. Movies are available in electronic form at http://www.aanda.org

Star-triangle and star-star relations in statistical mechanics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baxter, R.J.

1997-01-20

The homogeneous three-layer Zamolodchikov model is equivalent to a four-state model on the checkerboard lattice which closely resembles the four-state critical Potts model, but with some of its Boltzmann weights negated. Here the author shows that it satisfies a star-to-reverse-star (or simply star-star) relation, even though they know of no star-triangle relation for this model. For any nearest-neighbor checkerboard model, they show that this star-star relation is sufficient to ensure that the decimated model (where half the spins have been summed over) satisfies a twisted Yang-Baxter relation. This ensures that the transfer matrices of the original model commute in pairs,more » which is an adequate condition for solvability.« less

Development of a Robust star identification technique for use in attitude determination of the ACE spacecraft

NASA Technical Reports Server (NTRS)

Woodard, Mark; Rohrbaugh, Dave

1995-01-01

The Advanced Composition Explorer (ACE) spacecraft is designed to fly in a spin-stabilized attitude. The spacecraft will carry two attitude sensors - a digital fine Sun sensor and a charge coupled device (CCD) star tracker - to allow ground-based determination of the spacecraft attitude and spin rate. Part of the processing that must be performed on the CCD star tracker data is the star identification. Star data received from the spacecraft must be matched with star information in the SKYMAP catalog to determine exactly which stars the sensor is tracking. This information, along with the Sun vector measured by the Sun sensor, is used to determine the spacecraft attitude. Several existing star identification (star ID) systems were examined to determine whether they could be modified for use on the ACE mission. Star ID systems which exist for three-axis stabilized spacecraft tend to be complex in nature and many require fairly good knowledge of the spacecraft attitude, making their use for ACE excessive. Star ID systems used for spinners carrying traditional slit star sensors would have to be modified to model the CCD star tracker. The ACE star ID algorithm must also be robust, in that it will be able to correctly identify stars even though the attitude is not known to a high degree of accuracy, and must be very efficient to allow real-time star identification. The paper presents the star ID algorithm that was developed for ACE. Results from prototype testing are also presented to demonstrate the efficiency, accuracy, and robustness of the algorithm.

A hybrid method for accurate star tracking using star sensor and gyros.

PubMed

Lu, Jiazhen; Yang, Lie; Zhang, Hao

2017-10-01

Star tracking is the primary operating mode of star sensors. To improve tracking accuracy and efficiency, a hybrid method using a star sensor and gyroscopes is proposed in this study. In this method, the dynamic conditions of an aircraft are determined first by the estimated angular acceleration. Under low dynamic conditions, the star sensor is used to measure the star vector and the vector difference method is adopted to estimate the current angular velocity. Under high dynamic conditions, the angular velocity is obtained by the calibrated gyros. The star position is predicted based on the estimated angular velocity and calibrated gyros using the star vector measurements. The results of the semi-physical experiment show that this hybrid method is accurate and feasible. In contrast with the star vector difference and gyro-assisted methods, the star position prediction result of the hybrid method is verified to be more accurate in two different cases under the given random noise of the star centroid.

Activity in X-ray-selected late-type stars

NASA Technical Reports Server (NTRS)

Takalo, Leo O.; Nousek, J. A.

1988-01-01

A spectroscopic study has been conducted of nine X-ray bright late-type stars selected from two Einstein X-ray surveys: the Columbia Astrophysical Laboratory Survey (five stars) and the CFA Medium Sensitivity Survey (MSS; four stars). Spectral classes were determined and radial and V sin(i) velocities were measured for the stars. Four of the Columbia Survey stars were found to be new RS CVn-type binaries. The fifth Columbia survey star was found to be an active G dwarf star without evidence for binarity. None of the four MSS stars were found to be either binaries or optically active stars. Activity in these stars was assessed by measuring the excess emission in H-alpha and the Ca II IRT (8498, 8542) lines in comparison with inactive stars of similar spectral types. A correlation was found between X-ray luminosity and V sin(i) and H-alpha line excess. The measured excess line emission in H-alpha was also correlated with V sin(i) but not with the IRT line excess.

Debris Disks Among the Shell Stars: Insights from Spitzer

NASA Technical Reports Server (NTRS)

Roberge, Aki; Weinberger, Alycia; Teske, Johanna

2008-01-01

Shell stars are a class of early-type stars that show narrow absorption lines in their spectra that appear to arise from circumstellar class. This observationally defined class contains a variety of objects, including evolved stars and classical Be stars. However, some of the main sequence shell stars harbor debris disks and younger protoplanetary disks, though this aspect of the class has been largely overlooked. We surveyed a set of main sequence stars for cool dust using Spitzer MIPS and found four additional systems with IR excesses at both 24 and 70 microns. This indicates that the stars have both circumstellar gas and dust, and are likely to be edge-on debris disks. Our estimate of the disk fraction among nearby main sequence shell stars is 48% +/- 14%. We discuss here the nature of the shell stars and present preliminary results from ground-based optical spectra of the survey target stars. We will also outline our planned studies aimed at further characterization of the shell star class.

Effect of attractive interactions between polymers on the effective force acting between colloids immersed in a polymer system: Analytic liquid-state theory.

PubMed

Chervanyov, A I

2016-12-28

By making use of the polymer reference interaction site model, we analytically study the effect of attractive interactions between polymers on the effective forces acting between colloids immersed in a polymer system. The performed theoretical analysis has no restrictions with respect to the polymer density and relative sizes of the colloids and polymers. The polymer mediated (PM) potential acting between colloids is shown to significantly depend on the strength and range of the polymer-polymer interactions. In the nano-particle limit, where the colloid radius is much smaller than the polymer gyration radius, the presence of attractive polymer-polymer interactions causes only quantitative changes to the PM potential. In the opposite limit of relatively large colloids, the polymer-polymer interactions revert the sign of the total effective force acting between colloids so that this force becomes attractive at sufficiently large polymer densities. With the objective to study an intricate interplay between the attractive PM forces and steric repulsion in different polymer density regimes, we calculate the second virial coefficient B of the total effective potential acting between colloids. The dependence of B on the polymer density is discussed in detail, revealing several novel features of the PM interactions caused by the presence of attractive polymer-polymer interactions.

The Fate of Merging Neutron Stars

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-08-01

A rapidly spinning, highly magnetized neutron star is one possible outcome when two smaller neutron stars merge. [Casey Reed/Penn State University]When two neutron stars collide, the new object that they make can reveal information about the interior physics of neutron stars. New theoretical work explores what we should be seeing, and what it can teach us.Neutron Star or Black Hole?So far, the only systems from which weve detected gravitational waves are merging black holes. But other compact-object binaries exist and are expected to merge on observable timescales in particular, binary neutron stars. When two neutron stars merge, the resulting object falls into one of three categories:a stable neutron star,a black hole, ora supramassive neutron star, a large neutron star thats supported by its rotation but will eventually collapse to a black hole after it loses angular momentum.Histograms of the initial (left) and final (right) distributions of objects in the authors simulations, for five different equations of state. Most cases resulted primarily in the formation of neutron stars (NSs) or supramassive neutron stars (sNSs), not black holes (BHs). [Piro et al. 2017]Whether a binary-neutron-star merger results in another neutron star, a black hole, or a supramassive neutron star depends on the final mass of the remnant and what the correct equation of state is that describes the interiors of neutron stars a longstanding astrophysical puzzle.In a recent study, a team of scientists led by Anthony Piro (Carnegie Observatories) estimated which of these outcomes we should expect for mergers of binary neutron stars. The teams results along with future observations of binary neutron stars may help us to eventually pin down the equation of state for neutron stars.Merger OutcomesPiro and collaborators used relativistic calculations of spinning and non-spinning neutron stars to estimate the mass range that neutron stars would have for several different realistic equations of state. They then combined this information with Monte Carlo simulations based on the mass distribution of neutron-star binaries in our galaxy. From these simulations, Piro and collaborators could predict the distribution of fates expected for merging neutron-star binaries, given different equations of state.The authors found that the fate of the merger could vary greatly depending on the equation of state you assume. Intriguingly, all equations of state resulted in a surprisingly high fraction of systems that merged to form a neutron star or a supramassive neutron star in fact, four out of the five equations of state predicted that 80100% of systems would result in a neutron star or a supermassive neutron star.Lessons from ObservationsThe frequency bands covered by various current and planned gravitational wave observatories. Advanced LIGO has the right frequency coverage to be able to explore a neutron-star remnant if the signal is loud enough. [Christopher Moore, Robert Cole and Christopher Berry]These results have important implications for our future observations. The high predicted fraction of neutron stars resulting from these mergers tells us that its especially important for gravitational-wave observatories to probe 14 kHz emission. This frequency range will enable us to study the post-merger neutron-star or supramassive-neutron-star remnants.Even if we cant observe the remnants behavior after it forms, we can still compare the distribution of remnants that we observe in the future to the predictions made by Piro and collaborators. This will potentially allow us to constrain the neutron-star equation of state, revealing the physics of neutron-star interiors even without direct observations.CitationAnthony L. Piro et al 2017 ApJL 844 L19. doi:10.3847/2041-8213/aa7f2f

Understand B-type stars

NASA Technical Reports Server (NTRS)

1982-01-01

When observations of B stars made from space are added to observations made from the ground and the total body of observational information is confronted with theoretical expectations about B stars, it is clear that nonthermal phenomena occur in the atmospheres of B stars. The nature of these phenomena and what they imply about the physical state of a B star and how a B star evolves are examined using knowledge of the spectrum of a B star as a key to obtaining an understanding of what a B star is like. Three approaches to modeling stellar structure (atmospheres) are considered, the characteristic properties of a mantle, and B stars and evolution are discussed.

Explosions in Majestic Spiral Beauties

NASA Astrophysics Data System (ADS)

2004-12-01

Images of beautiful galaxies, and in particular of spiral brethren of our own Milky Way, leaves no-one unmoved. It is difficult indeed to resist the charm of these impressive grand structures. Astronomers at Paranal Observatory used the versatile VIMOS instrument on the Very Large Telescope to photograph two magnificent examples of such "island universes", both of which are seen in a southern constellation with an animal name. But more significantly, both galaxies harboured a particular type of supernova, the explosion of a massive star during a late and fatal evolutionary stage. The first image (PR Photo 33a/04) is of the impressive spiral galaxy NGC 6118 [1], located near the celestial equator, in the constellation Serpens (The Snake). It is a comparatively faint object of 13th magnitude with a rather low surface brightness, making it pretty hard to see in small telescopes. This shyness has prompted amateur astronomers to nickname NGC 6118 the "Blinking Galaxy" as it would appear to flick into existence when viewed through their telescopes in a certain orientation, and then suddenly disappear again as the eye position shifted. There is of course no such problem for the VLT's enormous light-collecting power and ability to produce sharp images, and this magnificent galaxy is here seen in unequalled detail. The colour photo is based on a series of exposures behind different optical filters, obtained with the VIMOS multi-mode instrument on the 8.2-m VLT Melipal telescope during several nights around August 21, 2004. About 80 million light-years away, NGC 6118 is a grand-design spiral seen at an angle, with a very small central bar and several rather tightly wound spiral arms (it is classified as of type "SA(s)cd" [2]) in which large numbers of bright bluish knots are visible. Most of them are active star-forming regions and in some, very luminous and young stars can be perceived. Of particular interest is the comparatively bright stellar-like object situated directly North of the galaxy's centre, near the periphery (see PR Photo 33b/04): it is Supernova 2004dk that was first reported on August 1, 2004. Observations a few days later showed this to be a supernova of Type Ib or Ic [3], caught a few days before maximum light. This particular kind of supernova is believed to result from the demise of a massive star that has somehow lost its entire hydrogen envelope, probably as a result of mass transfer in a binary system, before exploding. Also visible on the image is the trail left by a satellite, which passed by during one of the exposures taken in the B filter, hence its blue colour. This is an illustration that even in such a remote place as the Paranal Observatory in the Atacama desert, astronomers are not completely sheltered from light pollution. ESO PR Photo 33c/04 ESO PR Photo 33c/04 NGC 7424 - VIMOS+VLT Colour composite [Preview - JPEG: 400 x 514 pix - 110k] [Normal - JPEG: 800 x 1028 pix - 995k] [FullRes - JPEG: 1887 x 2424 pix - 5.4M] Caption: ESO PR Photo 33c/04 shows a composite colour-coded image of another magnificent spiral galaxy, NGC 7424, at a distance of 40 million light-years. It is based on images obtained with the multi-mode VIMOS instrument on the ESO Very Large Telescope (VLT) in three different wavelength bands (see Technical information below). The image covers 6.5 x 7.2 arcmin on the sky. North is up and East is to the right. The second galaxy imaged by the VLT (ESO PR Photo 33c/04) is another spiral, the beautiful multi-armed NGC 7424 that is seen almost directly face-on. Located at a distance of roughly 40 million light-years in the constellation Grus (the Crane), this galaxy was discovered by Sir John Herschel while observing at the Cape of Good Hope. This other example of a "grand design" galaxy is classified as "SAB(rs)cd" [2], meaning that it is intermediate between normal spirals (SA) and strongly barred galaxies (SB) and that it has rather open arms with a small central region. It also shows many ionised regions as well as clusters of young and massive stars. Ten young massive star clusters can be identified whose size span the range from 1 to 200 light-years. The galaxy itself is roughly 100,000 light-years across, that is, quite similar in size to our own Milky Way galaxy. Because of its low surface brightness, this galaxy also demands dark skies and a clear night to be observed in this impressive detail. When viewed in a small telescope, it appears as a large elliptical haze with no trace of the many beautiful filamentary arms with a multitude of branches revealed in this striking VLT image. Note also the very bright and prominent bar in the middle. ESO PR Photo 33d/04 ESO PR Photo 33d/04 NGC 7424 and SN2001ig (FORS 2 and VIMOS + VLT) [Preview - JPEG: 400 x 596 pix - 44k] [Normal - JPEG: 800 x 1192 pix - 637k] Caption: ESO PR Photo 33d/04 shows two composite colour-coded image of a part of NGC 7424. The left image was made from an exposure taken with the FORS 2 instrument on VLT Yepun on June 16, 2002. In this, the supernova - although considerably fainter than when it was discovered six months earlier - is still well visible in the middle right of the image. The right image is part of PR Photo 33d/04 on the same scale. Obtained in October 2004, the supernova is no more apparent. The image covers 3.8 x 3.2 arcmin. North is up and East is to the right. On the evening of 10 December 2001, Australian amateur astronomer Reverend Robert Evans, observing from his backyard in the Blue Mountains west of Sydney, discovered with his 30cm telescope his 39th supernova, Supernova 2001ig in the outskirts of NGC 7424. Of magnitude 14.5 (that is, 3000 times fainter than the faintest star that can be seen with the unaided eye), this supernova brightened quickly by a factor 8 to magnitude 12.3. A few months later, it had faded to an insignificant object below 17th magnitude. By comparison, the entire galaxy is of magnitude 11: at the time of its maximum, the supernova was thus only three times fainter than the whole galaxy. It must have been a splendid firework indeed! By digging into the vast Science Archive of the ESO Very Large Telescope, it was possible to find an image of NGC 7424 taken on June 16, 2002 by Massimo Turatto (Observatorio di Padova-INAF, Italy) with the FORS 2 instrument on Yepun (UT4). Although, the supernova was already much fainter than at its maximum 6 months earlier, it is still very well visible on this image (see PR Photo 33d/04). Spectra taken with ESO's 3.6-m telescope at La Silla over the months following the explosion showed the object to evolve to a Type Ib/c supernova. By October 2002, the transition to a Type Ib/c supernova was complete. It is now believed that this supernova arose from the explosion of a very massive star, a so-called Wolf-Rayet star, which together with a massive hot companion belonged to a very close binary system in which the two stars orbited each other once every 100 days or so (read the details in the paper by Ryder et al. here ). Future detailed observations may reveal the presence of the companion star that survived this explosion but which is now doomed to explode as another supernova in due time.

Collisionless relaxation in spiral galaxy models

NASA Technical Reports Server (NTRS)

Hohl, F.

1974-01-01

The increase in random kinetic energy of stars by rapidly fluctuating gravitational fields (collisionless or violent relaxation) in disk galaxy models is investigated for three interaction potentials of the stars corresponding to (1) point stars, (2) rod stars of length 2 kpc, and (3) uniform density spherical stars of radius 2 kpc. To stabilize the galaxy against the large scale bar forming instability, a fixed field corresponding to a central core or halo component of stars was added with the stars containing at most 20 percent of the total mass of the galaxy. Considerable heating occurred for both the point stars and the rod stars, whereas the use of spherical stars resulted in a very low heating rate. The use of spherical stars with the resulting low heating rate will be desirable for the study of large scale galactic stability or density wave propagation, since collective heating effects will no longer mask the phenomena under study.

Strange stars

NASA Technical Reports Server (NTRS)

Alcock, Charles; Farhi, Edward; Olinto, Angela

1986-01-01

Strange matter, a form of quark matter that is postulated to be absolute stable, may be the true ground stage of the hadrons. If this hypothesis is correct, neutron stars may convert to 'strange stars'. The mass-radius relation for strange stars is very different from that of neutron stars; there is no minimum mass, and for mass of 1 solar mass or less, mass is proportional to the cube of the radius. For masses between 1 solar mass and 2 solar masses, the radii of strange stars are about 10 km, as for neutron stars. Strange stars may have an exposed quark surface, which is capable of radiating at rates greatly exceeding the Eddington limit, but has a low emissivity for X-ray photons. The stars may have a thin crust with the same composition as the preneutron drip outer layer of a conventional neutron star crust. Strange stars cool efficiently via neutrino emission.

Effective star tracking method based on optical flow analysis for star trackers.

PubMed

Sun, Ting; Xing, Fei; Wang, Xiaochu; Li, Jin; Wei, Minsong; You, Zheng

2016-12-20

Benefiting from rapid development of imaging sensor technology, modern optical technology, and a high-speed computing chip, the star tracker's accuracy, dynamic performance, and update rate have been greatly improved with low power consumption and miniature size. The star tracker is currently one of the most competitive attitude measurement sensors. However, due to restrictions of the optical imaging system, difficulties still exist in moving star spot detection and star tracking when in special motion conditions. An effective star tracking method based on optical flow analysis for star trackers is proposed in this paper. Spot-based optical flow, based on a gray gradient between two adjacent star images, is analyzed to distinguish the star spot region and obtain an accurate star spot position so that the star tracking can keep continuous under high dynamic conditions. The obtained star vectors and extended Kalman filter (EKF) are then combined to conduct an angular velocity estimation to ensure region prediction of the star spot; this can be combined with the optical flow analysis result. Experiment results show that the method proposed in this paper has advantages in conditions of large angular velocity and large angular acceleration, despite the presence of noise. Higher functional density and better performance can be achieved; thus, the star tracker can be more widely applied in small satellites, remote sensing, and other complex space missions.

Stars Can't Spin Out of Control (Artist's Animation)

NASA Technical Reports Server (NTRS)

2006-01-01

[figure removed for brevity, see original site] Click on the image for QuickTime Movie of Stars Can't Spin Out of Control

This artist's animation demonstrates how a dusty planet-forming disk can slow down a whirling young star, essentially saving the star from spinning itself to death. Evidence for this phenomenon comes from NASA's Spitzer Space Telescope.

The movie begins by showing a developing star (red ball). The star is basically a giant ball of gas that is collapsing onto itself. As it shrinks, it spins faster and faster, like a skater folding in his or her arms. The green lines represent magnetic fields.

As gravity continues to pull matter inward, the star spins so fast, it starts to flatten out. The same principle applies to the planet Saturn, whose spin has caused it to be slightly squashed or oblate.

A forming star can theoretically whip around fast enough to overcome gravity and flatten itself into a state where it can no longer become a full-fledged star. But stars don't spin out of control, possibly because swirling disks of dust slow them down. Such disks can be found orbiting young stars, and are filled with dust that might ultimately stick together to form planets.

The second half of the animation demonstrates how a disk is thought to keep its star's speed in check. A developing star is shown twirling inside its disk. As it turns, its magnetic fields pass through the disk and get bogged down like a spoon in molasses. This locks the star's rotation to the slower-turning disk, so the star, while continuing to shrink, does not spin faster.

Spitzer found evidence for star-slowing disks in a survey of nearly 500 forming stars in the Orion nebula. It observed that slowly spinning stars are five times more likely to host disks than rapidly spinning stars.

Be Stars in M31

NASA Astrophysics Data System (ADS)

Peters, Matthew L.; Wisniewski, John; Choi, Yumi; Williams, Ben; Lomax, Jamie; Bjorkman, Karen; Durbin, Meredith; Johnson, Lent Cliff; Lewis, Alexia; Lutz, Julie; Sigut, Aaron; Wallach, Aislynn; Dalcanton, Julianne

2018-01-01

We identify Be candidate stars in M31 using two-epoch F625W + F658N photometry from HST/ACS+WFC3 combined with the Panchromatic Hubble Andromeda Treasury (PHAT) Catalog. Using the PHAT catalog allows us to extract stellar parameters such as surface temperature and gravity, thereby allowing us to identify the main sequence B type stars in the field of view. Be candidate stars are identified by comparing their HST narrow-band Hα excess magnitudes with that predicted by Kurucz spectra. We find 314 Be candidate stars out of 5699 B + Be candidate stars (5.51%) in our first epoch and 301 Be candidate stars out of 5769 B + Be candidate stars (5.22%) in our second epoch. Our Be fraction, while lower than that of the SMC, LMC, and MW, is possibly consistent with the fact the M31 has a higher metallicity than the other galaxies because Be fraction varies inversely with metallicity. We note that earlier spectral types have the largest Be fraction, and that the Be fraction strictly declines as the spectral type increases to later types. We then match our Be candidate stars with clusters, establishing that 39 of 314 are cluster stars in epoch one and 36 of 301 stars are cluster stars in epoch two. We assign ages, using the cluster age to characterize cluster Be candidate stars and star formation histories to characterize field Be candidate stars. Finally, we determine which Be candidate stars exhibited disk loss or disk growth between epochs, finding that, of the Be stars that did not show source confusion or low SNR in one of the epochs, 65 / 265 (24.5%) showed disk loss or renewal, while 200 / 265 (75.5%) showed only small changes in Hα excess. Our research provides context for the parameters of candidate Be stars in M31, which will be useful in further determining the nature of Be stars. This paper was supported by a grant from STScI via GO-13857.

A Search for Nitrogen-enhanced Metal-poor Stars

NASA Astrophysics Data System (ADS)

Johnson, Jennifer A.; Herwig, Falk; Beers, Timothy C.; Christlieb, Norbert

2007-04-01

Theoretical models of very metal-poor intermediate-mass asymptotic giant branch (AGB) stars predict a large overabundance of primary nitrogen. The very metal-poor, carbon-enhanced, s-process-rich stars, which are thought to be the polluted companions of now extinct AGB stars, provide direct tests of the predictions of these models. Recent studies of the carbon and nitrogen abundances in metal-poor stars have focused on the most carbon-rich stars, leading to a potential selection bias against stars that have been polluted by AGB stars that produced large amounts of nitrogen and hence have small [C/N] ratios. We call these stars nitrogen-enhanced metal-poor (NEMP) stars and define them as having [N/Fe]>+0.5 and [C/N]<-0.5. In this paper we report on the [C/N] abundances of a sample of 21 carbon-enhanced stars, all but three of which have [C/Fe]<+2.0. If NEMP stars were made as easily as carbon-enhanced metal-poor (CEMP) stars, then we expected to find between two and seven NEMP stars. Instead, we found no NEMP stars in our sample. Therefore, this observational bias is not an important contributor to the apparent dearth of N-rich stars. Our [C/N] values are in the same range as values reported previously in the literature (-0.5 to +2.0), and all stars are in disagreement with the predicted [C/N] ratios for both low- and high-mass AGB stars. We suggest that the decrease in [C/N] from the low-mass AGB models is due to enhanced extramixing, while the lack of NEMP stars may be caused by unfavorable mass ratios in binaries or the difficulty of mass transfer in binary systems with large mass ratios. Based on observations obtained at Cerro Tololo Inter-American Observatory and Kitt Peak National Observatory, a division of the National Optical Astronomy Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under cooperative agreement with the National Science Foundation.

Status Report on Image Information Systems and Image Data Base Technology

DTIC Science & Technology

1989-12-01

PowerHouse, StarGate , StarNet. Significant Recent Developments: Acceptance major teaching Universities (Australia), U.S.A.F. Major Corporations. Future...scenario, all computers must be VAX). STARBASE StarBase StarNet, (Network server), StarBase StarGate , (SQL gateway). SYBASE Sybase is an inherently

Atoms, Stars, and Nebulae

NASA Astrophysics Data System (ADS)

Aller, Lawrence H.

1991-09-01

1. Introducing stars and nebulae; 2. Stellar rainbows; 3. Atoms and molecules; 4. The climate in a stellar atmosphere; 5. Analysing the stars; 6. Dwarfs, giants, and supergiants; 7. What makes a star shine?; 8. The youth and middle age of a common star; 9. Wind, dust and pulsations; 10. A star's last hurray?; 11. The interstellar medium and gaseous nebulae; 12. Uncommon stars and their sometimes violent behaviour; 13. High energy astronomy.

Chemical Evolution of Binary Stars

NASA Astrophysics Data System (ADS)

Izzard, R. G.

2013-02-01

Energy generation by nuclear fusion is the fundamental process that prevents stars from collapsing under their own gravity. Fusion in the core of a star converts hydrogen to heavier elements from helium to uranium. The signature of this nucleosynthesis is often visible in a single star only for a very short time, for example while the star is a red giant or, in massive stars, when it explodes. Contrarily, in a binary system nuclear-processed matter can captured by a secondary star which remains chemically polluted long after its more massive companion star has evolved and died. By probing old, low-mass stars we gain vital insight into the complex nucleosynthesis that occurred when our Galaxy was much younger than it is today. Stellar evolution itself is also affected by the presence of a companion star. Thermonuclear novae and type Ia supernovae result from mass transfer in binary stars, but big questions still surround the nature of their progenitors. Stars may even merge and one of the challenges for the future of stellar astrophysics is to quantitatively understand what happens in such extreme systems. Binary stars offer unique insights into stellar, galactic and extragalactic astrophysics through their plethora of exciting phenomena. Understanding the chemical evolution of binary stars is thus of high priority in modern astrophysics.

Study of the star catalogue (epoch AD 1396.0) recorded in ancient Korean astronomical almanac

NASA Astrophysics Data System (ADS)

Jeon, Junhyeok; Lee, Yong Bok; Lee, Yong-Sam

2015-11-01

The study of old star catalogues provides important astrometric data. Most of the researches based on the old star catalogues were manuscript published in Europe and from Arabic/Islam. However, the old star catalogues published in East Asia did not get attention. Therefore, among the East Asian star catalogues we focus on a particular catalogue recorded in a Korean almanac. Its catalogue contains 277 stars that are positioned in a region within 10° of the ecliptic plane. The stars in the catalogue were identified using the modern Hipparcos catalogue. We identified 274 among 277 stars, which is a rate of 98.9 per cent. The catalogue records the epoch of the stars' positions as AD 1396.0. However, by using all of the identified stars we found that the initial epoch of the catalogue is AD 1363.1 ± 3.2. In conclusion, the star catalogue was compiled and edited from various older star catalogues. We assume a correlation with the Almagest by Ptolemaios. This study presents newly analysed results from the historically important astronomical data discovered in East Asia. Therefore, this star catalogue will become important data for comparison with the star catalogues published in Europe and from Arabic/Islam.

A survey for pulsations in A-type stars using SuperWASP

NASA Astrophysics Data System (ADS)

Holdsworth, Daniel L.

2015-12-01

"It is sound judgement to hope that in the not too distant future we shall be competent to understand so simple a thing as a star." - Sir Arthur Stanley Eddington, The Internal Constitution of Stars, 1926 A survey of A-type stars is conducted with the SuperWASP archive in the search for pulsationally variable stars. Over 1.5 million stars are selected based on their (J-H) colour. Periodograms are calculated for light curves which have been extracted from the archive and cleaned of spurious points. Peaks which have amplitudes greater than 0.5 millimagnitude are identified in the periodograms. In total, 202 656 stars are identified to show variability in the range 5-300 c/d. Spectroscopic follow-up was obtained for 38 stars which showed high-frequency pulsations between 60 and 235 c/d, and a further object with variability at 636 c/d. In this sample, 13 were identified to be normal A-type δ Sct stars, 14 to be pulsating metallic-lined Am stars, 11 to be rapidly oscillating Ap (roAp) stars, and one to be a subdwarf B variable star. The spectra were used not only to classify the stars, but to determine an effective temperature through Balmer line fitting. Hybrid stars have been identified in this study, which show pulsations in both the high- and low-overtone domains; an observation not predicted by theory. These stars are prime targets to perform follow-up observations, as a confirmed detection of this phenomenon will have significant impact on the theory of pulsations in A-type stars. The detected number of roAp stars has expanded the known number of this pulsator class by 22 per cent. Within these results both the hottest and coolest roAp star have been identified. Further to this, one object, KIC 7582608, was observed by the Kepler telescope for 4 yr, enabling a detailed frequency analysis. This analysis has identified significant frequency variations in this star, leading to the hypothesis that this is the first close binary star of its type. The observational results presented in this thesis are able to present new challenges to the theory of pulsations in A-type stars, with potentially having the effect of further delaying the full understanding of 'so simple a thing as a star'.

Which of Kepler's Stars Flare?

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-12-01

The habitability of distant exoplanets is dependent upon many factors one of which is the activity of their host stars. To learn about which stars are most likely to flare, a recent study examines tens of thousands of stellar flares observed by Kepler.Need for a Broader SampleArtists rendering of a flaring dwarf star. [NASAs Goddard Space Flight Center/S. Wiessinger]Most of our understanding of what causes a star to flare is based on observations of the only star near enough to examine in detail the Sun. But in learning from a sample size of one, a challenge arises: we must determine which conclusions are unique to the Sun (or Sun-like stars), and which apply to other stellar types as well.Based on observations and modeling, astronomers think that stellar flares result from the reconnection of magnetic field lines in a stars outer atmosphere, the corona. The magnetic activity is thought to be driven by a dynamo caused by motions in the stars convective zone.HR diagram of the Kepler stars, with flaring main-sequence (yellow), giant (red) and A-star (green) stars in the authors sample indicated. [Van Doorsselaere et al. 2017]To test whether these ideas are true generally, we need to understand what types of stars exhibit flares, and what stellar properties correlate with flaring activity. A team of scientists led by Tom Van Doorsselaere (KU Leuven, Belgium) has now used an enormous sample of flares observed by Kepler to explore these statistics.Intriguing TrendsVan Doorsselaere and collaborators used a new automated flare detection and characterization algorithm to search through the raw light curves from Quarter 15 of the Kepler mission, building a sample of 16,850 flares on 6,662 stars. They then used these to study the dependence of the flare occurrence rate, duration, energy, and amplitude on the stellar spectral type and rotation period.This large statistical study led the authors to several interesting conclusions, including:Flare star incidence rate as a a function of Rossby number, which traces stellar rotation. Higher rotation rates correspond to lower Rossby numbers, so these data indicate that more rapidly rotating stars are more likely to exhibit flares. [Van Doorsselaere et al. 2017]Roughly 3.5% of Kepler stars in this sample are flaring stars.24 new A stars are found to show flaring activity. This is interesting because A stars arent thought to have an outer convective zone, which should prevent a magnetic dynamo from operating. Yet these flaring-star detections add to the body of evidence that at least some A stars do show magnetic activity.Most flaring stars in the sample are main-sequence stars, but 653 giants were found to have flaring activity. As with A stars, its unexpected that giant stars would have strong magnetic fields their increase in size and gradual spin-down over time should result in weakening of the surface fields. Nevertheless, it seems that the flare incidence of giant stars is similar to that of F or G main-sequence stars.All stellar types appear to have a small fraction of flare stars stars with an especially high rate of flare occurrence.Rapidly rotating stars are more likely to flare, tend to flare more often, and tend to have stronger flares than slowly rotating stars.As a next step, the authors plan to apply their flare detection algorithm to the larger sample of all Kepler data. In the meantime, this study has both deepened a few mysteries and moved us a step closer in our understanding of which stars flare and why.CitationTom Van Doorsselaere et al 2017 ApJS 232 26. doi:10.3847/1538-4365/aa8f9a

The Evolution of Carbon Stars

NASA Astrophysics Data System (ADS)

Chan, S. Josephine

1993-04-01

This dissertation is concerned with the nature of the carbon stars, unusual late-type stars in which the abundance of carbon in the photosphere is greater than that of oxygen. Data from the Infrared Astronomical Satellite (IRAS) survey has shown that carbon stars which were identified from optical surveys and those identified from the SiC dust features in their IRAS Low Resolution Spectrometer LRS spectra have different IRAS colours. The former (which will be referred to as visual carbon stars) are visually bright and have large excesses at 6 microns, while the latter group (which will be referred to as infrared carbon stars) have blackbody energy distributions. The origin of visual carbon stars has been discussed by Chan and Kwok (1988) based on the hypothesis of Willems and de Jong (1988). A complete sample of visual carbon stars detected by IRAS with 12 microns flux densities greater than 5 Jy was selected, and 207 LRS spectra were extracted for those sources without previous \\lrs data. Of these, 152 sources had new LRS spectra with reasonably good signal-to-noise ratio and 575 sources had previously released LRS spectra. All these spectra have been classified with the scheme of Volk and Cohen (1989). When the LRS spectra of these 727 IRAS CCGCS sources were examined, 15 were found to show the 9.7 microns silicate emission feature which is expected to occur only in an oxygen-rich circumstellar shell. Eight of these are reported for the first time in this dissertation. This group of visual carbon stars (hereafter called silicate carbon stars) may represent transition objects between oxygen-rich and carbon stars on the asymptotic giant branch (AGB) because the photosphere is carbon-rich while the circumstellar material resembles that from a typical M-type star. A radiative transfer dust shell model for these silicate carbon stars is presented. The model spectra produce excellent fits to the observed energy distributions of these silicate carbon stars. The J-type stars (^13C-rich carbon stars) have been suggested to be transition objects between M-type stars and C-type stars. An optical spectroscopic study of these silicate carbon stars was performed at the Dominion Astrophysical Observatory (DAO) in Victoria in 1991. CCGCS 1653, CCGCS 4222, CCGCS 4923 and CCGCS 5848 have been confirmed to be J stars. CCGCS 1158 and CCGCS 4729 are provisionally identified as J stars. A preliminary spectral analysis has also been carried out. Model calculations are presented on the evolution from the visual carbon stars to infrared carbon stars, and on the evolution of infrared carbon stars. A new empirical opacity function for the SiC grain is derived based on the LRS spectra of a selected sample of infrared carbon stars. A two-shell model has been developed with an oxygen-rich detached shell and a newly-forming SiC dust shell. The energy distributions of ~110 transition objects which are late-stage visual carbon stars or early-stage infrared carbon stars are fitted with this Interrupted Mass Loss Model. Furthermore, the model tracks successfully explain the "C" shaped distribution of the transition objects in the IRAS 12 microns/25 microns/60 microns colour-colour diagram. The energy distributions of ~150 infrared carbon stars are also matched with a radiative transfer dust shell model using only SiC dust. The colour evolution of infrared carbon stars can be explained with a continuous increase in mass loss rate on the AGB. An evolutionary scenario of AGB stars is suggested. There is a branching of M-type and C-type stars on the AGB with each branch evolving independently to the planetary nebula stage. The initial mass of the star in the main sequence may be the factor that determines which branch the star will follow. (SECTION: Dissertation Abstracts)

Collisions of dark matter axion stars with astrophysical sources

DOE PAGES

Eby, Joshua; Leembruggen, Madelyn; Leeney, Joseph; ...

2017-04-18

If QCD axions form a large fraction of the total mass of dark matter, then axion stars could be very abundant in galaxies. As a result, collisions with each other, and with other astrophysical bodies, can occur. We calculate the rate and analyze the consequences of three classes of collisions, those occurring between a dilute axion star and: another dilute axion star, an ordinary star, or a neutron star. In all cases we attempt to quantify the most important astrophysical uncertainties; we also pay particular attention to scenarios in which collisions lead to collapse of otherwise stable axion stars, and possible subsequent decay through number changing interactions. Collisions between two axion stars can occur with a high total rate, but the low relative velocity required for collapse to occur leads to a very low total rate of collapses. On the other hand, collisions between an axion star and an ordinary star have a large rate,more » $$\\Gamma_\\odot \\sim 3000$$ collisions/year/galaxy, and for sufficiently heavy axion stars, it is plausible that most or all such collisions lead to collapse. We identify in this case a parameter space which has a stable region and a region in which collision triggers collapse, which depend on the axion number ($N$) in the axion star, and a ratio of mass to radius cubed characterizing the ordinary star ($$M_s/R_s^3$$). Finally, we revisit the calculation of collision rates between axion stars and neutron stars, improving on previous estimates by taking cylindrical symmetry of the neutron star distribution into account. Finally, collapse and subsequent decay through collision processes, if occurring with a significant rate, can affect dark matter phenomenology and the axion star mass distribution.« less

Role of cell deformability in the two-dimensional melting of biological tissues

NASA Astrophysics Data System (ADS)

Li, Yan-Wei; Ciamarra, Massimo Pica

2018-04-01

The size and shape of a large variety of polymeric particles, including biological cells, star polymers, dendrimes, and microgels, depend on the applied stresses as the particles are extremely soft. In high-density suspensions these particles deform as stressed by their neighbors, which implies that the interparticle interaction becomes of many-body type. Investigating a two-dimensional model of cell tissue, where the single particle shear modulus is related to the cell adhesion strength, here we show that the particle deformability affects the melting scenario. On increasing the temperature, stiff particles undergo a first-order solid/liquid transition, while soft ones undergo a continuous solid/hexatic transition followed by a discontinuous hexatic/liquid transition. At zero temperature the melting transition driven by the decrease of the adhesion strength occurs through two continuous transitions as in the Kosterlitz, Thouless, Halperin, Nelson, and Young scenario. Thus, there is a range of adhesion strength values where the hexatic phase is stable at zero temperature, which suggests that the intermediate phase of the epithelial-to-mesenchymal transition could be hexatic type.

Penetrable square-well fluids: exact results in one dimension.

PubMed

Santos, Andrés; Fantoni, Riccardo; Giacometti, Achille

2008-05-01

We introduce a model of attractive penetrable spheres by adding a short-range attractive square well outside a penetrable core, and we provide a detailed analysis of structural and thermodynamical properties in one dimension using the exact impenetrable counterpart as a starting point. The model is expected to describe star polymers in regimes of good and moderate solvent under dilute conditions. We derive the exact coefficients of a low-density expansion up to second order for the radial distribution function and up to fourth order in the virial expansion. These exact results are used as a benchmark to test the reliability of approximate theories (Percus-Yevick and hypernetted chain). Notwithstanding the lack of an exact solution for arbitrary densities, our results are expected to be rather precise within a wide range of temperatures and densities. A detailed analysis of some limiting cases is carried out. In particular, we provide a complete solution of the sticky penetrable-sphere model in one dimension up to the same order in density. The issue of Ruelle's thermodynamics stability is analyzed and the region of a well-defined thermodynamic limit is identified.

Linear and Star Poly(ionic liquid) Assemblies: Surface Monolayers and Multilayers.

PubMed

Erwin, Andrew J; Xu, Weinan; He, Hongkun; Matyjaszewski, Krzysztof; Tsukruk, Vladimir V

2017-04-04

The surface morphology and organization of poly(ionic liquid)s (PILs), poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] are explored in conjunction with their molecular architecture, adsorption conditions, and postassembly treatments. The formation of stable PIL Langmuir and Langmuir-Blodgett (LB) monolayers at the air-water and air-solid interfaces is demonstrated. The hydrophobic bis(trifluoromethylsulfonyl)imide (Tf 2 N - ) is shown to be a critical agent governing the assembly morphology, as observed in the reversible condensation of LB monolayers into dense nanodroplets. The PIL is then incorporated as an unconventional polyelectrolyte component in the layer-by-layer (LbL) films of hydrophobic character. We demonstrate that the interplay of capillary forces, macromolecular mobility, and structural relaxation of the polymer chains influence the dewetting mechanisms in the PIL multilayers, thereby enabling access to a diverse set of highly textured, porous, and interconnected network morphologies for PIL LbL films that would otherwise be absent in conventional LbL films. Their compartmentalized internal structure is relevant to molecular separation membranes, ultrathin hydrophobic coatings, targeted cargo delivery, and highly conductive films.

An ellipsometric approach towards the description of inhomogeneous polymer-based Langmuir layers

PubMed Central

Rottke, Falko O; Schulz, Burkhard; Richau, Klaus; Kratz, Karl

2016-01-01

Summary The applicability of nulling-based ellipsometric mapping as a complementary method next to Brewster angle microscopy (BAM) and imaging ellipsometry (IE) is presented for the characterization of ultrathin films at the air–water interface. First, the methodology is demonstrated for a vertically nonmoving Langmuir layer of star-shaped, 4-arm poly(ω-pentadecalactone) (PPDL-D4). Using nulling-based ellipsometric mapping, PPDL-D4-based inhomogeneously structured morphologies with a vertical dimension in the lower nm range could be mapped. In addition to the identification of these structures, the differentiation between a monolayer and bare water was possible. Second, the potential and limitations of this method were verified by applying it to more versatile Langmuir layers of telechelic poly[(rac-lactide)-co-glycolide]-diol (PLGA). All ellipsometric maps were converted into thickness maps by introduction of the refractive index that was derived from independent ellipsometric experiments, and the result was additionally evaluated in terms of the root mean square roughness, R q. Thereby, a three-dimensional view into the layers was enabled and morphological inhomogeneity could be quantified. PMID:27826490

Nanoscale Motion of Soft Nanoparticles in Unentangled and Entangled Polymer Matrices

NASA Astrophysics Data System (ADS)

Lungova, M.; Krutyeva, M.; Pyckhout-Hintzen, W.; Wischnewski, A.; Monkenbusch, M.; Allgaier, J.; Ohl, M.; Sharp, M.; Richter, D.

2016-09-01

We have studied the motion of polyhedral oligomeric silsesquioxane (POSS) nanoparticles modified with poly(ethylene glycol) (PEG) arms immersed in PEG matrices of different molecular weight. Employing neutron spin echo spectroscopy in combination with pulsed field gradient (PFG) NMR we found the following. (i) For entangled matrices the center of mass mean square displacement (MSD) of the PEG-POSS particles is subdiffusive following a t0.56 power law. (ii) The diffusion coefficient as well as the crossover to Fickian diffusion is independent of the matrix molecular weight and takes place as soon as the center of mass has moved a distance corresponding to the particle radius—this holds also for unentangled hosts. (iii) For the entangled matrices Rubinstein's scaling theory is validated; however, the numbers indicate that beyond Rouse friction the entanglement constraints appear to strongly increase the effective friction even on the nanoparticle length scale imposing a caveat on the interpretation of microrheological experiments. (iv) The oligomer decorated PEG-POSS particles exhibit the dynamics of a Gaussian star with an internal viscosity that rises with an increase of the host molecular weight.

Favorable effect of in-situ generated platinum in the membrane on fuel cell membrane durability

NASA Astrophysics Data System (ADS)

Macauley, Natalia; Wong, Ka Hung; Watson, Mark; Kjeang, Erik

2015-12-01

The overall lifetime of polymer electrolyte fuel cells is often determined by the membrane durability. Platinum, which may dissolve from the catalyst layers during fuel cell operation and deposit in the membrane, has been shown to have both positive and negative effects on membrane stability. In the present work, we analyze what specific conditions are required in order to reach a favorable, membrane stabilizing effect with the controlled use of platinum in the membrane. Using accelerated membrane durability testing, field operated membrane samples, and electron microscopy, we demonstrate that a high platinum concentration with specific particle shapes and sizes is essential for enhanced membrane stability. Specifically, star shaped and dendritic particles with high particle density and high surface area are shown to be preferable. These particles contain high levels of Pt(111) and are expected to have high catalytic activity toward peroxide quenching and crossover gas consumption, thereby mitigating chemical membrane degradation. On the other hand, small, dispersed cubic particles are found to have no effect or the opposite, negative effect on membrane stability.

Structure of xanthan gum and cell ultrastructure at different times of alkali stress

PubMed Central

de Mello Luvielmo, Márcia; Borges, Caroline Dellinghausen; de Oliveira Toyama, Daniela; Vendruscolo, Claire Tondo; Scamparini, Adilma Regina Pippa

2016-01-01

The effect of alkali stress on the yield, viscosity, gum structure, and cell ultrastructure of xanthan gum was evaluated at the end of fermentation process of xanthan production by Xanthomonas campestris pv. manihotis 280-95. Although greater xanthan production was observed after a 24 h-alkali stress process, a lower viscosity was observed when compared to the alkali stress-free gum, regardless of the alkali stress time. However, this outcome is not conclusive as further studies on gum purification are required to remove excess sodium, verify the efficiency loss and the consequent increase in the polymer viscosity. Alkali stress altered the structure of xanthan gum from a polygon-like shape to a star-like form. At the end of the fermentation, early structural changes in the bacterium were observed. After alkali stress, marked structural differences were observed in the cells. A more vacuolated cytoplasm and discontinuities in the membrane cells evidenced the cell lysis. Xanthan was observed in the form of concentric circles instead of agglomerates as observed prior to the alkali stress. PMID:26887232

Polymers All Around You!

ERIC Educational Resources Information Center

Gertz, Susan

Background information on natural polymers, synthetic polymers, and the properties of polymers is presented as an introduction to this curriculum guide. Details are provided on the use of polymer products in consumer goods, polymer recycling, polymer densities, the making of a polymer such as GLUEP, polyvinyl alcohol, dissolving plastics, polymers…

Robotic surgery in children: adopt now, await, or dismiss?

PubMed

Cundy, Thomas P; Marcus, Hani J; Hughes-Hallett, Archie; Khurana, Sanjeev; Darzi, Ara

2015-12-01

The role of robot-assisted surgery in children remains controversial. This article aims to distil this debate into an evidence informed decision-making taxonomy; to adopt this technology (1) now, (2) later, or (3) not at all. Robot-assistance is safe, feasible and effective in selected cases as an adjunctive tool to enhance capabilities of minimally invasive surgery, as it is known today. At present, expectations of rigid multi-arm robotic systems to deliver higher quality care are over-estimated and poorly substantiated by evidence. Such systems are associated with high costs. Further comparative effectiveness evidence is needed to define the case-mix for which robot-assistance might be indicated. It seems unlikely that we should expect compelling patient benefits when it is only the mode of minimally invasive surgery that differs. Only large higher-volume institutions that share the robot amongst multiple specialty groups are likely to be able to sustain higher associated costs with today's technology. Nevertheless, there is great potential for next-generation surgical robotics to enable better ways to treat childhood surgical diseases through less invasive techniques that are not possible today. This will demand customized technology for selected patient populations or procedures. Several prototype robots exclusively designed for pediatric use are already under development. Financial affordability must be a high priority to ensure clinical accessibility.

A Bayesian adaptive design for biomarker trials with linked treatments

PubMed Central

Wason, James M S; Abraham, Jean E; Baird, Richard D; Gournaris, Ioannis; Vallier, Anne-Laure; Brenton, James D; Earl, Helena M; Mander, Adrian P

2015-01-01

Background: Response to treatments is highly heterogeneous in cancer. Increased availability of biomarkers and targeted treatments has led to the need for trial designs that efficiently test new treatments in biomarker-stratified patient subgroups. Methods: We propose a novel Bayesian adaptive randomisation (BAR) design for use in multi-arm phase II trials where biomarkers exist that are potentially predictive of a linked treatment's effect. The design is motivated in part by two phase II trials that are currently in development. The design starts by randomising patients to the control treatment or to experimental treatments that the biomarker profile suggests should be active. At interim analyses, data from treated patients are used to update the allocation probabilities. If the linked treatments are effective, the allocation remains high; if ineffective, the allocation changes over the course of the trial to unlinked treatments that are more effective. Results: Our proposed design has high power to detect treatment effects if the pairings of treatment with biomarker are correct, but also performs well when alternative pairings are true. The design is consistently more powerful than parallel-groups stratified trials. Conclusions: This BAR design is a powerful approach to use when there are pairings of biomarkers with treatments available for testing simultaneously. PMID:26263479

Comparison of design strategies for a three-arm clinical trial with time-to-event endpoint: Power, time-to-analysis, and operational aspects.

PubMed

Asikanius, Elina; Rufibach, Kaspar; Bahlo, Jasmin; Bieska, Gabriele; Burger, Hans Ulrich

2016-11-01

To optimize resources, randomized clinical trials with multiple arms can be an attractive option to simultaneously test various treatment regimens in pharmaceutical drug development. The motivation for this work was the successful conduct and positive final outcome of a three-arm randomized clinical trial primarily assessing whether obinutuzumab plus chlorambucil in patients with chronic lympocytic lymphoma and coexisting conditions is superior to chlorambucil alone based on a time-to-event endpoint. The inference strategy of this trial was based on a closed testing procedure. We compare this strategy to three potential alternatives to run a three-arm clinical trial with a time-to-event endpoint. The primary goal is to quantify the differences between these strategies in terms of the time it takes until the first analysis and thus potential approval of a new drug, number of required events, and power. Operational aspects of implementing the various strategies are discussed. In conclusion, using a closed testing procedure results in the shortest time to the first analysis with a minimal loss in power. Therefore, closed testing procedures should be part of the statistician's standard clinical trials toolbox when planning multiarm clinical trials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tug-of-war model for the two-bandit problem: nonlocally-correlated parallel exploration via resource conservation.

PubMed

Kim, Song-Ju; Aono, Masashi; Hara, Masahiko

2010-07-01

We propose a model - the "tug-of-war (TOW) model" - to conduct unique parallel searches using many nonlocally-correlated search agents. The model is based on the property of a single-celled amoeba, the true slime mold Physarum, which maintains a constant intracellular resource volume while collecting environmental information by concurrently expanding and shrinking its branches. The conservation law entails a "nonlocal correlation" among the branches, i.e., volume increment in one branch is immediately compensated by volume decrement(s) in the other branch(es). This nonlocal correlation was shown to be useful for decision making in the case of a dilemma. The multi-armed bandit problem is to determine the optimal strategy for maximizing the total reward sum with incompatible demands, by either exploiting the rewards obtained using the already collected information or exploring new information for acquiring higher payoffs involving risks. Our model can efficiently manage the "exploration-exploitation dilemma" and exhibits good performances. The average accuracy rate of our model is higher than those of well-known algorithms such as the modified -greedy algorithm and modified softmax algorithm, especially, for solving relatively difficult problems. Moreover, our model flexibly adapts to changing environments, a property essential for living organisms surviving in uncertain environments.

Functional Contour-following via Haptic Perception and Reinforcement Learning.

PubMed

Hellman, Randall B; Tekin, Cem; van der Schaar, Mihaela; Santos, Veronica J

2018-01-01

Many tasks involve the fine manipulation of objects despite limited visual feedback. In such scenarios, tactile and proprioceptive feedback can be leveraged for task completion. We present an approach for real-time haptic perception and decision-making for a haptics-driven, functional contour-following task: the closure of a ziplock bag. This task is challenging for robots because the bag is deformable, transparent, and visually occluded by artificial fingertip sensors that are also compliant. A deep neural net classifier was trained to estimate the state of a zipper within a robot's pinch grasp. A Contextual Multi-Armed Bandit (C-MAB) reinforcement learning algorithm was implemented to maximize cumulative rewards by balancing exploration versus exploitation of the state-action space. The C-MAB learner outperformed a benchmark Q-learner by more efficiently exploring the state-action space while learning a hard-to-code task. The learned C-MAB policy was tested with novel ziplock bag scenarios and contours (wire, rope). Importantly, this work contributes to the development of reinforcement learning approaches that account for limited resources such as hardware life and researcher time. As robots are used to perform complex, physically interactive tasks in unstructured or unmodeled environments, it becomes important to develop methods that enable efficient and effective learning with physical testbeds.

Network meta-analysis, electrical networks and graph theory.

PubMed

Rücker, Gerta

2012-12-01

Network meta-analysis is an active field of research in clinical biostatistics. It aims to combine information from all randomized comparisons among a set of treatments for a given medical condition. We show how graph-theoretical methods can be applied to network meta-analysis. A meta-analytic graph consists of vertices (treatments) and edges (randomized comparisons). We illustrate the correspondence between meta-analytic networks and electrical networks, where variance corresponds to resistance, treatment effects to voltage, and weighted treatment effects to current flows. Based thereon, we then show that graph-theoretical methods that have been routinely applied to electrical networks also work well in network meta-analysis. In more detail, the resulting consistent treatment effects induced in the edges can be estimated via the Moore-Penrose pseudoinverse of the Laplacian matrix. Moreover, the variances of the treatment effects are estimated in analogy to electrical effective resistances. It is shown that this method, being computationally simple, leads to the usual fixed effect model estimate when applied to pairwise meta-analysis and is consistent with published results when applied to network meta-analysis examples from the literature. Moreover, problems of heterogeneity and inconsistency, random effects modeling and including multi-armed trials are addressed. Copyright © 2012 John Wiley & Sons, Ltd. Copyright © 2012 John Wiley & Sons, Ltd.

Broadband W-band Rapid Frequency Sweep Considerations for Fourier Transform EPR.

PubMed

Strangeway, Robert A; Hyde, James S; Camenisch, Theodore G; Sidabras, Jason W; Mett, Richard R; Anderson, James R; Ratke, Joseph J; Subczynski, Witold K

2017-12-01

A multi-arm W-band (94 GHz) electron paramagnetic resonance spectrometer that incorporates a loop-gap resonator with high bandwidth is described. A goal of the instrumental development is detection of free induction decay following rapid sweep of the microwave frequency across the spectrum of a nitroxide radical at physiological temperature, which is expected to lead to a capability for Fourier transform electron paramagnetic resonance. Progress toward this goal is a theme of the paper. Because of the low Q-value of the loop-gap resonator, it was found necessary to develop a new type of automatic frequency control, which is described in an appendix. Path-length equalization, which is accomplished at the intermediate frequency of 59 GHz, is analyzed. A directional coupler is favored for separation of incident and reflected power between the bridge and the loop-gap resonator. Microwave leakage of this coupler is analyzed. An oversize waveguide with hyperbolic-cosine tapers couples the bridge to the loop-gap resonator, which results in reduced microwave power and signal loss. Benchmark sensitivity data are provided. The most extensive application of the instrument to date has been the measurement of T 1 values using pulse saturation recovery. An overview of that work is provided.

Bayesian adaptive phase II screening design for combination trials

PubMed Central

Cai, Chunyan; Yuan, Ying; Johnson, Valen E

2013-01-01

Background Trials of combination therapies for the treatment of cancer are playing an increasingly important role in the battle against this disease. To more efficiently handle the large number of combination therapies that must be tested, we propose a novel Bayesian phase II adaptive screening design to simultaneously select among possible treatment combinations involving multiple agents. Methods Our design is based on formulating the selection procedure as a Bayesian hypothesis testing problem in which the superiority of each treatment combination is equated to a single hypothesis. During the trial conduct, we use the current values of the posterior probabilities of all hypotheses to adaptively allocate patients to treatment combinations. Results Simulation studies show that the proposed design substantially outperforms the conventional multiarm balanced factorial trial design. The proposed design yields a significantly higher probability for selecting the best treatment while allocating substantially more patients to efficacious treatments. Limitations The proposed design is most appropriate for the trials combining multiple agents and screening out the efficacious combination to be further investigated. Conclusions The proposed Bayesian adaptive phase II screening design substantially outperformed the conventional complete factorial design. Our design allocates more patients to better treatments while providing higher power to identify the best treatment at the end of the trial. PMID:23359875

A multiple multicomponent approach to chimeric peptide-peptoid podands.

PubMed

Rivera, Daniel G; León, Fredy; Concepción, Odette; Morales, Fidel E; Wessjohann, Ludger A

2013-05-10

The success of multi-armed, peptide-based receptors in supramolecular chemistry traditionally is not only based on the sequence but equally on an appropriate positioning of various peptidic chains to create a multivalent array of binding elements. As a faster, more versatile and alternative access toward (pseudo)peptidic receptors, a new approach based on multiple Ugi four-component reactions (Ugi-4CR) is proposed as a means of simultaneously incorporating several binding and catalytic elements into organizing scaffolds. By employing α-amino acids either as the amino or acid components of the Ugi-4CRs, this multiple multicomponent process allows for the one-pot assembly of podands bearing chimeric peptide-peptoid chains as appended arms. Tripodal, bowl-shaped, and concave polyfunctional skeletons are employed as topologically varied platforms for positioning the multiple peptidic chains formed by Ugi-4CRs. In a similar approach, steroidal building blocks with several axially-oriented isocyano groups are synthesized and utilized to align the chimeric chains with conformational constrains, thus providing an alternative to the classical peptido-steroidal receptors. The branched and hybrid peptide-peptoid appendages allow new possibilities for both rational design and combinatorial production of synthetic receptors. The concept is also expandable to other multicomponent reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinematic evidence for feedback-driven star formation in NGC 1893

NASA Astrophysics Data System (ADS)

Lim, Beomdu; Sung, Hwankyung; Bessell, Michael S.; Lee, Sangwoo; Lee, Jae Joon; Oh, Heeyoung; Hwang, Narae; Park, Byeong-Gon; Hur, Hyeonoh; Hong, Kyeongsoo; Park, Sunkyung

2018-06-01

OB associations are the prevailing star-forming sites in the Galaxy. Up to now, the process of how OB associations were formed remained a mystery. A possible process is self-regulating star formation driven by feedback from massive stars. However, although a number of observational studies uncovered various signposts of feedback-driven star formation, the effectiveness of such feedback has been questioned. Stellar and gas kinematics is a promising tool to capture the relative motion of newborn stars and gas away from ionizing sources. We present high-resolution spectroscopy of stars and gas in the young open cluster NGC 1893. Our findings show that newborn stars and the tadpole nebula Sim 130 are moving away from the central cluster containing two O-type stars, and that the time-scale of sequential star formation is about 1 Myr within a 9 pc distance. The newborn stars formed by feedback from massive stars account for at least 18 per cent of the total stellar population in the cluster, suggesting that this process can play an important role in the formation of OB associations. These results support the self-regulating star formation model.

Search for OB stars running away from young star clusters. II. The NGC 6357 star-forming region

NASA Astrophysics Data System (ADS)

Gvaramadze, V. V.; Kniazev, A. Y.; Kroupa, P.; Oh, S.

2011-11-01

Dynamical few-body encounters in the dense cores of young massive star clusters are responsible for the loss of a significant fraction of their massive stellar content. Some of the escaping (runaway) stars move through the ambient medium supersonically and can be revealed via detection of their bow shocks (visible in the infrared, optical or radio). In this paper, which is the second of a series of papers devoted to the search for OB stars running away from young ( ≲ several Myr) Galactic clusters and OB associations, we present the results of the search for bow shocks around the star-forming region NGC 6357. Using the archival data of the Midcourse Space Experiment (MSX) satellite and the Spitzer Space Telescope, and the preliminary data release of the Wide-Field Infrared Survey Explorer (WISE), we discovered seven bow shocks, whose geometry is consistent with the possibility that they are generated by stars expelled from the young (~1-2 Myr) star clusters, Pismis 24 and AH03 J1725-34.4, associated with NGC 6357. Two of the seven bow shocks are driven by the already known OB stars, HD 319881 and [N78] 34. Follow-up spectroscopy of three other bow-shock-producing stars showed that they are massive (O-type) stars as well, while the 2MASS photometry of the remaining two stars suggests that they could be B0 V stars, provided that both are located at the same distance as NGC 6357. Detection of numerous massive stars ejected from the very young clusters is consistent with the theoretical expectation that star clusters can effectively lose massive stars at the very beginning of their dynamical evolution (long before the second mechanism for production of runaway stars, based on a supernova explosion in a massive tight binary system, begins to operate) and lends strong support to the idea that probably all field OB stars have been dynamically ejected from their birth clusters. A by-product of our search for bow shocks around NGC 6357 is the detection of three circular shells typical of luminous blue variable and late WN-type Wolf-Rayet stars.

Lithium abundances among solar-type pre-main-sequence stars

NASA Technical Reports Server (NTRS)

Strom, Karen M.; Wilkin, Francis P.; Strom, Stephen E.; Seaman, Robert L.

1989-01-01

Measurements of Li I 6707 A line strengths were carried out for two samples of pre-main-sequence (PMS) stars (L 1641 and Taurus-Auriga), and the Li abundances estimated for PMS stars are compared with those deduced from observations of Li line strengths for main-sequence stars in the Alpha Persei cluster. It was found that the maximum Li abundances among the PMS stars with solar mass values greater than 1.0 exceed the maximum abundances for Alpha Per stars by at least 0.3 dex. Some PMS stars, including few apparently young stars, showed large (greater than 1.0 dex) Li depletion, and some apparently old PMS stars showed little or no depletion.

Bursting star formation and the overabundance of Wolf-Rayet stars

NASA Technical Reports Server (NTRS)

Bodigfee, G.; Deloore, C.

1985-01-01

The ratio of the number of WR-stars to their OB progenitors appears to be significantly higher in some extragalactic systems than in our Galaxy. This overabundance of Wolf-Rayet-stars can be explained as a consequence of a recent burst of star formation. It is suggested that this burst is the manifestation of a long period nonlinear oscillation in the star formation process, produced by positive feedback effects between young stars and the interstellar medium. Star burst galaxies with large numbers of WR-stars must generate gamma - fluxes but due to the distance, all of them are beyond the reach of present-day ray detectors, except probably 30 Dor.

A deep survey for Galactic Wolf-Rayet stars. I - Motivation, search technique, and first results

NASA Technical Reports Server (NTRS)

Shara, Michael M.; Smith, Lindsey F.; Potter, Michael; Moffat, Anthony F. J.

1991-01-01

Results are presented from a survey of large areas of the southern Milky Way for Wolf-Rayet (WR) stars to 17-18th magnitude, carried out using direct narrowband and broadband Schmidt plates. Thirteen new WR stars were detected in an about 40-deg-sq region in Carina, where 24 WR stars were already known; the new stars were found to be significantly redder, fainter, and farther away than the known stars. Of the new WR stars, 11 are of subtype WN, and two are WC, compared to the 17 WN and seven WC stars among the previously known WR stars in the same area.

Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning.

PubMed

Gilbert, Dorothea; Witt, Gesine; Smedes, Foppe; Mayer, Philipp

2016-06-07

Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer-polymer partitioning as the basis for a deeper insight into partitioning differences of HOCs between polymers, calibrating analytical methods, and consistency checking of existing and calculation of new partition coefficients. Polymer-polymer partition coefficients were determined for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs) by equilibrating 13 silicones, including polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) in methanol-water solutions. Methanol as cosolvent ensured that all polymers reached equilibrium while its effect on the polymers' properties did not significantly affect silicone-silicone partition coefficients. However, we noticed minor cosolvent effects on determined polymer-polymer partition coefficients. Polymer-polymer partition coefficients near unity confirmed identical absorption capacities of several PDMS materials, whereas larger deviations from unity were indicated within the group of silicones and between silicones and LDPE. Uncertainty in polymer volume due to imprecise coating thickness or the presence of fillers was identified as the source of error for partition coefficients. New polymer-based (LDPE-lipid, PDMS-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients, recognizing that polymers can serve as a linking third phase for a quantitative understanding of equilibrium partitioning of HOCs between any two phases.

Rechargeable solid polymer electrolyte battery cell

DOEpatents

Skotheim, Terji

1985-01-01

A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

Starquakes, Heating Anomalies, and Nuclear Reactions in the Neutron Star Crust

NASA Astrophysics Data System (ADS)

Deibel, Alex Thomas

When the most massive stars perish, their cores may remain intact in the form of extremely dense and compact stars. These stellar remnants, called neutron stars, are on the cusp of becoming black holes and reach mass densities greater than an atomic nucleus in their centers. Although the interiors of neutron stars were difficult to investigate at the time of their discovery, the advent of modern space-based telescopes (e.g., Chandra X-ray Observatory) has pushed our understanding of the neutron star interior into exciting new realms. It has been shown that the neutron star interior spans an enormous range of densities and contains many phases of matter, and further theoretical progress must rely on numerical calculations of neutron star phenomena built with detailed nuclear physics input. To further investigate the properties of the neutron star interior, this dissertation constructs numerical models of neutron stars, applies models to various observations of neutron star high-energy phenomena, and draws new conclusions about the neutron star interior from these analyses. In particular, we model the neutron star's outermost ? 1 km that encompasses the neutron star's envelope, ocean, and crust. The model must implement detailed nuclear physics to properly simulate the hydrostatic and thermal structure of the neutron star. We then apply our model to phenomena that occur in these layers, such as: thermonuclear bursts in the envelope, g-modes in the ocean, torsional oscillations of the crust, and crust cooling of neutron star transients. A comparison of models to observations provides new insights on the properties of dense matter that are often difficult to probe through terrestrial experiments. For example, models of the quiescent cooling of neutron stars, such as the accreting transient MAXI J0556-332, at late times into quiescence probe the thermal transport properties of the deep neutron star crust. This modeling provides independent data from astronomical observations on the nature of neutron superfluidity and the thermal conductivity of nuclear pasta. Our neutron star modeling efforts also pose new questions. For instance, reaction networks find that neutrino emission from cycling nuclear reactions is present in the neutron star ocean and crust, and potentially cools an accreting neutron star. This is a theory we attempt to verify using observations of neutron star transients and thermonuclear bursts, although it remains unclear if this cooling occurs. Furthermore, on some accreting neutron stars, more heat than supplied by nuclear reactions is needed to explain their high temperatures at the outset of quiescence. Although the presence of heating anomalies seems common, the source of extra heating is difficult to determine.

Color excesses, intrinsic colors, and absolute magnitudes of Galactic and Large Magellanic Cloud Wolf-Rayet stars

NASA Technical Reports Server (NTRS)

Vacca, William D.; Torres-Dodgen, Ana V.

1990-01-01

A new method of determining the color excesses of WR stars in the Galaxy and the LMC has been developed and is used to determine the excesses for 44 Galactic and 32 LMC WR stars. The excesses are combined with line-free, narrow-band spectrophotometry to derive intrinsic colors of the WR stars of nearly all spectral subtypes. No correlation of UV spectral index or intrinsic colors with spectral subtype is found for the samples of single WN or WC stars. There is evidence that early WN stars in the LMC have flatter UV continua and redder intrinsic colors than early WN stars in the Galaxy. No separation is found between the values derived for Galactic WC stars and those obtained for LMC WC stars. The intrinsic colors are compared with those calculated from model atmospheres of WR stars and generally good agreement is found. Absolute magnitudes are derived for WR stars in the LMC and for those Galactic WR stars located in clusters and associations for which there are reliable distance estimates.

Method of making molecularly doped composite polymer material

DOEpatents

Affinito, John D [Tucson, AZ; Martin, Peter M [Kennewick, WA; Graff, Gordon L [West Richland, WA; Burrows, Paul E [Kennewick, WA; Gross, Mark E. , Sapochak, Linda S.

2005-06-21

A method of making a composite polymer of a molecularly doped polymer. The method includes mixing a liquid polymer precursor with molecular dopant forming a molecularly doped polymer precursor mixture. The molecularly doped polymer precursor mixture is flash evaporated forming a composite vapor. The composite vapor is cryocondensed on a cool substrate forming a composite molecularly doped polymer precursor layer, and the cryocondensed composite molecularly doped polymer precursor layer is cross linked thereby forming a layer of the composite polymer layer of the molecularly doped polymer.

Catalog of far-ultraviolet objective-prism spectrophotometry: Skylab experiment S-019, ultraviolet steller astronomy

NASA Technical Reports Server (NTRS)

Henize, K. G.; Wray, J. D.; Parsons, S. B.; Benedict, G. F.

1979-01-01

Ultraviolet stellar spectra in the wavelength region from 1300 to 5000 A (130 to 500) were photographed during the three manned Skylab missions using a 15 cm aperture objective-prism telescope. The prismatic dispersion varied from 58 A mm/1 at 1400 A to 1600 A mm/1 at 3000 A. Approximately 1000 spectra representing 500 stars were measured and reduced to observed fluxes. About 100 stars show absorption lines of Si IV, C IV, or C II. Numerous line features are also recorded in supergiant stars, shell stars, A and F stars, and Wolf-Rayet stars. Most of the stars in the catalog are of spectral class B, with a number of O and A type stars and a sampling of WC, WN, F and C type stars. Spectrophotometric results are tabulated for these 500 stars.

A key factor to the spin parameter of uniformly rotating compact stars: crust structure

NASA Astrophysics Data System (ADS)

Qi, Bin; Zhang, Nai-Bo; Sun, Bao-Yuan; Wang, Shou-Yu; Gao, Jian-Hua

2016-04-01

We study the dimensionless spin parameter j ≡ cJ/(GM2) of different kinds of uniformly rotating compact stars, including traditional neutron stars, hyperonic neutron stars and hybrid stars, based on relativistic mean field theory and the MIT bag model. It is found that jmax ˜ 0.7, which had been suggested in traditional neutron stars, is sustained for hyperonic neutron stars and hybrid stars with M > 0.5 M⊙. Not the interior but rather the crust structure of the stars is a key factor to determine jmax for three kinds of selected compact stars. Furthermore, a universal formula j = 0.63(f/fK) - 0.42(f/fK)2 + 0.48(f/fK)3 is suggested to determine the spin parameter at any rotational frequency f smaller than the Keplerian frequency fK.

High Resolution Spectroscopy of Vega-like Stars: Abundances and Circumstellar Gas

NASA Technical Reports Server (NTRS)

Dunkin, S. K.; Barlow, M. J.; Ryan, Sean G.

1996-01-01

Vega-like stars are main-sequence stars exhibiting excess infrared emission. In an effort to improve the information available on this class of star, 13 stars have been analyzed which have been classed as Vega-like, or have an infra-red excess attributable to dust in their circumstellar environment. In a separate paper stellar properties such as effective temperature and log g have been derived and in this poster we highlight the results of the photospheric abundance analysis also carried out during this work. King recently drew attention to the possible link between Vega-like stars and the photospheric metal-depleted class of A-stars, the Lambda Bootis stars. Since Vega-like stars are thought to have disks of dust, it might be expected that accretion of depleted gas onto the surface of these stars may cause this same phenomenon. In the 6 stars studied for depletions, none showed the extreme underabundance patterns observed in Lambda Bootis stars. However, depletions of silicon and magnesium were found in two of the sample, suggesting that these elements are in silicate dust grains in the circumstellar environment of these stars. Absorption lines attributed to circumstellar gas have been positively identified in three stars in our sample. Individual cases show evidence either of high-velocity outflowing gas, variability in the circumstellar lines observed, or evidence of circumstellar gas in excited lines of Fe II. No previous identification of circumstellar material has been made for two of the stars in question.

The Morphology and Uniformity of Circumstellar OH/H2O Masers around OH/IR Stars

NASA Astrophysics Data System (ADS)

Felli, Derek Sean

Even though low mass stars ( 8 solar masses), the more massive stars drive the chemical evolution of galaxies from which the next generation of stars and planets can form. Understanding mass loss of asymptotic giant branch stars contributes to our understanding of the chemical evolution of the galaxy, stellar populations, and star formation history. Stars with mass 8 solar masses go supernova. In both cases, these stars enrich their environments with elements heavier than simple hydrogen and helium molecules. While some general info about how stars die and form planetary nebulae are known, specific details are missing due to a lack of high-resolution observations and analysis of the intermediate stages. For example, we know that mass loss in stars creates morphologically diverse planetary nebulae, but we do not know the uniformity of these processes, and therefore lack detailed models to better predict how spherically symmetric stars form asymmetric nebulae. We have selected a specific group of late-stage stars and observed them at different scales to reveal the uniformity of mass loss through different layers close to the star. This includes observing nearby masers that trace the molecular shell structure around these stars. This study revealed detailed structure that was analyzed for uniformity to place constraints on how the mass loss processes behave in models. These results will feed into our ability to create more detailed models to better predict the chemical evolution of the next generation of stars and planets.

THE INFRARED SPECTRAL PROPERTIES OF MAGELLANIC CARBON STARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sloan, G. C.; Kraemer, K. E.; McDonald, I.

2016-07-20

The Infrared Spectrograph on the Spitzer Space Telescope observed 184 carbon stars in the Magellanic Clouds. This sample reveals that the dust-production rate (DPR) from carbon stars generally increases with the pulsation period of the star. The composition of the dust grains follows two condensation sequences, with more SiC condensing before amorphous carbon in metal-rich stars, and the order reversed in metal-poor stars. MgS dust condenses in optically thicker dust shells, and its condensation is delayed in more metal-poor stars. Metal-poor carbon stars also tend to have stronger absorption from C{sub 2}H{sub 2} at 7.5 μ m. The relation betweenmore » DPR and pulsation period shows significant apparent scatter, which results from the initial mass of the star, with more massive stars occupying a sequence parallel to lower-mass stars, but shifted to longer periods. Accounting for differences in the mass distribution between the carbon stars observed in the Small and Large Magellanic Clouds reveals a hint of a subtle decrease in the DPR at lower metallicities, but it is not statistically significant. The most deeply embedded carbon stars have lower variability amplitudes and show SiC in absorption. In some cases they have bluer colors at shorter wavelengths, suggesting that the central star is becoming visible. These deeply embedded stars may be evolving off of the asymptotic giant branch and/or they may have non-spherical dust geometries.« less

Deep coupling of star tracker and MEMS-gyro data under highly dynamic and long exposure conditions

NASA Astrophysics Data System (ADS)

Sun, Ting; Xing, Fei; You, Zheng; Wang, Xiaochu; Li, Bin

2014-08-01

Star trackers and gyroscopes are the two most widely used attitude measurement devices in spacecrafts. The star tracker is supposed to have the highest accuracy in stable conditions among different types of attitude measurement devices. In general, to detect faint stars and reduce the size of the star tracker, a method with long exposure time method is usually used. Thus, under dynamic conditions, smearing of the star image may appear and result in decreased accuracy or even failed extraction of the star spot. This may cause inaccuracies in attitude measurement. Gyros have relatively good dynamic performance and are usually used in combination with star trackers. However, current combination methods focus mainly on the data fusion of the output attitude data levels, which are inadequate for utilizing and processing internal blurred star image information. A method for tracking deep coupling stars and MEMS-gyro data is proposed in this work. The method achieves deep fusion at the star image level. First, dynamic star image processing is performed based on the angular velocity information of the MEMS-gyro. Signal-to-noise ratio (SNR) of the star spot could be improved, and extraction is achieved more effectively. Then, a prediction model for optimal estimation of the star spot position is obtained through the MEMS-gyro, and an extended Kalman filter is introduced. Meanwhile, the MEMS-gyro drift can be estimated and compensated though the proposed method. These enable the star tracker to achieve high star centroid determination accuracy under dynamic conditions. The MEMS-gyro drift can be corrected even when attitude data of the star tracker are unable to be solved and only one navigation star is captured in the field of view. Laboratory experiments were performed to verify the effectiveness of the proposed method and the whole system.

Pulsating B and Be stars in the Small Magellanic Cloud

NASA Astrophysics Data System (ADS)

Diago, P. D.; Gutiérrez-Soto, J.; Fabregat, J.; Martayan, C.

2008-03-01

Context: Stellar pulsations in main-sequence B-type stars are driven by the κ-mechanism due to the Fe-group opacity bump. The current models do not predict the presence of instability strips in the B spectral domain at very low metallicities. As the metallicity of the SMC is lower than Z = 0.005, it constitutes a very suitable object to test these predictions. Aims: The main objective is to investigate the existence of B-type pulsators at low metallicities, searching for short-term periodic variability in absorption-line B and Be stars in the SMC. The analysis has been performed in a sample of 313 B and Be stars with fundamental astrophysical parameters accurately determined from high-resolution spectroscopy. Methods: Photometric light curves of the MACHO project have been analyzed using standard Fourier techniques and linear and non-linear least squares fitting methods. The position of the pulsating stars in the HR diagram has been used to ascertain their nature and to map the instability regions in the SMC. Results: We have detected 9 absorption-line B stars showing short-period variability, two among them being multiperiodic. One star is most likely a β Cephei variable and the remaining 8 are SPB stars. The SPB instability strip in the SMC is shifted towards higher temperatures than the Galaxy. In the Be star sample, 32 stars are short-period variables, 20 among them multiperiodic. 4.9% of B stars and 25.3% of Be stars are pulsating stars. Conclusions: β Cephei and SPB stars do exist at the SMC metallicity. The fractions of SPB stars and pulsating Be stars in the SMC are lower than in the Galaxy. The fraction of pulsating Be stars in the SMC is much higher than the fraction of pulsating absorption-line B stars, as in the Galaxy.

Anomalous double-mode RR Lyrae stars in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Soszyński, I.; Smolec, R.; Dziembowski, W. A.; Udalski, A.; Szymański, M. K.; Wyrzykowski, Ł.; Ulaczyk, K.; Poleski, R.; Pietrukowicz, P.; Kozłowski, S.; Skowron, D.; Skowron, J.; Mróz, P.; Pawlak, M.

2016-12-01

We report the discovery of a new subclass of double-mode RR Lyrae stars in the Large and Small Magellanic Clouds. The sample of 22 pulsating stars has been extracted from the latest edition of the Optical Gravitational Lensing Experiment collection of RR Lyrae variables in the Magellanic System. The stars pulsating simultaneously in the fundamental (F) and first-overtone (1O) modes have distinctly different properties than regular double-mode RR Lyrae variables (RRd stars). The P1O/PF period ratios of our anomalous RRd stars are within a range of 0.725-0.738, while `classical' double-mode RR Lyrae variables have period ratios in the range of 0.742-0.748. In contrast to the typical RRd stars, in the majority of the anomalous pulsators, the F-mode amplitudes are higher than the 1O-mode amplitudes. The light curves associated with the F-mode in the anomalous RRd stars show different morphology than the light curves of, both, regular RRd stars and single-mode RRab stars. Most of the anomalous double-mode stars show long-term modulations of the amplitudes (Blazhko-like effect). Translating the period ratios into the abundance parameter, Z, we find for our stars Z ∈ (0.002, 0.005) - an order of magnitude higher values than typical for RR Lyrae stars. The mass range of the RRd stars inferred from the WI versus PF diagram is (0.55-0.75) M⊙. These parameters cannot be accounted for with single star evolution assuming a Reimers-like mass-loss. Much greater mass-loss caused by interaction with other stars is postulated. We blame the peculiar pulsation properties of our stars to the parametric resonance instability of the 1O-mode to excitation of the F- and 2O-modes as with the inferred parameters of the stars 2ω1O ≈ ωF + ω2O.

Monolayers and multilayers of conjugated polymers as nanosized electronic components.

PubMed

Zotti, Gianni; Vercelli, Barbara; Berlin, Anna

2008-09-01

Conjugated polymers (CPs) are interesting materials for preparing devices based on nanoscopic molecular architectures because they exhibit electrical, electronic, magnetic, and optical properties similar to those of metals or semiconductors while maintaining the flexibility and ease of processing of polymers. The production of well-defined mono- and multilayers of CPs on electrodes with nanometer-scale, one-dimensional resolution remains, however, an important challenge. In this Account, we describe the preparation and conductive properties of nanometer-sized CP molecular structures formed on electrode surfaces--namely, self-assembled monolayer (SAM), brush-type, and self-assembled multilayer CPs--and in combination with gold nanoparticles (AuNPs). We have electrochemically polymerized SAMs of carboxyalkyl-functionalized terthiophenes aligned either perpendicular or parallel to the electrode surface. Anodic coupling of various pyrrole- and thiophene-based monomers in solution with the oligothiophene-based SAMs produced brush-like films. Microcontact printing of these SAMs produced patterns that, after heterocoupling, exhibited large height enhancements, as measured using atomic force microscopy (AFM). We have employed layer-by-layer self-assembly of water-soluble polythiophene-based polyelectrolytes to form self-assembled multilayers. The combination of isostructural polycationic and polyanionic polythiophenes produced layers of chains aligned parallel to the substrate plane. These stable, robust, and dense layers formed with high regularity on the preformed monolayers, with minimal interchain penetration. Infrared reflection/adsorption spectroscopy and X-ray diffraction analyses revealed unprecedented degrees of order. Deposition of soluble polypyrroles produced molecular layers that, when analyzed using a gold-coated AFM tip, formed gold-polymer-gold junctions that were either ohmic or rectifying, depending of the layer sequence. We also describe the electronic conduction of model alpha,omega-capped sexithiophenes featuring a range of electron donor/acceptor units and lengths of additional conjugation. The sexithiophene cores exhibit redox-type conductivity, developing at the neutral/cation and cation/dication levels with values depending the nature of the substitution and the redox system. Extending the conjugation beyond the sexithiophene frame introduces further oxidation processes displaying enhanced conductivity. Finally, we discuss the ability of CP-based monolayers to coordinate AuNPs. Although thiophene- and pyrrole-based oligomers aggregate toluene-soluble AuNPs, alkyl substitution inhibits the aggregation process through steric restraint. Consequently, we investigated the interactions between AuNPs and polypyrrole or polythiophene monolayers, including those formed from star-shaped molecules. The hindered aggregation provided by alkyl substituents allowed us to adsorb thiol-functionalized oligothiophenes and oligopyrroles directly onto preformed AuNPs. Novel materials incorporating AuNPs of the same size but bearing different conjugated ends or bridges have great promise for applications in electrocatalysis, electroanalysis, and organic electronics.

Binary Neutron Stars with Arbitrary Spins in Numerical Relativity

NASA Astrophysics Data System (ADS)

Pfeiffer, Harald; Tacik, Nick; Foucart, Francois; Haas, Roland; Kaplan, Jeffrey; Muhlberger, Curran; Duez, Matt; Kidder, Lawrence; Scheel, Mark; Szilagyi, Bela

2015-04-01

We present a code to construct initial data for binary neutron star where the stars are rotating. Our code, based on the formalism developed by Tichy, allows for arbitrary rotation axes of the neutron stars and is able to achieve rotation rates near rotational breakup. We demonstrate that orbital eccentricity of the binary neutron stars can be controlled to ~ 0 . 1 % . Preliminary evolutions show that spin- and orbit-precession of Neutron stars is well described by post-Newtonian approximation. The neutron stars show quasi-normal mode oscillations at an amplitude which increases with the rotation rate of the stars.

X-ray emission from an Ap star /Phi Herculis/ and a late B star /Pi Ceti/

NASA Technical Reports Server (NTRS)

Cash, W.; Snow, T. P., Jr.; Charles, P.

1979-01-01

Using the HEAO 1 soft X-ray sky survey, a search was conducted for X-ray emission from 18 stars in the spectral range B5-A7. The detection of 0.25 keV X-ray sources consistent with the positions of Pi Ceti, a normal B7 V star, and Phi Herculis, a classic Ap star was reported. The detection of these stars argues for large mass motions in the upper layers of stars in this spectral range, and argues against radiative diffusion as the source of abundance anomalies in Ap stars.

Gemini Spectroscopic Survey of Young Intermediate-Mass Star-Forming Regions

NASA Astrophysics Data System (ADS)

Lundquist, Michael; Kobulnicky, Henry

2018-01-01

The majority of stars form in embedded clusters. Current research into star formation has focused on either high-mass star-forming regions or low-mass star-forming regions. We present the results from a Gemini spectroscopic survey of young intermediate-mass star-forming regions. These are star forming regions selected to produce stars up to but not exceeding 8 solar masses. We obtained spectra of these regions with GNIRS on Gemini North and Flamingos-2 on Gemini South. We also combine this with near-infrared imaging from 2MASS, UKIDSS, and VVV to study the stellar content.

Spectral Analysis of the O(He)-Type Central Stars of the Planetary Nebulae K 1-27 and LoTr 4

NASA Technical Reports Server (NTRS)

Reindl, N.; Ringat, E.; Rauch, T.; Werner, K.; Kruk, J. W.

2011-01-01

The four known O(He) stars are the only amongst the hottest post-AGB stars whose atmospheres are composed of almost pure helium. Thus, their evolution deviates from the hydrogen-defiCient post-AGB evolutionary sequence of carbon-dominated stars like e.g. PG 1159 stars. The origin of the O(He) stars is still not explained. They might be either post-early AGB stars or the progeny of R Coronae Borealis stars. We present preliminary results of a non-LTE spectral analysis based on FUSE and HST/COS observations.

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

X-ray studies of coeval star samples. II - The Pleiades cluster as observed with the Einstein Observatory

NASA Technical Reports Server (NTRS)

Micela, G.; Sciortino, S.; Vaiana, G. S.; Harnden, F. R., Jr.; Rosner, R.

1990-01-01

Coronal X-ray emission of the Pleiades stars is investigated, and maximum likelihood, integral X-ray luminosity functions are computed for Pleiades members in selected color-index ranges. A detailed search is conducted for long-term variability in the X-ray emission of those stars observed more than once. An overall comparison of the survey results with those of previous surveys confirms the ubiquity of X-ray emission in the Pleiades cluster stars and its higher rate of emission with respect to older stars. It is found that the X-ray emission from dA and early dF stars cannot be proven to be dissimilar to that of Hyades and field stars of the same spectral type. The Pleiades cluster members show a real rise of the X-ray luminosity from dA stars to early dF stars. X-ray emission for the young, solarlike Pleiades stars is about two orders of magnitude more intense than for the nearby solarlike stars.

STANDARD STARS AND EMPIRICAL CALIBRATIONS FOR Hα AND Hβ PHOTOMETRY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joner, Michael D.; Hintz, Eric G., E-mail: joner@byu.edu, E-mail: hintz@byu.edu

2015-12-15

We define an Hα photometric system that is designed as a companion to the well established Hβ index. The new system is built on spectrophotometric observations of field stars as well as stars in benchmark open clusters. We present data for 75 field stars, 12 stars from the Coma star cluster, 24 stars from the Hyades, 17 stars from the Pleiades, and 8 stars from NGC 752 to be used as primary standard stars in the new systems. We show that the system transformations are relatively insensitive to the shape of the filter functions. We make comparisons of the Hαmore » index to the Hβ index and illustrate the relationship between the two systems. In addition, we present relations that relate both hydrogen indices to equivalent width and effective temperature. We derive equations to calibrate both systems for Main Sequence stars with spectral types in the range O9 to K2 for equivalent width and A2 to K2 for effective temperature.« less

Theory of Radiation Transfer in Neutron Star Atmospheres

NASA Technical Reports Server (NTRS)

Zavlin, Vyacheslav

2006-01-01

The possibility for direct investigation of thermal emission from isolated neutron stars opened about a quarter of century ago with the launch of the first X-ray observatories Einstein and EXOSAT stimulated developing models of the neutron star surface radiation which began at the end of 80's. Confronting observational data with theoretical models of thermal emission allows one to infer the surface temperatures, magnetic fields, chemical composition, and neutron star masses and radii. This information, supplemented with the model equations of state and neutron star cooling models, provides an opportunity to understand the fundamental properties of the superdense matter in the stars' interiors. Almost all available models are based on the assumption that thermal radiation emitted by a neutron star is formed in the superficial star's layers--atmosphere. The neutron star atmospheres are very different from those of usual stars due to the immense gravity and huge magnetic fields. In this presentation we review the current status of the neutron star atmosphere modeling, present most important results, discuss problems and possible future developments.

Novel approach to improve the attitude update rate of a star tracker.

PubMed

Zhang, Shuo; Xing, Fei; Sun, Ting; You, Zheng; Wei, Minsong

2018-03-05

The star tracker is widely used in attitude control systems of spacecraft for attitude measurement. The attitude update rate of a star tracker is important to guarantee the attitude control performance. In this paper, we propose a novel approach to improve the attitude update rate of a star tracker. The electronic Rolling Shutter (RS) imaging mode of the complementary metal-oxide semiconductor (CMOS) image sensor in the star tracker is applied to acquire star images in which the star spots are exposed with row-to-row time offsets, thereby reflecting the rotation of star tracker at different times. The attitude estimation method with a single star spot is developed to realize the multiple attitude updates by a star image, so as to reach a high update rate. The simulation and experiment are performed to verify the proposed approaches. The test results demonstrate that the proposed approach is effective and the attitude update rate of a star tracker is increased significantly.

Properties of evolved mass-losing stars in the Milky Way and variations in the interstellar dust composition

NASA Technical Reports Server (NTRS)

Thronson, Harley A., Jr.; Latter, William B.; Black, John H.; Bally, John; Hacking, Perry

1987-01-01

A large sample of evolved carbon-rich and oxygen-rich objects has been studied using data from the IRAS Point Source Catalog. The number density of infrared-emitting 'carbon' stars shows no variation with Galactocentric radius, while the evolved 'oxygen' star volume density can be well fitted by a given law. A law is given for the number of carbon stars; a total is found in the Galaxy of 48,000 highly evolved oxygen stars. The mass-return rate for all evolved stars is found to be 0.35 solar mass/yr, with a small percentage contribution from carbon stars. The mass-loss rates for both types of stars are dominated by the small number of objects with the smallest rates. A mean lifetime of about 200,000 yr is obtained for both carbon and oxygen stars. Main-sequence stars in the mass range of three to five solar masses are the probable precursors of the carbon stars.

The s-Process Nucleosynthesis in Extremely Metal-Poor Stars as the Generating Mechanism of Carbon Enhanced Metal-Poor Stars

NASA Astrophysics Data System (ADS)

Suda, Takuma; Yamada, Shimako; Fujimoto, Masayuki Y.

The origin of carbon-enhanced metal-poor (CEMP) stars plays a key role in characterising the formation and evolution of the first stars and the Galaxy since the extremely-metal-poor (EMP) stars with [Fe/H] ≤ -2.5 share the common features of carbon enhancement in their surface chemical compositions. The origin of these stars is not yet established due to the controversy of the origin of CEMP stars without the enhancement of s-process element abundances, i.e., so called CEMP-no stars. In this paper, we elaborate the s-process nucleosynthesis in the EMP AGB stars and explore the origin of CEMP stars. We find that the efficiency of the s-process is controlled by O rather than Fe at [Fe/H] ≲ -2. We demonstrate that the relative abundances of Sr, Ba, Pb to C are explained in terms of the wind accretion from AGB stars in binary systems.

Radiative and Kinetic Feedback by Low-Mass Primordial Stars

NASA Astrophysics Data System (ADS)

Whalen, Daniel; Hueckstaedt, Robert M.; McConkie, Thomas O.

2010-03-01

Ionizing UV radiation and supernova (SN) flows amidst clustered minihalos at high redshift regulated the rise of the first stellar populations in the universe. Previous studies have addressed the effects of very massive primordial stars on the collapse of nearby halos into new stars, but the absence of the odd-even nucleosynthetic signature of pair-instability SNe in ancient metal-poor stars suggests that Population III stars may have been less than 100 M sun. We extend our earlier survey of local UV feedback on star formation to 25-80 M sun stars and include kinetic feedback by SNe for 25-40 M sun stars. We find radiative feedback to be relatively uniform over this mass range, primarily because the larger fluxes of more massive stars are offset by their shorter lifetimes. Our models demonstrate that prior to the rise of global UV backgrounds, Lyman-Werner (LW) photons from nearby stars cannot prevent halos from forming new stars. These calculations also reveal that violent dynamical instabilities can erupt in the UV radiation front enveloping a primordial halo, but that they ultimately have no effect on the formation of a star. Finally, our simulations suggest that relic H II regions surrounding partially evaporated halos may expel LW backgrounds at lower redshifts, allowing stars to form that were previously suppressed. We provide fits to radiative and kinetic feedback on star formation for use in both semianalytic models and numerical simulations.

Mechanism of mRNA-STAR domain interaction: Molecular dynamics simulations of Mammalian Quaking STAR protein.

PubMed

Sharma, Monika; Anirudh, C R

2017-10-03

STAR proteins are evolutionary conserved mRNA-binding proteins that post-transcriptionally regulate gene expression at all stages of RNA metabolism. These proteins possess conserved STAR domain that recognizes identical RNA regulatory elements as YUAAY. Recently reported crystal structures show that STAR domain is composed of N-terminal QUA1, K-homology domain (KH) and C-terminal QUA2, and mRNA binding is mediated by KH-QUA2 domain. Here, we present simulation studies done to investigate binding of mRNA to STAR protein, mammalian Quaking protein (QKI). We carried out conventional MD simulations of STAR domain in presence and absence of mRNA, and studied the impact of mRNA on the stability, dynamics and underlying allosteric mechanism of STAR domain. Our unbiased simulations results show that presence of mRNA stabilizes the overall STAR domain by reducing the structural deviations, correlating the 'within-domain' motions, and maintaining the native contacts information. Absence of mRNA not only influenced the essential modes of motion of STAR domain, but also affected the connectivity of networks within STAR domain. We further explored the dissociation of mRNA from STAR domain using umbrella sampling simulations, and the results suggest that mRNA binding to STAR domain occurs in multi-step: first conformational selection of mRNA backbone conformations, followed by induced fit mechanism as nucleobases interact with STAR domain.

Hubble Observes One-of-a-Kind Star Nicknamed ‘Nasty’

NASA Image and Video Library

2015-03-21

Astronomers using NASA’s Hubble Space Telescope have uncovered surprising new clues about a hefty, rapidly aging star whose behavior has never been seen before in our Milky Way galaxy. In fact, the star is so weird that astronomers have nicknamed it “Nasty 1,” a play on its catalog name of NaSt1. The star may represent a brief transitory stage in the evolution of extremely massive stars. First discovered several decades ago, Nasty 1 was identified as a Wolf-Rayet star, a rapidly evolving star that is much more massive than our sun. The star loses its hydrogen-filled outer layers quickly, exposing its super-hot and extremely bright helium-burning core. But Nasty 1 doesn’t look like a typical Wolf-Rayet star. The astronomers using Hubble had expected to see twin lobes of gas flowing from opposite sides of the star, perhaps similar to those emanating from the massive star Eta Carinae, which is a Wolf-Rayet candidate. Instead, Hubble revealed a pancake-shaped disk of gas encircling the star. The vast disk is nearly 2 trillion miles wide, and may have formed from an unseen companion star that snacked on the outer envelope of the newly formed Wolf-Rayet. Based on current estimates, the nebula surrounding the stars is just a few thousand years old, and as close as 3,000 light-years from Earth. Credits: NASA/Hubble

Star formation inside a galactic outflow.

PubMed

Maiolino, R; Russell, H R; Fabian, A C; Carniani, S; Gallagher, R; Cazzoli, S; Arribas, S; Belfiore, F; Bellocchi, E; Colina, L; Cresci, G; Ishibashi, W; Marconi, A; Mannucci, F; Oliva, E; Sturm, E

2017-04-13

Recent observations have revealed massive galactic molecular outflows that may have the physical conditions (high gas densities) required to form stars. Indeed, several recent models predict that such massive outflows may ignite star formation within the outflow itself. This star-formation mode, in which stars form with high radial velocities, could contribute to the morphological evolution of galaxies, to the evolution in size and velocity dispersion of the spheroidal component of galaxies, and would contribute to the population of high-velocity stars, which could even escape the galaxy. Such star formation could provide in situ chemical enrichment of the circumgalactic and intergalactic medium (through supernova explosions of young stars on large orbits), and some models also predict it to contribute substantially to the star-formation rate observed in distant galaxies. Although there exists observational evidence for star formation triggered by outflows or jets into their host galaxy, as a consequence of gas compression, evidence for star formation occurring within galactic outflows is still missing. Here we report spectroscopic observations that unambiguously reveal star formation occurring in a galactic outflow at a redshift of 0.0448. The inferred star-formation rate in the outflow is larger than 15 solar masses per year. Star formation may also be occurring in other galactic outflows, but may have been missed by previous observations owing to the lack of adequate diagnostics.

Metal-rich SX Phe stars in the Kepler field

NASA Astrophysics Data System (ADS)

Nemec, James M.; Balona, Luis A.; Murphy, Simon J.; Kinemuchi, Karen; Jeon, Young-Beom

2017-04-01

A spectroscopic and photometric analysis has been carried out for 32 candidate SX Phe variable blue straggler stars in the Kepler field. Radial velocities (RVs), space motions (U, V, W), projected rotation velocities (vsin I), spectral types and atmospheric characteristics (Teff, log g, [Fe/H], ξt, ζRT, etc.) are presented for 30 of the 32 stars. Although several stars are metal-weak with extreme halo orbits, the mean [Fe/H] of the sample is near-solar, thus the stars are more metal-rich than expected for a typical sample of Pop. II stars and more like halo metal-rich A-type stars. Two-thirds of the stars are fast rotators with vsin I > 50 km s-1, including four stars with vsin I > 200 km s-1. Three of the stars have (negative) RVs > 250 km s-1, five have retrograde space motions and 21 have total speeds (relative to the Local Standard of Rest) >400 km s-1. All but one of the 30 stars have positions in a Toomre diagram consistent with the kinematics of bona fide halo stars (the exception being a thick-disc star). Observed Rømer time delays, pulsation frequency modulations and light curves suggest that at least one-third of the stars are in binary (or triple) systems with orbital periods ranging from 2.3 d to more than four years.

The Magnetic Properties of Galactic OB Stars from the Magnetism in Massive Stars Project

NASA Astrophysics Data System (ADS)

Wade, Gregg A.; Grunhut, Jason; Petit, Veronique; Neiner, Coralie; Alecian, Evelyne; Landstreet, John; MiMeS Collaboration

2013-06-01

The Magnetism in Massive Stars (MiMeS) project represents the largest systematic survey of stellar magnetism ever undertaken. Comprising nearly 4500 high resolution polarised spectra of nearly 550 Galactic B and O-type stars, the MiMeS survey aims to address interesting and fundamental questions about the magnetism of hot, massive stars: How and when are massive star magnetic fields generated, and how do they evolve throughout stellar evolution? How do magnetic fields couple to and interact with the powerful winds of OB stars, and what are the consequences for the wind structure, momentum flux and energetics? What are the detailed physical mechanisms that lead to the anomalously slow rotation of many magnetic massive stars? What is the ultimate impact of stellar magnetic fields -- both direct and indirect -- on the evolution of massive stars? In this talk we report results from the analysis of the B-type stars observed within the MiMeS survey. The sample consists of over 450 stars ranging in spectral type from B9 to B0, and in evolutionary stage from the pre-main sequence to the post-main sequence. In addition to general statistical results concerning field incidence, strength and topology, we will elaborate our conclusions for subsamples of special interest, including the Herbig and classical Be stars, pulsating B stars and chemically peculiar B stars.

Design of Stomach Acid-Stable and Mucin-Binding Enzyme Polymer Conjugates.

PubMed

Cummings, Chad S; Campbell, Alan S; Baker, Stefanie L; Carmali, Sheiliza; Murata, Hironobu; Russell, Alan J

2017-02-13

The reduced immunogenicity and increased stability of protein-polymer conjugates has made their use in therapeutic applications particularly attractive. However, the physicochemical interactions between polymer and protein, as well as the effect of this interaction on protein activity and stability, are still not fully understood. In this work, polymer-based protein engineering was used to examine the role of polymer physicochemical properties on the activity and stability of the chymotrypsin-polymer conjugates and their degree of binding to intestinal mucin. Four different chymotrypsin-polymer conjugates, each with the same polymer density, were synthesized using "grafting-from" atom transfer radical polymerization. The influence of polymer charge on chymotrypsin-polymer conjugate mucin binding, bioactivity, and stability in stomach acid was determined. Cationic polymers covalently attached to chymotrypsin showed high mucin binding, while zwitterionic, uncharged, and anionic polymers showed no mucin binding. Cationic polymers also increased chymotrypsin activity from pH 6-8, while zwitterionic polymers had no effect, and uncharged and anionic polymers decreased enzyme activity. Lastly, cationic polymers decreased the tendency of chymotrypsin to structurally unfold at extremely low pH, while uncharged and anionic polymers induced unfolding more quickly. We hypothesized that when polymers are covalently attached to the surface of a protein, the degree to which those polymers interact with the protein surface is the predominant determinant of whether the polymer will stabilize or inactivate the protein. Preferential interactions between the polymer and the protein lead to removal of water from the surface of the protein, and this, we believe, inactivates the enzyme.

Converting neutron stars into strange stars

NASA Technical Reports Server (NTRS)

Olinto, A. V.

1991-01-01

If strange matter is formed in the interior of a neutron star, it will convert the entire neutron star into a strange star. The proposed mechanisms are reviewed for strange matter seeding and the possible strange matter contamination of neutron star progenitors. The conversion process that follows seeding and the recent calculations of the conversion timescale are discussed.

On the Evolution of O(He)-Type Stars

NASA Technical Reports Server (NTRS)

Kruk, Jeffrey W.; Reindl, N.; Rauch, T.; Werner, K.

2012-01-01

O(He) stars represent a small group of four very hot post-AGB stars whose atmospheres are composed of almost pure helium. Their evolution deviates from the hydrogen-deficient post-AGO evolutionary sequence of carbon-dominated stars like e.g. PG 1159 or Wolf- Rayet stars. While (very) late thermal pulse evolutionary models can explain the observed He/C/O abundances in these objects, they do not reproduce He-dominated surface abundances. Currently it seems most likely that the O(He) stars originate from a double helium white dwarf merger and so they could be the successors of the luminous helium-rich sdO-stars. An other possibility is that O(He)-stars could be successors of RCB or EHe stars.

The Spots and Activity of Stars in the Beehive Cluster Observed by the Kepler Space Telescope (K2)

NASA Astrophysics Data System (ADS)

Savanov, I. S.; Kalinicheva, E. S.; Dmitrienko, E. S.

2018-05-01

The spottedness parameters S (the fraction of the visible surface of the star occupied by spots) characterizing the activity of 674 stars in the Beehive Cluster (age 650 Myr) are estimated, together with variations of this parameter as a function of the rotation period, Rossby number Ro and other characteristics of the stars. The activity of the stars in this cluster is lower than the activity of stars in the younger Pleiades (125 Myr). The average S value for the Beehive Cluster stars is 0.014, while Pleiades stars have the much higher average value 0.052. The activity parameters of 61 solar-type stars in the Beehive Cluster, similar Hyades stars (of about the same age), and stars in the younger Pleiades are compared. The average S value of such objects in the Beehive Cluster is 0.014± 0.008, nearly coincident with the estimate obtained for solar-type Hyades stars. The rotation periods of these objects are 9.1 ± 3.4 day, on average, in agreement with the average rotation period of the Hyades stars (8.6 d ). Stars with periods exceeding 3-4 d are more numerous in the Beehive Cluster than in the Pleiades, and their periods have a larger range, 3-30 d . The characteristic dependence with a kink at Ro (saturation) = 0.13 is not observed in the S-Rossby number diagram for the Beehive and Hyades stars, only a clump of objects with Rossby numbers Ro > 0.7. The spottedness data for the Beehive Cluster and Hyades stars are in good agreement with the S values for dwarfs with ages of 600-700 Myr. This provides evidence for the reliability of the results of gyrochronological calibrations. The data for the Beehive and Pleiades stars are used to analyze variations in the spot-forming activity for a large number of stars of the same age that are members of a single cluster. A joint consideration of the data for two clusters can be used to draw conclusions about the time evolution of the activity of stars of different masses (over a time interval of the order of 500 Myr).

Early-type objects in NGC 6611 and the Eagle Nebula

NASA Astrophysics Data System (ADS)

Martayan, C.; Floquet, M.; Hubert, A. M.; Neiner, C.; Frémat, Y.; Baade, D.; Fabregat, J.

2008-10-01

Aims: An important question about Be stars is whether they are born as such or whether they have become Be stars during their evolution. It is necessary to observe young clusters to answer this question. Methods: To this end, observations of stars in NGC 6611 and the star-formation region of Eagle Nebula were carried out with the ESO-WFI in slitless spectroscopic mode and at the VLT-GIRAFFE (R ≃ 6400-17 000). The targets for the GIRAFFE observations were pre-selected from the literature and our catalogue of emission-line stars based on the WFI study. GIRAFFE observations allowed us to study the population of the early-type stars accurately both with and without emission lines. For this study, we determined the fundamental parameters of OBA stars thanks to the GIRFIT code. We also studied the status of the objects (main sequence or pre-main sequence stars) by using IR data, membership probabilities, and location in HR diagrams. Results: The nature of the early-type stars with emission-line stars in NGC 6611 and its surrounding environment is derived. The slitless observations with the WFI clearly indicate a small number of emission-line stars in M16. We observed with GIRAFFE 101 OBA stars, among them 9 are emission-line stars with circumstellar emission in Hα. We found that W080 could be a new He-strong star, like W601. W301 is a possible classical Be star, W503 is a mass-transfer eclipsing binary with an accretion disk, and the other ones are possible Herbig Ae/Be stars. We also found that the rotational velocities of main sequence B stars are 18% lower than those of pre-main sequence B stars, in good agreement with theory about the evolution of rotational velocities. Combining adaptive optics, IR data, spectroscopy, and radial velocity indications, we found that 27% of the B-type stars are binaries. We also redetermined the age of NGC 6611 found equal to 1.2-1.8 Myears, in good agreement with the most recent determinations.

Massive runaway stars in the Large Magellanic Cloud

NASA Astrophysics Data System (ADS)

Gvaramadze, V. V.; Kroupa, P.; Pflamm-Altenburg, J.

2010-09-01

The origin of massive field stars in the Large Magellanic Cloud (LMC) has long been an enigma. The recent measurements of large offsets (˜ 100 km s-1) between the heliocentric radial velocities of some very massive (O2-type) field stars and the systemic LMC velocity provides a possible explanation of this enigma and suggests that the field stars are runaway stars ejected from their birthplaces at the very beginning of their parent cluster's dynamical evolution. A straightforward way to prove this explanation is to measure the proper motions of the field stars and to show that they are moving away from one of the nearby star clusters or OB associations. This approach is, however, complicated by the long distance to the LMC, which makes accurate proper motion measurements difficult. We used an alternative approach for solving the problem (first applied for Galactic field stars), based on the search for bow shocks produced by runaway stars. The geometry of detected bow shocks would allow us to infer the direction of stellar motion, thereby determining their possible parent clusters. In this paper we present the results of a search for bow shocks around six massive field stars that have been proposed as candidate runaway stars. Using archival Spitzer Space Telescope data, we found a bow shock associated with one of our programme stars, the O2 V((f*)) star BI 237, which is the first-ever detection of bow shocks in the LMC. Orientation of the bow shock suggests that BI 237 was ejected from the OB association LH 82 (located at ≃ 120 pc in projection from the star). A by-product of our search is the detection of bow shocks generated by four OB stars in the field of the LMC and an arc-like structure attached to the candidate luminous blue variable R81 (HD 269128). The geometry of two of these bow shocks is consistent with the possibility that their associated stars were ejected from the 30 Doradus star-forming complex. We discuss implications of our findings for the problem of the origin of runaway stars and the early dynamical evolution of star clusters.

B- and A-Type Stars in the Taurus-Auriga Star-Forming Region

NASA Technical Reports Server (NTRS)

Mooley, Kunal; Hillenbrand, Lynne; Rebull, Luisa; Padgett, Deborah; Knapp, Gillian

2013-01-01

We describe the results of a search for early-type stars associated with the Taurus-Auriga molecular cloud complex, a diffuse nearby star-forming region noted as lacking young stars of intermediate and high mass. We investigate several sets of possible O, B, and early A spectral class members. The first is a group of stars for which mid-infrared images show bright nebulae, all of which can be associated with stars of spectral-type B. The second group consists of early-type stars compiled from (1) literature listings in SIMBAD, (2) B stars with infrared excesses selected from the Spitzer Space Telescope survey of the Taurus cloud, (3) magnitude- and color-selected point sources from the Two Micron All Sky Survey, and (4) spectroscopically identified early-type stars from the Sloan Digital Sky Survey coverage of the Taurus region. We evaluated stars for membership in the Taurus-Auriga star formation region based on criteria involving: spectroscopic and parallactic distances, proper motions and radial velocities, and infrared excesses or line emission indicative of stellar youth. For selected objects, we also model the scattered and emitted radiation from reflection nebulosity and compare the results with the observed spectral energy distributions to further test the plausibility of physical association of the B stars with the Taurus cloud. This investigation newly identifies as probable Taurus members three B-type stars: HR 1445 (HD 28929), t Tau (HD 29763), 72 Tau (HD 28149), and two A-type stars: HD 31305 and HD 26212, thus doubling the number of stars A5 or earlier associated with the Taurus clouds. Several additional early-type sources including HD 29659 and HD 283815 meet some, but not all, of the membership criteria and therefore are plausible, though not secure, members.

Hubble:WFPC2 and ESO:2.2-m Composite Image of 30 Dor Runaway Star

NASA Image and Video Library

2017-12-08

NASA image release May 11, 2010 Hubble Catches Heavyweight Runaway Star Speeding from 30 Doradus Image: Hubble/WFPC2 and ESO/2.2-m Composite Image of 30 Dor Runaway Star A blue-hot star, 90 times more massive than our Sun, is hurtling across space fast enough to make a round trip from Earth to the Moon in merely two hours. Though the speed is not a record-breaker, it is unique to find a homeless star that has traveled so far from its nest. The only way the star could have been ejected from the star cluster where it was born is through a tussle with a rogue star that entered the binary system where the star lived, which ejected the star through a dynamical game of stellar pinball. This is strong circumstantial evidence for stars as massive as 150 times our Sun's mass living in the cluster. Only a very massive star would have the gravitational energy to eject something weighing 90 solar masses. The runaway star is on the outskirts of the 30 Doradus nebula, a raucous stellar breeding ground in the nearby Large Magellanic Cloud. The finding bolsters evidence that the most massive stars in the local universe reside in 30 Doradus, making it a unique laboratory for studying heavyweight stars. 30 Doradus, also called the Tarantula Nebula, is roughly 170,000 light-years from Earth. To learn more about this image go to: www.nasa.gov/mission_pages/hubble/science/runaway-star.html Credit: NASA, ESA, J. Walsh (ST-ECF), and ESO NASA Goddard Space Flight Center is home to the nation's largest organization of combined scientists, engineers and technologists that build spacecraft, instruments and new technology to study the Earth, the sun, our solar system, and the universe.

Lithium Inventory of 2 Solar Mass Red Clump Stars in Open Clusters: A Test of the Helium Flash Mechanism

NASA Technical Reports Server (NTRS)

Carlberg, Joleen K.; Cunha, Katia; Smith, Verne V.

2016-01-01

The temperature distribution of field Li-rich red giants suggests the presence of a population of Li-rich red clump (RC) stars. One proposed explanation for this population is that all stars with masses near 2 solar mass experience a shortlived phase of Li-richness at the onset of core He-burning. Many of these stars have low C-12/C-13, a signature of deep mixing that is presumably associated with the Li regeneration. To test this purported mechanism of Li enrichment, we measured abundances in 38 RC stars and 6 red giant branch (RGB) stars in four open clusters selected to have RC masses near 2 solar mass. We find six Li-rich stars (A(Li) greater than or equal to 1.50 dex) of which only two may be RC stars. None of the RC stars have Li exceeding the levels observed in the RGB stars, but given the brevity of the suggested Li-rich phase and the modest sample size, it is probable that stars with larger Li-enrichments were missed simply by chance. However, we find very few stars in our sample with low C-12/C-13. Such low C-12/C-13, seen in many field Li-rich stars, should persist even after lithium has returned to normal low levels. Thus, if Li synthesis during the He flash occurs, it is a rare, but potentially long-lived occurrence rather than a short-lived phase for all stars. We estimate a conservative upper limit of the fraction of stars going through a Li-rich phase to be less than 47%, based on stars that have low C-12/C-13 for their observed A(Li).

Induced Star Formation

NASA Astrophysics Data System (ADS)

Kennicutt, Robert C., Jr.

Overview: Induced Star Formation and Interactions Introduction Historical Background: First Hints Systematic Studies: Starbursts Interactions and Nuclear activity IRAS and Ultralumious starburst Galaxies The 1990's: HST, Supercomputers, and the Distant Universe Key Questions and Issues Organization of Lectures Star Formation Properties of Normal Galaxies Observational Techniques Results: Star Formation in Normal Galaxies Interpretation: Star Formation Histories Global Star Formation in interacting Galaxies A Gallery of Interactions and Mergers Star Formation Statistics: Guilt By Association Tests SFRs in Interacting vs Noninteracting Galaxies Kinematic Properties and Regulation of SFRs Induced Nuclear Activity and Star Formation Background: Nuclear Spectra and Classification Nuclear Star Formation and Starbursts Nuclear Star Formation and Interactions Induced AGN Activity: Statistics of Seyfert Galaxies Environments of Quasars Kinematic Clues to the Triggering of AGNs Infrared Luminous Galaxies and Starbursts Background: IR Luminous Galaxies and IRAS Infrared Luminosity Function and Spectra Infrared Structure and Morphology Interstellar Gas X-Ray Emission and Superwinds Optical, UV, and Near-Infrared Spectra Radio Continuum Emission Evidence for Interactions and Mergers The Power Source: Starbursts or Dusty AGNs? Spectral Diagnostics of Starbursts Evolutionary Synthesis Models Applications: Integrated Colors of Interacting Galaxies Applications: Hα Emission, Colors, and SFRs Applications: Spectral Modelling of Evolved Starbursts Infrared Starbursts and the IMF in starbursts Triggering and Regulation of Star Formation: The Problem Introduction: Star Formation as a Nonlinear Process The schmidt Law in Normal Galaxies Star Formation Regimes in Interacting Galaxies Summary Triggering and Regulation of Starbusts: Theoretical Ideas Gravitational Star Formation Thresholds Cloud Collision Models Radial Transport of Gas: Clues from Barred Galaxies Simulations of Starbursts in Merging Galaxies The Cosmological Role of Interactions and Starbursts Interactions in Hierarchical Cosmology Interaction-Induced Star Formation Today Interaction-Induced Star Formation in the Past Disk kinematics and the Merger Rate Global Effects of Starbursts and Superwinds Concluding Remarks References

Design and DSP implementation of star image acquisition and star point fast acquiring and tracking

NASA Astrophysics Data System (ADS)

Zhou, Guohui; Wang, Xiaodong; Hao, Zhihang

2006-02-01

Star sensor is a special high accuracy photoelectric sensor. Attitude acquisition time is an important function index of star sensor. In this paper, the design target is to acquire 10 samples per second dynamic performance. On the basis of analyzing CCD signals timing and star image processing, a new design and a special parallel architecture for improving star image processing are presented in this paper. In the design, the operation moving the data in expanded windows including the star to the on-chip memory of DSP is arranged in the invalid period of CCD frame signal. During the CCD saving the star image to memory, DSP processes the data in the on-chip memory. This parallelism greatly improves the efficiency of processing. The scheme proposed here results in enormous savings of memory normally required. In the scheme, DSP HOLD mode and CPLD technology are used to make a shared memory between CCD and DSP. The efficiency of processing is discussed in numerical tests. Only in 3.5ms is acquired the five lightest stars in the star acquisition stage. In 43us, the data in five expanded windows including stars are moved into the internal memory of DSP, and in 1.6ms, five star coordinates are achieved in the star tracking stage.

Constraints on pre-main-sequence evolution from stellar pulsations

NASA Astrophysics Data System (ADS)

Casey, M. P.; Zwintz, K.; Guenther, D. B.

2014-02-01

Pulsating pre-main-sequence (PMS) stars afford the earliest opportunity in the lifetime of a star to which the concepts of asteroseismology can be applied. PMS stars should be structurally simpler than their evolved counterparts, thus (hopefully!) making any asteroseismic analysis relatively easier. Unfortunately, this isn't necessarily the case. The majority of these stars (around 80) are δ Scuti pulsators, with a couple of γ Doradus, γ Doradus - δ Scuti hybrids, and slowly pulsating B stars thrown into the mix. The majority of these stars have only been discovered within the last ten years, with the community still uncovering the richness of phenomena associated with these stars, many of which defy traditional asteroseismic analysis. A systematic asteroseismic analysis of all of the δ Scuti PMS stars was performed in order to get a better handle on the properties of these stars as a group. Some strange results have been found, including one star pulsating up to the theoretical acoustic cut-off frequency of the star, and a number of stars in which the most basic asteroseismic analysis suggests problems with the stars' positions in the Hertzsprung-Russell diagram. From this we get an idea of the\\break constraints - or lack thereof - that these results can put on PMS stellar evolution.

An Autonomous Star Identification Algorithm Based on One-Dimensional Vector Pattern for Star Sensors

PubMed Central

Luo, Liyan; Xu, Luping; Zhang, Hua

2015-01-01

In order to enhance the robustness and accelerate the recognition speed of star identification, an autonomous star identification algorithm for star sensors is proposed based on the one-dimensional vector pattern (one_DVP). In the proposed algorithm, the space geometry information of the observed stars is used to form the one-dimensional vector pattern of the observed star. The one-dimensional vector pattern of the same observed star remains unchanged when the stellar image rotates, so the problem of star identification is simplified as the comparison of the two feature vectors. The one-dimensional vector pattern is adopted to build the feature vector of the star pattern, which makes it possible to identify the observed stars robustly. The characteristics of the feature vector and the proposed search strategy for the matching pattern make it possible to achieve the recognition result as quickly as possible. The simulation results demonstrate that the proposed algorithm can effectively accelerate the star identification. Moreover, the recognition accuracy and robustness by the proposed algorithm are better than those by the pyramid algorithm, the modified grid algorithm, and the LPT algorithm. The theoretical analysis and experimental results show that the proposed algorithm outperforms the other three star identification algorithms. PMID:26198233

An Autonomous Star Identification Algorithm Based on One-Dimensional Vector Pattern for Star Sensors.

PubMed

Luo, Liyan; Xu, Luping; Zhang, Hua

2015-07-07

In order to enhance the robustness and accelerate the recognition speed of star identification, an autonomous star identification algorithm for star sensors is proposed based on the one-dimensional vector pattern (one_DVP). In the proposed algorithm, the space geometry information of the observed stars is used to form the one-dimensional vector pattern of the observed star. The one-dimensional vector pattern of the same observed star remains unchanged when the stellar image rotates, so the problem of star identification is simplified as the comparison of the two feature vectors. The one-dimensional vector pattern is adopted to build the feature vector of the star pattern, which makes it possible to identify the observed stars robustly. The characteristics of the feature vector and the proposed search strategy for the matching pattern make it possible to achieve the recognition result as quickly as possible. The simulation results demonstrate that the proposed algorithm can effectively accelerate the star identification. Moreover, the recognition accuracy and robustness by the proposed algorithm are better than those by the pyramid algorithm, the modified grid algorithm, and the LPT algorithm. The theoretical analysis and experimental results show that the proposed algorithm outperforms the other three star identification algorithms.

Rejuvenation of the Innocent Bystander: Results from a Pilot X-ray Study of Dwarf Carbon Stars

NASA Astrophysics Data System (ADS)

Mazzoni, Fernando; Montez, Rodolfo; Green, Paul

2018-01-01

We present the results of a pilot study by the Chandra X-ray Observatory of X-ray emission from dwarf Carbon (dC) stars. Carbon stars were thought to be exclusively AGB stars but main sequence dwarfs showing carbon molecular bands appear to be the dominant variety. The existence of dC stars is surprising since dwarf stars cannot intrinsically produce carbon as an AGB star can. It is hypothesized that dC stars are polluted by an evolved companion star. Evidence of past pollution can appear in X-ray emission where increased coronal activity (“spin-up”) or mass accretion via a disk can be detected. Using the Chandra X-ray Observatory we detected X-ray photons in the vicinity of all the dC stars in our a pilot sample. For each detection we characterized the X-ray emission and compared to the emission expected from potential emission scenarios. Although the process that produces the X-ray emission from dC stars is presently unclear and our pilot sample is small, our results suggest that X-ray emission might be a universal characteristic of dC stars. Further examination of the X-ray emission plus future X-ray and multiwavelength observations will help us better understand the nature of these intriguing stars.

The mass distribution of Population III stars

NASA Astrophysics Data System (ADS)

Fraser, M.; Casey, A. R.; Gilmore, G.; Heger, A.; Chan, C.

2017-06-01

Extremely metal-poor (EMP) stars are uniquely informative on the nature of massive Population III stars. Modulo a few elements that vary with stellar evolution, the present-day photospheric abundances observed in EMP stars are representative of their natal gas cloud composition. For this reason, the chemistry of EMP stars closely reflects the nucleosynthetic yields of supernovae from massive Population III stars. Here we collate detailed abundances of 53 EMP stars from the literature and infer the masses of their Population III progenitors. We fit a simple initial mass function (IMF) to a subset of 29 of the inferred Population III star masses, and find that the mass distribution is well represented by a power-law IMF with exponent α = 2.35^{+0.29}_{-0.24}. The inferred maximum progenitor mass for supernovae from massive Population III stars is M_{max} = 87^{+13}_{-33} M⊙, and we find no evidence in our sample for a contribution from stars with masses above ˜120 M⊙. The minimum mass is strongly consistent with the theoretical lower mass limit for Population III supernovae. We conclude that the IMF for massive Population III stars is consistent with the IMF of present-day massive stars and there may well have formed stars much below the supernova mass limit that could have survived to the present day.

Composite membranes, methods of making same, and applications of same

DOEpatents

Pintauro, Peter N.; Park, Andrew; Ballengee, Jason

2016-05-24

In one aspect of the present invention, a method of fabricating a composite membrane includes: forming a first polymer solution from a first polymer and a second polymer solution from a second polymer, respectively, where the first polymer includes a charged polymer and the second polymer includes an uncharged polymer; electrospinning, separately and simultaneously, the first and second polymer solutions to form a dual fiber mat with first polymer fibers and second polymer fibers; and processing the dual fiber mat by softening and flowing one of the first or second polymer fibers to fill in the void space between the other of the first and second polymer fibers so as to form the composite membrane. In some embodiments, the composite membrane may be a proton exchange membrane (PEM) or an anion exchange membrane (AEM).

A triangle voting algorithm based on double feature constraints for star sensors

NASA Astrophysics Data System (ADS)

Fan, Qiaoyun; Zhong, Xuyang

2018-02-01

A novel autonomous star identification algorithm is presented in this study. In the proposed algorithm, each sensor star constructs multi-triangle with its bright neighbor stars and obtains its candidates by triangle voting process, in which the triangle is considered as the basic voting element. In order to accelerate the speed of this algorithm and reduce the required memory for star database, feature extraction is carried out to reduce the dimension of triangles and each triangle is described by its base and height. During the identification period, the voting scheme based on double feature constraints is proposed to implement triangle voting. This scheme guarantees that only the catalog star satisfying two features can vote for the sensor star, which improves the robustness towards false stars. The simulation and real star image test demonstrate that compared with the other two algorithms, the proposed algorithm is more robust towards position noise, magnitude noise and false stars.

Spectroscopic observations of X-ray selected late type stars

NASA Technical Reports Server (NTRS)

Takalo, L. O.

1988-01-01

A spectroscopic survey of nine X-ray selected late type stars was conducted. These stars are serendipitously discovered EINSTEIN X-ray sources, selected from two large x-ray surveys: the Columbia Astrophysical Laboratory survey (five stars) and the CFA Medium Sensitivity survey (four stars). Four of the Columbia survey stars were found to be short period binaries. The fifth was found to be an active single G dwarf. None of the Medium Sensitivity survey stars were found to be either binaries or active stars. Activity was measured by comparing the H-alpha and the CaII infrared triplet (8498, 8542) lines in these stars to the lines in inactive stars of similar spectral type. A correlation was found between the excess H-alpha lime emission and V sin(i) and between the excess H-alpha line emission and X-ray luminosity. No correlation was found between the infrared line emission and any other measured quantity.

Identifying the stars on Johann Bayer's Chart of the South Polar Sky

NASA Astrophysics Data System (ADS)

Ridpath, I.

2014-04-01

The first chart of the stars in the region around the south celestial pole was published in 1603 by Johann Bayer (1572-1625) as part of his monumental star atlas called Uranometria. This south polar chart depicted 12 entirely new constellations that had been created only a few years earlier from stars observed during the first Dutch expedition to the East Indies in 1595-97. Bayer's chart plotted 121 stars in the 12 newly invented constellations. Five more stars formed a southern extension of the existing constellation Eridanus, while another twelve stars were left 'unformed', i.e. unattached to any constellation. Whereas Bayer famously applied Greek or Roman letters to the stars in the 48 Ptolemaic constellations, he left the stars in the newly invented constellations unlabelled. This paper attempts to identify the stars plotted on Bayer's chart. It also discusses the source of Bayer's data and the origin of the 12 new southern constellations.

(C-12)O emission from the envelopes of cool stars in the solar neighborhood

NASA Technical Reports Server (NTRS)

Margulis, M.; Van Blerkom, D. J.; Snell, R. L.; Kleinmann, S. G.

1990-01-01

Results are presented on observations of the CO J = 1-0 line emission from all M giants, S stars, and C stars listed in the Two-Micron Sky Survey having strong FIR emission and lying north of delta = -10 deg. The data from this survey and other data for C and S stars show that the line profiles of these stars look like flattened parabolas and have roughly the same shape for different stars. In contrast, the shapes of the spectral lines from giant M stars are diverse, ranging from triangular to spiked and asymmetric, suggesting that the envelopes of M stars have complex kinematics and structure. The outflow velocities inferred from the line profiles of the stars surveyed span a range of more than an order of magnitude, with the velocities of C stars correlating with IR color.

Smoke ring for a halo

NASA Image and Video Library

2015-10-26

Two stars shine through the centre of a ring of cascading dust in this image taken by the NASA/ESA Hubble Space Telescope. The star system is named DI Cha, and while only two stars are apparent, it is actually a quadruple system containing two sets of binary stars. As this is a relatively young star system it is surrounded by dust. The young stars are moulding the dust into a wispy wrap. The host of this alluring interaction between dust and star is the Chamaeleon I dark cloud — one of three such clouds that comprise a large star-forming region known as the Chamaeleon Complex. DI Cha's juvenility is not remarkable within this region. In fact, the entire system is among not only the youngest but also the closest collections of newly formed stars to be found and so provides an ideal target for studies of star formation.

Cannonballs Shoot from Star (Artist Concept)

NASA Image and Video Library

2016-10-06

This four-panel graphic illustrates how the binary-star system V Hydrae is launching balls of plasma into space. Panel 1 shows the two stars orbiting each other. One of the stars is nearing the end of its life and has swelled in size, becoming a red giant. In panel 2, the smaller star's orbit carries the star into the red giant's expanded atmosphere. As the star moves through the atmosphere, it gobbles up material from the red giant that settles into a disk around the star. The buildup of material reaches a tipping point and is eventually ejected as blobs of hot plasma along the star's spin axis, as shown in panel 3. This ejection process is repeated every eight years, which is the time it takes for the orbiting star to make another pass through the bloated red giant's envelope, as shown in panel 4. http://photojournal.jpl.nasa.gov/catalog/PIA21071

Blurred Star Image Processing for Star Sensors under Dynamic Conditions

PubMed Central

Zhang, Weina; Quan, Wei; Guo, Lei

2012-01-01

The precision of star point location is significant to identify the star map and to acquire the aircraft attitude for star sensors. Under dynamic conditions, star images are not only corrupted by various noises, but also blurred due to the angular rate of the star sensor. According to different angular rates under dynamic conditions, a novel method is proposed in this article, which includes a denoising method based on adaptive wavelet threshold and a restoration method based on the large angular rate. The adaptive threshold is adopted for denoising the star image when the angular rate is in the dynamic range. Then, the mathematical model of motion blur is deduced so as to restore the blurred star map due to large angular rate. Simulation results validate the effectiveness of the proposed method, which is suitable for blurred star image processing and practical for attitude determination of satellites under dynamic conditions. PMID:22778666

Observations of Nonthermal Radio Emission from Early-type Stars

NASA Technical Reports Server (NTRS)

Abbott, D. C.; Bieging, J. H.; Churchwell, E.

1985-01-01

As a part of a wider survey of radio emission from O, B, and Wolf-Rayet (WR) stars, five new stars whose radio emission is dominated by a nonthermal mechanism of unknown origin were discovered. From statistics of distance-limited samples of stars, it is estimated that the minimum fraction of stars which are nonthermal emitters is 25% for the OB stars and 10% for the WR stars. The characteristics of this new class of nonthermal radio emitter are investigated.

Four new Delta Scuti stars

NASA Technical Reports Server (NTRS)

Schutt, R. L.

1991-01-01

Four new Delta Scuti stars are reported. Power, modified into amplitude, spectra, and light curves are used to determine periodicities. A complete frequency analysis is not performed due to the lack of a sufficient time base in the data. These new variables help verify the many predictions that Delta Scuti stars probably exist in prolific numbers as small amplitude variables. Two of these stars, HR 4344 and HD 107513, are possibly Am stars. If so, they are among the minority of variable stars which are also Am stars.

Star formation across cosmic time and its influence on galactic dynamics

NASA Astrophysics Data System (ADS)

Freundlich, Jonathan

2015-12-01

Observations show that ten billion years ago, galaxies formed their stars at rates up to twenty times higher than now. As stars are formed from cold molecular gas, a high star formation rate means a significant gas supply, and galaxies near the peak epoch of star formation are indeed much more gas-rich than nearby galaxies. Is the decline of the star formation rate mostly driven by the diminishing cold gas reservoir, or are the star formation processes also qualitatively different earlier in the history of the Universe? Ten billion years ago, young galaxies were clumpy and prone to violent gravitational instabilities, which may have contributed to their high star formation rate. Stars indeed form within giant, gravitationally-bound molecular clouds. But the earliest phases of star formation are still poorly understood. Some scenarii suggest the importance of interstellar filamentary structures as a first step towards core and star formation. How would their filamentary geometry affect pre-stellar cores? Feedback mechanisms related to stellar evolution also play an important role in regulating star formation, for example through powerful stellar winds and supernovae explosions which expel some of the gas and can even disturb the dark matter distribution in which each galaxy is assumed to be embedded. This PhD work focuses on three perspectives: (i) star formation near the peak epoch of star formation as seen from observations at sub-galactic scales; (ii) the formation of pre-stellar cores within the filamentary structures of the interstellar medium; and (iii) the effect of feedback processes resulting from star formation and evolution on the dark matter distribution.

Two massive stars possibly ejected from NGC 3603 via a three-body encounter

NASA Astrophysics Data System (ADS)

Gvaramadze, V. V.; Kniazev, A. Y.; Chené, A.-N.; Schnurr, O.

2013-03-01

We report the discovery of a bow-shock-producing star in the vicinity of the young massive star cluster NGC 3603 using archival data of the Spitzer Space Telescope. Follow-up optical spectroscopy of this star with Gemini-South led to its classification as O6 V. The orientation of the bow shock and the distance to the star (based on its spectral type) suggest that the star was expelled from the cluster, while the young age of the cluster (˜2 Myr) implies that the ejection was caused by a dynamical few-body encounter in the cluster's core. The relative position on the sky of the O6 V star and a recently discovered O2 If*/WN6 star (located on the opposite side of NGC 3603) allows us to propose that both objects were ejected from the cluster via the same dynamical event - a three-body encounter between a single (O6 V) star and a massive binary (now the O2 If*/WN6 star). If our proposal is correct, then one can `weigh' the O2 If*/WN6 star using the conservation of the linear momentum. Given a mass of the O6 V star of ≈30 M⊙, we found that at the moment of ejection the mass of the O2 If*/WN6 star was ≈175 M⊙. Moreover, the observed X-ray luminosity of the O2 If*/WN6 star (typical of a single star) suggests that the components of this originally binary system have merged (e.g., because of encounter hardening).

The magnetic early B-type stars I: magnetometry and rotation

NASA Astrophysics Data System (ADS)

Shultz, M. E.; Wade, G. A.; Rivinius, Th; Neiner, C.; Alecian, E.; Bohlender, D.; Monin, D.; Sikora, J.; MiMeS Collaboration; BinaMIcS Collaboration

2018-04-01

The rotational and magnetic properties of many magnetic hot stars are poorly characterized, therefore the Magnetism in Massive Stars and Binarity and Magnetic Interactions in various classes of Stars collaborations have collected extensive high-dispersion spectropolarimetric data sets of these targets. We present longitudinal magnetic field measurements for 52 early B-type stars (B5-B0), with which we attempt to determine their rotational periods Prot. Supplemented with high-resolution spectroscopy, low-resolution Dominion Astrophysical Observatory circular spectropolarimetry, and archival Hipparcos photometry, we determined Prot for 10 stars, leaving only five stars for which Prot could not be determined. Rotational ephemerides for 14 stars were refined via comparison of new to historical magnetic measurements. The distribution of Prot is very similar to that observed for the cooler Ap/Bp stars. We also measured v sin i and vmac for all stars. Comparison to non-magnetic stars shows that v sin i is much lower for magnetic stars, an expected consequence of magnetic braking. We also find evidence that vmac is lower for magnetic stars. Least-squares deconvolution profiles extracted using single-element masks revealed widespread, systematic discrepancies in between different elements: this effect is apparent only for chemically peculiar stars, suggesting it is a consequence of chemical spots. Sinusoidal fits to H line measurements (which should be minimally affected by chemical spots), yielded evidence of surface magnetic fields more complex than simple dipoles in six stars for which this has not previously been reported; however, in all six cases, the second- and third-order amplitudes are small relative to the first-order (dipolar) amplitudes.

Extreme isolation of WN3/O3 stars and implications for their evolutionary origin as the elusive stripped binaries

NASA Astrophysics Data System (ADS)

Smith, Nathan; Götberg, Ylva; de Mink, Selma E.

2018-03-01

Recent surveys of the Magellanic Clouds have revealed a subtype of Wolf-Rayet (WR) star with peculiar properties. WN3/O3 spectra exhibit both WR-like emission and O3 V-like absorption - but at lower luminosity than O3 V or WN stars. We examine the projected spatial distribution of WN3/O3 stars in the Large Magellanic Cloud as compared to O-type stars. Surprisingly, WN3/O3 stars are among the most isolated of all classes of massive stars; they have a distribution similar to red supergiants dominated by initial masses of 10-15 M⊙, and are far more dispersed than classical WR stars or luminous blue variables. Their lack of association with clusters of O-type stars suggests strongly that WN3/O3 stars are not the descendants of single massive stars (30 M⊙ or above). Instead, they are likely products of interacting binaries at lower initial mass (10-18 M⊙). Comparison with binary models suggests a probable origin with primaries in this mass range that were stripped of their H envelopes through non-conservative mass transfer by a low-mass secondary. We show that model spectra and positions on the Hertzsprung-Russell diagram for binary-stripped stars are consistent with WN3/O3 stars. Monitoring radial velocities with high-resolution spectra can test for low-mass companions or runaway velocities. With lower initial mass and environments that avoid very massive stars, the WN3/O3 stars fit expectations for progenitors of Type Ib and possibly Type Ibn supernovae.

Measurements of mass accretion rates in Herbig Ae/Be stars

NASA Astrophysics Data System (ADS)

Donehew, Brian

Herbig Ae/Be stars(HAeBes) are young stellar objects of spectral class F2 through B0, with the central star often surrounded by a circumstellar disk of gas and dust. They are the higher mass analogs to T Tauri stars. The interaction between the star and the disk is not well understood, nor is the disk structure. The central star will often accrete mass from the disk, and the mass accretion rate is an important parameter for modeling the disk structure and evolution. The methods for measuring mass accretion rates of T Tauri stars are generally not applicable to HAeBe stars. As such, reliable measurements of mass accretion rates for HAeBes are rare. Garrison(1978) saw that the Balmer Discontinuity of HAeBes was veiled, and attributed this veiling to accretion luminosity. Building on Garrison(1978) and the work of Muzerolle et al. (2004), I determine the mass accretion rates and accretion luminosities of a large sample of HAeBe stars by measuring the veiling of the Balmer Discontinuity due to the accretion luminosity. Muzerolle et al. (1998) established a strong correlation between the accretion luminosity of T Tauri stars and the luminosity of Br gamma, and this correlation seems to extend to the evolutionary precursors to HAeBes, intermediate T Tauri stars, as well Calvet et al. (2004). I test this correlation for HAeBes and discover that it is valid for HAe stars but not for HBe stars. From examining the HAeBes of my sample from spectral range A3 to B7, there does not seem to be a particular spectral type at which the correlation fails. A few of the late HBe stars are consistent with the correlation, but most of the HBe stars have Br gamma luminosities much larger than what one would expect from the correlation. This suggests that there might be a significant stellar wind component to the Br gamma luminosity for many of the HBe stars. T Tauri stars accrete mass from their disks magnetospherically, in which the strong stellar field of the star truncates the disk at some distance from the star and the disk material than falls to the stellar surface along the magnetic field lines. HAeBe stars are not expected to have strong stellar magnetic fields, and observations have failed to find any such fields for most HAeBes (Alecian 2007). However, circumstantial evidence suggests that some HAeBe stars are accreting magnetospherically (Muzerolle et al. 2004, Brittain et al. 2009). Since the correlation between accretion luminosity and Br γ luminosity is valid for both T Tauri stars and HAe stars, this suggests that the same basic accretion process is occuring for both.

The Sun: A Star at the Center of Our Solar System

NASA Technical Reports Server (NTRS)

Adams, Mitzi L.

2016-01-01

There is a star at the center of our solar system! But what is a star? How do stars work? What are the characteristics of our Sun and how are these traits different from other stars? How does the Sun compare to stars such as Betelgeuse and Rigel? "Will the Sun end its life with a bang or a whimper?"

Space Science in Action: Stars [Videotape].

ERIC Educational Resources Information Center

1999

This videotape recording shows students the many ways scientists look at the stars and how they can use what they see to answer questions such as What are stars made of?, How far away are they?, and How old are the stars? Students learn about the life span of stars and the various stages they pass through from protostar to main sequence star to…

Observing the First Stars in Luminous, Red Galaxies

NASA Technical Reports Server (NTRS)

Heap, Sally; Lindler, Don

2010-01-01

Modern cosmological simulations predict that the first stars are to be found today in luminous, red galaxies. Although observing such stars individually against a background of younger, metal-rich stars is impossible, the first stars should make their presence known by their strong, line-free ultraviolet flux. We have found evidence for a UV-bright stellar population in Sloan spectra of LRG's at z=0.4-0.5. We present arguments for interpreting this UV-bright stellar population as the oldest stars, rather than other types of stellar populations (e.g. young stars or blue straggler stars in the dominant, metal-rich stellar population

No evidence of disk destruction by OB stars

NASA Astrophysics Data System (ADS)

Richert, Alexander J. W.; Feigelson, Eric

2015-01-01

It has been suggested that the hostile environments observed in massive star forming regions are inhospitable to protoplanetary disks and therefore to the formation of planets. The Orion Proplyds show disk evaporation by extreme ultraviolet (EUV) photons from Theta1 Orionis C (spectral type O6). In this work, we examine the spatial distributions of disk-bearing and non-disk bearing young stellar objects (YSOs) relative to OB stars in 17 massive star forming regions in the MYStIX (Massive Young Star-Forming Complex Study in Infrared and X-ray) survey. Any tendency of disky YSOs, identified by their infrared excess, to avoid OB stars would reveal complete disk destruction.We consider a sample of MYStIX that includes 78 O3-O9 stars, 256 B stars, 5,606 disky YSOs, and 5,794 non-disky YSOs. For each OB star, we compare the cumulative distribution functions of distances to disky and non-disky YSOs. We find no significant avoidance of OB stars by disky YSOs. This result indicates that OB stars are not sufficiently EUV-luminous and long-lived to completely destroy a disk within its ordinary lifetime. We therefore conclude that massive star forming regions are not clearly hostile to the formation of planets.

CEMP Stars in Dwarf Galaxies

NASA Astrophysics Data System (ADS)

Thidemann Hansen, Terese

2018-06-01

Exploration of the metal-poor stellar halo population of the Milky Way over the past decades has revealed a large number of stars strongly enhanced in carbon (CEMP stars). However, these stars are not as commonly detected in the dwarf galaxy satellites of the Milky Way (MW). The present-day satellites are thought to be similar to systems from which the MW and in particular its halo was formed via hierarchical mergers. I will present the results of abundance analysis for new samples of extremely metal-poor stars in Sculptor and Carina exploring the fraction of CEMP stars at low metallicity in these systems. I will also present the detailed abundance analyses of six CEMP stars detected in the Carina dwarf spheroidal galaxy. Five of these stars also show enhancement in slow neutron-capture elements and can thus be classified as CEMP-s stars, while the most metal-poor star with [Fe/H]=-2.5 shows no such enhancement and belongs to the CEMP-no class. The detection of CEMP stars in dwarf galaxies supports the hierarchical assembly of the MW halo and by providing a birth environment, can help to further constrain the formation of these stars.

Exposure Time Optimization for Highly Dynamic Star Trackers

PubMed Central

Wei, Xinguo; Tan, Wei; Li, Jian; Zhang, Guangjun

2014-01-01

Under highly dynamic conditions, the star-spots on the image sensor of a star tracker move across many pixels during the exposure time, which will reduce star detection sensitivity and increase star location errors. However, this kind of effect can be compensated well by setting an appropriate exposure time. This paper focuses on how exposure time affects the star tracker under highly dynamic conditions and how to determine the most appropriate exposure time for this case. Firstly, the effect of exposure time on star detection sensitivity is analyzed by establishing the dynamic star-spot imaging model. Then the star location error is deduced based on the error analysis of the sub-pixel centroiding algorithm. Combining these analyses, the effect of exposure time on attitude accuracy is finally determined. Some simulations are carried out to validate these effects, and the results show that there are different optimal exposure times for different angular velocities of a star tracker with a given configuration. In addition, the results of night sky experiments using a real star tracker agree with the simulation results. The summarized regularities in this paper should prove helpful in the system design and dynamic performance evaluation of the highly dynamic star trackers. PMID:24618776

Nuclear Phosphatidylinositol-Phosphate Type I Kinase α-Coupled Star-PAP Polyadenylation Regulates Cell Invasion

PubMed Central

A.P., Sudheesh

2017-01-01

ABSTRACT Star-PAP, a nuclear phosphatidylinositol (PI) signal-regulated poly(A) polymerase (PAP), couples with type I PI phosphate kinase α (PIPKIα) and controls gene expression. We show that Star-PAP and PIPKIα together regulate 3′-end processing and expression of pre-mRNAs encoding key anti-invasive factors (KISS1R, CDH1, NME1, CDH13, FEZ1, and WIF1) in breast cancer. Consistently, the endogenous Star-PAP level is negatively correlated with the cellular invasiveness of breast cancer cells. While silencing Star-PAP or PIPKIα increases cellular invasiveness in low-invasiveness MCF7 cells, Star-PAP overexpression decreases invasiveness in highly invasive MDA-MB-231 cells in a cellular Star-PAP level-dependent manner. However, expression of the PIPKIα-noninteracting Star-PAP mutant or the phosphodeficient Star-PAP (S6A mutant) has no effect on cellular invasiveness. These results strongly indicate that PIPKIα interaction and Star-PAP S6 phosphorylation are required for Star-PAP-mediated regulation of cancer cell invasion and give specificity to target anti-invasive gene expression. Our study establishes Star-PAP–PIPKIα-mediated 3′-end processing as a key anti-invasive mechanism in breast cancer. PMID:29203642

Nuclear Phosphatidylinositol-Phosphate Type I Kinase α-Coupled Star-PAP Polyadenylation Regulates Cell Invasion.

PubMed

A P, Sudheesh; Laishram, Rakesh S

2018-03-01

Star-PAP, a nuclear phosphatidylinositol (PI) signal-regulated poly(A) polymerase (PAP), couples with type I PI phosphate kinase α (PIPKIα) and controls gene expression. We show that Star-PAP and PIPKIα together regulate 3'-end processing and expression of pre-mRNAs encoding key anti-invasive factors ( KISS1R , CDH1 , NME1 , CDH13 , FEZ1 , and WIF1 ) in breast cancer. Consistently, the endogenous Star-PAP level is negatively correlated with the cellular invasiveness of breast cancer cells. While silencing Star-PAP or PIPKIα increases cellular invasiveness in low-invasiveness MCF7 cells, Star-PAP overexpression decreases invasiveness in highly invasive MDA-MB-231 cells in a cellular Star-PAP level-dependent manner. However, expression of the PIPKIα-noninteracting Star-PAP mutant or the phosphodeficient Star-PAP (S6A mutant) has no effect on cellular invasiveness. These results strongly indicate that PIPKIα interaction and Star-PAP S6 phosphorylation are required for Star-PAP-mediated regulation of cancer cell invasion and give specificity to target anti-invasive gene expression. Our study establishes Star-PAP-PIPKIα-mediated 3'-end processing as a key anti-invasive mechanism in breast cancer. Copyright © 2018 A.P. and Laishram.

A CATALOG OF NEW SPECTROSCOPICALLY CONFIRMED MASSIVE OB STARS IN CARINA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexander, Michael J.; Hanes, Richard J.; McSwain, M. Virginia

2016-12-01

The Carina star-forming region is one of the largest in the Galaxy, and its massive star population is still being unveiled. The large number of stars combined with high, and highly variable, interstellar extinction makes it inherently difficult to find OB stars in this type of young region. We present the results of a spectroscopic campaign to study the massive star population of the Carina Nebula, with the primary goal to confirm or reject previously identified Carina OB star candidates. A total of 141 known O- and B-type stars and 94 candidates were observed, of which 73 candidates had highmore » enough signal-to-noise ratio to classify. We find 23 new OB stars within the Carina Nebula, a 32% confirmation rate. One of the new OB stars has blended spectra and is suspected to be a double-lined spectroscopic binary (SB2). We also reclassify the spectral types of the known OB stars and discover nine new SB2s among this population. Finally, we discuss the spatial distribution of these new OB stars relative to known structures in the Carina Nebula.« less