Constitutive Modeling and Testing of Polymer Matrix Composites Incorporating Physical Aging at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Veazie, David R.

1998-01-01

Advanced polymer matrix composites (PMC's) are desirable for structural materials in diverse applications such as aircraft, civil infrastructure and biomedical implants because of their improved strength-to-weight and stiffness-to-weight ratios. For example, the next generation military and commercial aircraft requires applications for high strength, low weight structural components subjected to elevated temperatures. A possible disadvantage of polymer-based composites is that the physical and mechanical properties of the matrix often change significantly over time due to the exposure of elevated temperatures and environmental factors. For design, long term exposure (i.e. aging) of PMC's must be accounted for through constitutive models in order to accurately assess the effects of aging on performance, crack initiation and remaining life. One particular aspect of this aging process, physical aging, is considered in this research.

Method for separating biological cells. [suspended in aqueous polymer systems

NASA Technical Reports Server (NTRS)

Brooks, D. E. (Inventor)

1980-01-01

A method for separating biological cells by suspending a mixed cell population in a two-phase polymer system is described. The polymer system consists of droplet phases with different surface potentials for which the cell populations exhibit different affinities. The system is subjected to an electrostatic field of sufficient intensity to cause migration of the droplets with an attendant separation of cells.

Non-integer viscoelastic constitutive law to model soft biological tissues to in-vivo indentation.

PubMed

Demirci, Nagehan; Tönük, Ergin

2014-01-01

During the last decades, derivatives and integrals of non-integer orders are being more commonly used for the description of constitutive behavior of various viscoelastic materials including soft biological tissues. Compared to integer order constitutive relations, non-integer order viscoelastic material models of soft biological tissues are capable of capturing a wider range of viscoelastic behavior obtained from experiments. Although integer order models may yield comparably accurate results, non-integer order material models have less number of parameters to be identified in addition to description of an intermediate material that can monotonically and continuously be adjusted in between an ideal elastic solid and an ideal viscous fluid. In this work, starting with some preliminaries on non-integer (fractional) calculus, the "spring-pot", (intermediate mechanical element between a solid and a fluid), non-integer order three element (Zener) solid model, finally a user-defined large strain non-integer order viscoelastic constitutive model was constructed to be used in finite element simulations. Using the constitutive equation developed, by utilizing inverse finite element method and in vivo indentation experiments, soft tissue material identification was performed. The results indicate that material coefficients obtained from relaxation experiments, when optimized with creep experimental data could simulate relaxation, creep and cyclic loading and unloading experiments accurately. Non-integer calculus viscoelastic constitutive models, having physical interpretation and modeling experimental data accurately is a good alternative to classical phenomenological viscoelastic constitutive equations.

Biologically Inspired Technology Using Electroactive Polymers (EAP)

NASA Technical Reports Server (NTRS)

Bar-Cohen, Yoseph

2006-01-01

Evolution allowed nature to introduce highly effective biological mechanisms that are incredible inspiration for innovation. Humans have always made efforts to imitate nature's inventions and we are increasingly making advances that it becomes significantly easier to imitate, copy, and adapt biological methods, processes and systems. This brought us to the ability to create technology that is far beyond the simple mimicking of nature. Having better tools to understand and to implement nature's principles we are now equipped like never before to be inspired by nature and to employ our tools in far superior ways. Effectively, by bio-inspiration we can have a better view and value of nature capability while studying its models to learn what can be extracted, copied or adapted. Using electroactive polymers (EAP) as artificial muscles is adding an important element to the development of biologically inspired technologies.

Controlled polymer synthesis--from biomimicry towards synthetic biology.

PubMed

Pasparakis, George; Krasnogor, Natalio; Cronin, Leroy; Davis, Benjamin G; Alexander, Cameron

2010-01-01

The controlled assembly of synthetic polymer structures is now possible with an unprecedented range of functional groups and molecular architectures. In this critical review we consider how the ability to create artificial materials over lengthscales ranging from a few nm to several microns is generating systems that not only begin to mimic those in nature but also may lead to exciting applications in synthetic biology (139 references).

High-temperature viscoelastic creep constitutive equations for polymer composites: Homogenization theory and experiments

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

Skontorp, A.; Wang, S.S.; Shibuya, Y.

1994-12-31

In this paper, a homogenization theory is developed to determine high-temperature effective viscoelastic constitutive equations for fiber-reinforced polymer composites. The homogenization theory approximates the microstructure of a fiber composite, and determine simultaneously effective macroscopic constitutive properties of the composite and the associated microscopic strain and stress in the heterogeneous material. The time-temperature dependent homogenization theory requires that the viscoelastic constituent properties of the matrix phase at elevated temperatures, the governing equations for the composites, and the boundary conditions of the problem be Laplace transformed to a conjugate problem. The homogenized effective properties in the transformed domain are determined, using amore » two-scale asymptotic expansion of field variables and an averaging procedure. Field solutions in the unit cell are determined from basic and first-order governing equations with the aid of a boundary integral method (BIM). Effective viscoelastic constitutive properties of the composite at elevated temperatures are determined by an inverse transformation, as are the microscopic stress and deformation in the composite. Using this method, interactions among fibers and between the fibers and the matrix can be evaluated explicitly, resulting in accurate solutions for composites with high-volume fraction of reinforcing fibers. Examples are given for the case of a carbon-fiber reinforced thermoplastic polyamide composite in an elevated temperature environment. The homogenization predictions are in good agreement with experimental data available for the composite.« less

Coordination polymer gels with important environmental and biological applications.

PubMed

Jung, Jong Hwa; Lee, Ji Ha; Silverman, Julian R; John, George

2013-02-07

Coordination Polymer Gels (CPGs) constitute a subset of solid-like metal ion and bridging organic ligand structures (similar to metal-organic frameworks) that form multi-dimensional networks through a trapped solvent as a result of non-covalent interactions. While physical properties of these gels are similar to conventional high molecular weight organic polymer gels, coordination polymer gel systems are often fully reversible and can be assembled and disassembled in the presence of additional energy (heat, sonication, shaking) to give a solution of solvated gelators. Compared to gels resulting from purely organic self-assembled low molecular weight gelators, metal ions incorporated into the fibrilar networks spanning the bulk solvent can impart CPGs with added functionalities. The solid/liquid nature of the gels allows for species to migrate through the gel system and interact with metals, ligands, and the solvent. Chemosensing, catalysis, fluorescence, and drug-delivery applications are some of the many potential uses for these dynamic systems, taking advantage of the metal ion's coordination, the organic polydentate ligand's orientation and functionality, or a combination of these properties. By fine tuning these systems through metal ion and ligand selection and by directing self-assembly with external stimuli the rational synthesis of practical systems can be envisaged.

Impact of constitutional copy number variants on biological pathway evolution.

PubMed

Poptsova, Maria; Banerjee, Samprit; Gokcumen, Omer; Rubin, Mark A; Demichelis, Francesca

2013-01-23

Inherited Copy Number Variants (CNVs) can modulate the expression levels of individual genes. However, little is known about how CNVs alter biological pathways and how this varies across different populations. To trace potential evolutionary changes of well-described biological pathways, we jointly queried the genomes and the transcriptomes of a collection of individuals with Caucasian, Asian or Yoruban descent combining high-resolution array and sequencing data. We implemented an enrichment analysis of pathways accounting for CNVs and genes sizes and detected significant enrichment not only in signal transduction and extracellular biological processes, but also in metabolism pathways. Upon the estimation of CNV population differentiation (CNVs with different polymorphism frequencies across populations), we evaluated that 22% of the pathways contain at least one gene that is proximal to a CNV (CNV-gene pair) that shows significant population differentiation. The majority of these CNV-gene pairs belong to signal transduction pathways and 6% of the CNV-gene pairs show statistical association between the copy number states and the transcript levels. The analysis suggested possible examples of positive selection within individual populations including NF-kB, MAPK signaling pathways, and Alu/L1 retrotransposition factors. Altogether, our results suggest that constitutional CNVs may modulate subtle pathway changes through specific pathway enzymes, which may become fixed in some populations.

Strategies for interfacing inorganic nanocrystals with biological systems based on polymer-coating.

PubMed

Palui, Goutam; Aldeek, Fadi; Wang, Wentao; Mattoussi, Hedi

2015-01-07

Interfacing inorganic nanoparticles and biological systems with the aim of developing novel imaging and sensing platforms has generated great interest and much activity. However, the effectiveness of this approach hinges on the ability of the surface ligands to promote water-dispersion of the nanoparticles with long term colloidal stability in buffer media. These surface ligands protect the nanostructures from the harsh biological environment, while allowing coupling to target molecules, which can be biological in nature (e.g., proteins and peptides) or exhibit specific photo-physical characteristics (e.g., a dye or a redox-active molecule). Amphiphilic block polymers have provided researchers with versatile molecular platforms with tunable size, composition and chemical properties. Hence, several groups have developed a wide range of polymers as ligands or micelle capsules to promote the transfer of a variety of inorganic nanomaterials to buffer media (including magnetic nanoparticles and semiconductor nanocrystals) and render them biocompatible. In this review, we first summarize the established synthetic routes to grow high quality nanocrystals of semiconductors, metals and metal oxides. We then provide a critical evaluation of the recent developments in the design, optimization and use of various amphiphilic copolymers to surface functionalize the above nanocrystals, along with the strategies used to conjugate them to target biomolecules. We finally conclude by providing a summary of the most promising applications of these polymer-coated inorganic platforms in sensor design, and imaging of cells and tissues.

Polymer Dynamics from Synthetic to Biological Macromolecules

NASA Astrophysics Data System (ADS)

Richter, D.; Niedzwiedz, K.; Monkenbusch, M.; Wischnewski, A.; Biehl, R.; Hoffmann, B.; Merkel, R.

2008-02-01

High resolution neutron scattering together with a meticulous choice of the contrast conditions allows to access the large scale dynamics of soft materials including biological molecules in space and time. In this contribution we present two examples. One from the world of synthetic polymers, the other from biomolecules. First, we will address the peculiar dynamics of miscible polymer blends with very different component glass transition temperatures. Polymethylmetacrylate (PMMA), polyethyleneoxide (PEO) are perfectly miscible but exhibit a difference in the glass transition temperature by 200 K. We present quasielastic neutron scattering investigations on the dynamics of the fast component in the range from angströms to nanometers over a time frame of five orders of magnitude. All data may be consistently described in terms of a Rouse model with random friction, reflecting the random environment imposed by the nearly frozen PMMA matrix on the fast mobile PEO. In the second part we touch on some new developments relating to large scale internal dynamics of proteins by neutron spin echo. We will report results of some pioneering studies which show the feasibility of such experiments on large scale protein motion which will most likely initiate further studies in the future.

Temperature-Responsive Polymers for Biological Applications

DTIC Science & Technology

2003-06-01

polymer temperature response in water by varying chemical composition of the monomer. In order to achieve this a series of polymers were designed and...varying the m/n composition and polymer type. Polymer grafting onto the silicon surface exhibits similar solubility behaviour. Adhesion energy...Driven by the high promise for biomedical applications, polymers that exhibit a response in water at about 37ºC are of particular interest. Taylor and

Accommodating Ontologies to Biological Reality—Top-Level Categories of Cumulative-Constitutively Organized Material Entities

PubMed Central

Vogt, Lars; Grobe, Peter; Quast, Björn; Bartolomaeus, Thomas

2012-01-01

Background The Basic Formal Ontology (BFO) is a top-level formal foundational ontology for the biomedical domain. It has been developed with the purpose to serve as an ontologically consistent template for top-level categories of application oriented and domain reference ontologies within the Open Biological and Biomedical Ontologies Foundry (OBO). BFO is important for enabling OBO ontologies to facilitate in reliably communicating and managing data and metadata within and across biomedical databases. Following its intended single inheritance policy, BFO's three top-level categories of material entity (i.e. ‘object’, ‘fiat object part’, ‘object aggregate’) must be exhaustive and mutually disjoint. We have shown elsewhere that for accommodating all types of constitutively organized material entities, BFO must be extended by additional categories of material entity. Methodology/Principal Findings Unfortunately, most biomedical material entities are cumulative-constitutively organized. We show that even the extended BFO does not exhaustively cover cumulative-constitutively organized material entities. We provide examples from biology and everyday life that demonstrate the necessity for ‘portion of matter’ as another material building block. This implies the necessity for further extending BFO by ‘portion of matter’ as well as three additional categories that possess portions of matter as aggregate components. These extensions are necessary if the basic assumption that all parts that share the same granularity level exhaustively sum to the whole should also apply to cumulative-constitutively organized material entities. By suggesting a notion of granular representation we provide a way to maintain the single inheritance principle when dealing with cumulative-constitutively organized material entities. Conclusions/Significance We suggest to extend BFO to incorporate additional categories of material entity and to rearrange its top-level material

How Discourses of Biology Textbooks Work to Constitute Subjectivity: From the Ethical to the Colonial

NASA Astrophysics Data System (ADS)

Bazzul, Jesse

This thesis examines how discourses of biology textbooks can work to constitute various kinds of subjectivities. Using a Foucauldian archaeological approach to discourse analysis I examine how four Ontario secondary school biology textbooks discursively delimit what can be thought and acted upon, and in the process work to partially constitute students/teachers as sex/gendered; neocolonial; neoliberal (and a subject of work), and ethical subjects and subjectivities. This thesis engages the topic of how discourse can constitute subjectivity in science in three basic ways: First, on a theoretical level, in terms of working out an understanding of subject constitution/interpellation that would also be useful when engaging with other sociopolitical and ethical questions in science education. Secondly, in terms of an empirically based critical discourse analysis that examines how various statements within these four textbooks could set limits on what is possible for students to think and act upon in relation to themselves, science, and the world. Thirdly, this thesis represents a narrative of scholarly development that moves from an engagement of my personal experiences in science education and current science education literature towards the general politico-philosophical topic of subjectivity and biopolitics. This thesis begins with a discussion of my experiences as a science teacher, a review of relevant science education literature, and considerations of subjectivity that relate specifically ii to the specific methodological approach I employ when examining these textbooks. After this I present five chapters, each of which can be thought of as a somewhat separate analysis concerning how the discourses of these textbooks can work to constitute specific subjectivities (each involving different theoretical/methodological considerations). I conclude with a reflection/synthesis chapter and a call to see science education as a site for biopolitical struggle.

A 1D thermomechanical network transition constitutive model coupled with multiple structural relaxation for shape memory polymers

NASA Astrophysics Data System (ADS)

Zeng, Hao; Xie, Zhimin; Gu, Jianping; Sun, Huiyu

2018-03-01

A new thermomechanical network transition constitutive model is proposed in the study to describe the viscoelastic behavior of shape memory polymers (SMPs). Based on the microstructure of semi-crystalline SMPs, a new simplified transformation equation is proposed to describe the transform of transient networks. And the generalized fractional Maxwell model is introduced in the paper to estimate the temperature-dependent storage modulus. In addition, a neo-KAHR theory with multiple discrete relaxation processes is put forward to study the structural relaxation of the nonlinear thermal strain in cooling/heating processes. The evolution equations of the time- and temperature-dependent stress and strain response are developed. In the model, the thermodynamical and mechanical characteristics of SMPs in the typical thermomechanical cycle are described clearly and the irreversible deformation is studied in detail. Finally, the typical thermomechanical cycles are simulated using the present constitutive model, and the simulation results agree well with the experimental results.

Finite element simulation and analysis of local stress concentration in polymers with a nonlinear viscoelastic constitutive model

NASA Astrophysics Data System (ADS)

Chea, Limdara O.

Given a nonlinear viscoelastic (NLVE) constitutive model for a polymer, this numerical study aims at simulating local stress concentrations in a boundary value problem with a corner stress singularity. A rectangular sample of Polyvinyl Acetate (PVAc)-like cross-linked polymer clamped by two metallic rigid grips and subjected to a compression and tension load is numerically simulated. A modified version of the finite element code FEAP, that incorporated a NLVE model based on the free volume theory, was used. First, the program was validated by comparing numerical and analytical results. Two simple mechanical tests (a uniaxial and a simple shear test) were performed on a Standard Linear Solid material model, using a linear viscoelastic (LVE) constitutive model. The LVE model was obtained by setting the proportionality coefficient [...] to zero in the free volume theory equations. Second, the LVE model was used on the corner singularity boundary value problem for three material models with different bulk relaxation functions K(t). The time-dependent stress field distribution was investigated using two sets of plots: the stress distribution contour plots and the stress time curves. Third, using the NLVE constitutive model, compression and tension cases were compared using the stress results (normal stress [...] and shear stress [...]). These two cases assessed the effect of the creep retardation-creep acceleration phenomena. The shift between the beginning of the relaxation moduli was shown to play an important role. This parameter affects strongly the fluctuation pattern of the stress curves. For two different shift values, in one case, the stress response presents a 'double peak' and 'stress inversion' characteristic whereas, in the other case, it presents a 'single peak' and no 'inversion'. Another important factor was the material's compressibility. In the case of a nearly-incompressible material, the LVE and NLVE models yielded identical results; thus, the simpler

Impact of constitutional copy number variants on biological pathway evolution

PubMed Central

2013-01-01

Background Inherited Copy Number Variants (CNVs) can modulate the expression levels of individual genes. However, little is known about how CNVs alter biological pathways and how this varies across different populations. To trace potential evolutionary changes of well-described biological pathways, we jointly queried the genomes and the transcriptomes of a collection of individuals with Caucasian, Asian or Yoruban descent combining high-resolution array and sequencing data. Results We implemented an enrichment analysis of pathways accounting for CNVs and genes sizes and detected significant enrichment not only in signal transduction and extracellular biological processes, but also in metabolism pathways. Upon the estimation of CNV population differentiation (CNVs with different polymorphism frequencies across populations), we evaluated that 22% of the pathways contain at least one gene that is proximal to a CNV (CNV-gene pair) that shows significant population differentiation. The majority of these CNV-gene pairs belong to signal transduction pathways and 6% of the CNV-gene pairs show statistical association between the copy number states and the transcript levels. Conclusions The analysis suggested possible examples of positive selection within individual populations including NF-kB, MAPK signaling pathways, and Alu/L1 retrotransposition factors. Altogether, our results suggest that constitutional CNVs may modulate subtle pathway changes through specific pathway enzymes, which may become fixed in some populations. PMID:23342974

Polymer Fluid Dynamics.

ERIC Educational Resources Information Center

Bird, R. Byron

1980-01-01

Problems in polymer fluid dynamics are described, including development of constitutive equations, rheometry, kinetic theory, flow visualization, heat transfer studies, flows with phase change, two-phase flow, polymer unit operations, and drag reduction. (JN)

Silica passivated conjugated polymer nanoparticles for biological imaging applications

NASA Astrophysics Data System (ADS)

Bourke, Struan; Urbano, Laura; Olona, Antoni; Valderrama, Ferran; Dailey, Lea Ann; Green, Mark A.

2017-02-01

Colorectal and prostate cancers are major causes of cancer-related death, with early detection key to increased survival. However, as symptoms occur during advanced stages and current diagnostic methods have limitations, there is a need for new fluorescent probes that remain bright, are biocompatible and can be targeted. Conjugated polymer nanoparticles have shown great promise in biological imaging due to their unique optical properties. We have synthesised small, bright, photo-stable CN-PPV, nanoparticles encapsulated with poloxamer polymer and a thin silica shell. By incubating the CN-PPV silica shelled cross-linked (SSCL) nanoparticles in mammalian (HeLa) cells; we were able to show that cellular uptake occurred. Uptake was also shown by incubating the nanoparticles in RWPE-1, WPE1-NB26 and WPE1- NA22 prostate cancer cell lines. Finally, HEK cells were used to show the particles had limited cytotoxicity.

Polymer application for separation/filtration of biological active compounds

NASA Astrophysics Data System (ADS)

Tylkowski, B.; Tsibranska, I.

2017-06-01

Membrane technology is an important part of the engineer's toolbox. This is especially true for industries that process food and other products with their primary source from nature. This review is focused on ongoing development work using membrane technologies for concentration and separation of biologically active compounds, such as polyphenols and flavonoids. We provide the readers not only with the last results achieve in this field but also, we deliver detailed information about the membrane types and polymers used for their preparation.

The biology and polymer physics underlying large‐scale chromosome organization

PubMed Central

2017-01-01

Chromosome large‐scale organization is a beautiful example of the interplay between physics and biology. DNA molecules are polymers and thus belong to the class of molecules for which physicists have developed models and formulated testable hypotheses to understand their arrangement and dynamic properties in solution, based on the principles of polymer physics. Biologists documented and discovered the biochemical basis for the structure, function and dynamic spatial organization of chromosomes in cells. The underlying principles of chromosome organization have recently been revealed in unprecedented detail using high‐resolution chromosome capture technology that can simultaneously detect chromosome contact sites throughout the genome. These independent lines of investigation have now converged on a model in which DNA loops, generated by the loop extrusion mechanism, are the basic organizational and functional units of the chromosome. PMID:29105235

Smiles2Monomers: a link between chemical and biological structures for polymers.

PubMed

Dufresne, Yoann; Noé, Laurent; Leclère, Valérie; Pupin, Maude

2015-01-01

The monomeric composition of polymers is powerful for structure comparison and synthetic biology, among others. Many databases give access to the atomic structure of compounds but the monomeric structure of polymers is often lacking. We have designed a smart algorithm, implemented in the tool Smiles2Monomers (s2m), to infer efficiently and accurately the monomeric structure of a polymer from its chemical structure. Our strategy is divided into two steps: first, monomers are mapped on the atomic structure by an efficient subgraph-isomorphism algorithm ; second, the best tiling is computed so that non-overlapping monomers cover all the structure of the target polymer. The mapping is based on a Markovian index built by a dynamic programming algorithm. The index enables s2m to search quickly all the given monomers on a target polymer. After, a greedy algorithm combines the mapped monomers into a consistent monomeric structure. Finally, a local branch and cut algorithm refines the structure. We tested this method on two manually annotated databases of polymers and reconstructed the structures de novo with a sensitivity over 90 %. The average computation time per polymer is 2 s. s2m automatically creates de novo monomeric annotations for polymers, efficiently in terms of time computation and sensitivity. s2m allowed us to detect annotation errors in the tested databases and to easily find the accurate structures. So, s2m could be integrated into the curation process of databases of small compounds to verify the current entries and accelerate the annotation of new polymers. The full method can be downloaded or accessed via a website for peptide-like polymers at http://bioinfo.lifl.fr/norine/smiles2monomers.jsp.Graphical abstract:.

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

PubMed

Pekkanen, Allison M; Mondschein, Ryan J; Williams, Christopher B; Long, Timothy E

2017-09-11

Supramolecular chemistry continues to experience widespread growth, as fine-tuned chemical structures lead to well-defined bulk materials. Previous literature described the roles of hydrogen bonding, ionic aggregation, guest/host interactions, and π-π stacking to tune mechanical, viscoelastic, and processing performance. The versatility of reversible interactions enables the more facile manufacturing of molded parts with tailored hierarchical structures such as tissue engineered scaffolds for biological applications. Recently, supramolecular polymers and additive manufacturing processes merged to provide parts with control of the molecular, macromolecular, and feature length scales. Additive manufacturing, or 3D printing, generates customizable constructs desirable for many applications, and the introduction of supramolecular interactions will potentially increase production speed, offer a tunable surface structure for controlling cell/scaffold interactions, and impart desired mechanical properties through reinforcing interlayer adhesion and introducing gradients or self-assembled structures. This review details the synthesis and characterization of supramolecular polymers suitable for additive manufacture and biomedical applications as well as the use of supramolecular polymers in additive manufacturing for drug delivery and complex tissue scaffold formation. The effect of supramolecular assembly and its dynamic behavior offers potential for controlling the anisotropy of the printed objects with exquisite geometrical control. The potential for supramolecular polymers to generate well-defined parts, hierarchical structures, and scaffolds with gradient properties/tuned surfaces provides an avenue for developing next-generation biomedical devices and tissue scaffolds.

Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

NASA Astrophysics Data System (ADS)

Mukherjee, Sanjoy; Boudouris, Bryan

The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

The biology and polymer physics underlying large-scale chromosome organization.

PubMed

Sazer, Shelley; Schiessel, Helmut

2018-02-01

Chromosome large-scale organization is a beautiful example of the interplay between physics and biology. DNA molecules are polymers and thus belong to the class of molecules for which physicists have developed models and formulated testable hypotheses to understand their arrangement and dynamic properties in solution, based on the principles of polymer physics. Biologists documented and discovered the biochemical basis for the structure, function and dynamic spatial organization of chromosomes in cells. The underlying principles of chromosome organization have recently been revealed in unprecedented detail using high-resolution chromosome capture technology that can simultaneously detect chromosome contact sites throughout the genome. These independent lines of investigation have now converged on a model in which DNA loops, generated by the loop extrusion mechanism, are the basic organizational and functional units of the chromosome. © 2017 The Authors. Traffic published by John Wiley & Sons Ltd.

Constitutive Modeling of Piezoelectric Polymer Composites

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Tom (Technical Monitor)

2003-01-01

A new modeling approach is proposed for predicting the bulk electromechanical properties of piezoelectric composites. The proposed model offers the same level of convenience as the well-known Mori-Tanaka method. In addition, it is shown to yield predicted properties that are, in most cases, more accurate or equally as accurate as the Mori-Tanaka scheme. In particular, the proposed method is used to determine the electromechanical properties of four piezoelectric polymer composite materials as a function of inclusion volume fraction. The predicted properties are compared to those calculated using the Mori-Tanaka and finite element methods.

Mechanics of biological polymer composites

NASA Astrophysics Data System (ADS)

Lomakin, Joseph

2009-12-01

displayed a darker coloration and significantly increased n of 0.0470.004, suggesting both cuticles to be less cross-linked, a finding consistent with reduced beta-alanine metabolism. Suppression of the tanning enzyme laccase2 (TcLac2) resulted in a pale cuticle with an n of 0.043+/-0.005, implicating laccases in the formation of both pigments and cross-links during sclerotization. Cuticular cross-linking was increased and n decreased with decreased expression of structural proteins, CP10 and CP20. This work establishes n as an important novel parameter for confirming metabolic pathways within load bearing tissues and for understanding structure function relationships within biological polymer composites. Additionally, Tribolium castaneum elytral indentation modulus (800+/-200 MPa) was determined by nanoindentation and a 4nm regular hexagonal pattern on the dorsal side of elytra investigated via scanning, transmission and atomic microscopy. Based on studied biological materials, the combination of rigid macromolecules immersed in a ductile matrix was found to be significant in achieving exceptional mechanical performance. Inspired by this biological design principle, the synthesis, properties and structure of Poly(ethylene glycol) diacrylate/agarose semi-interpenetrating network hydrogels were explored. The resulting novel composite materials were 9x stiffer than agarose and 5x tougher than PEGDA alone and showed good biocompatibility, suggesting promise as a scaffold material for tissue engineering constructs for cartilage regeneration.

Constitutive expression of tdTomato protein as a cytotoxicity and proliferation marker for space radiation biology

NASA Astrophysics Data System (ADS)

Chishti, Arif A.; Hellweg, Christine E.; Berger, Thomas; Baumstark-Khan, Christa; Feles, Sebastian; Kätzel, Thorben; Reitz, Günther

2015-01-01

The radiation risk assessment for long-term space missions requires knowledge on the biological effectiveness of different space radiation components, e.g. heavy ions, on the interaction of radiation and other space environmental factors such as microgravity, and on the physical and biological dose distribution in the human body. Space experiments and ground-based experiments at heavy ion accelerators require fast and reliable test systems with an easy readout for different endpoints. In order to determine the effect of different radiation qualities on cellular proliferation and the biological depth dose distribution after heavy ion exposure, a stable human cell line expressing a novel fluorescent protein was established and characterized. tdTomato, a red fluorescent protein of the new generation with fast maturation and high fluorescence intensity, was selected as reporter of cell proliferation. Human embryonic kidney (HEK/293) cells were stably transfected with a plasmid encoding tdTomato under the control of the constitutively active cytomegalovirus (CMV) promoter (ptdTomato-N1). The stably transfected cell line was named HEK-ptdTomato-N1 8. This cytotoxicity biosensor was tested by ionizing radiation (X-rays and accelerated heavy ions) exposure. As biological endpoints, the proliferation kinetics and the cell density reached 100 h after irradiation reflected by constitutive expression of the tdTomato were investigated. Both were reduced dose-dependently after radiation exposure. Finally, the cell line was used for biological weighting of heavy ions of different linear energy transfer (LET) as space-relevant radiation quality. The relative biological effectiveness of accelerated heavy ions in reducing cellular proliferation peaked at an LET of 91 keV/μm. The results of this study demonstrate that the HEK-ptdTomato-N1 reporter cell line can be used as a fast and reliable biosensor system for detection of cytotoxic damage caused by ionizing radiation.

Effect of Dendritic Polymer Architecture on Biological Behaviors of Self-Assembled Nanocarriers

NASA Astrophysics Data System (ADS)

Hsu, Hao-Jui

Polymeric self-assembled nanocarriers represent one of the most versatile platforms for drug delivery. Through tailoring the physiochemical properties of amphiphilic block copolymers, self-assembled nanocarriers with great thermodynamic stability and desired biological properties could be achieved. The PEGylated dendron-based copolymers (PDCs) are one of the novel amphiphilic copolymers that have attracted a great deal of scientific interest due to their unique dendritic structure and properties. While the dendritic polymer architecture of PDC has been shown to enhance the thermodynamic stability of the self-assembling PDCs, dendron micelles, the effect of this polymer architecture on the biological properties of dendron micelles has not yet been studied. Therefore, this dissertation research is focused on understanding the role of dendritic polymer structure on moderating the biological properties of various self-assembled nanocarriers. To systematically investigate this, three studies have been designed and performed. First, we studied whether the dendritic structure of PDC allows dendron micelles to behave non-specific cellular interactions in a similar way that dendrimers would do. Second, cell-specific interactions of dendron micelles mediated by conjugated ligands were investigated. Third, we investigated the influence of dendritic PEG outer shell on micelle-serum protein interactions and its subsequent implication. Our results revealed that both non-specific and specific cellular interactions of dendron micelles were controllable through modulation of the PEG corona length. While the non-specific charge-dependent cellular interactions of dendron micelles were tunable through controlling the length of PEG corona, the use of long PEG tether was found to enhance the ligand-mediated cellular interactions of dendron micelles. With the ligand tethers, a 27-fold enhancement in ligand-mediated cellular interactions can be achieved, compared to non-targeted dendron

Combined Mechanical and Electrical Study of Polymers of Biological Origin

NASA Astrophysics Data System (ADS)

Zsoldos, G.; Szoda, K.; Marossy, K.

2017-02-01

Thermally Simulated Depolarization Current measurement is an excellent but not widely used method for identifying relaxation processes in polymers. The DMA method is used here to analyze the mechanical changes depend on temperature in biopolymers. The two techniques take advantage of the energy changes involved in the various phase transitions of certain polymer molecules. This allows for several properties of the material to be ascertained; melting points, enthalpies of melting, crystallization temperatures, glass transition temperatures and degradation temperatures. The examined biopolymer films are made from biological materials such as proteins and polysaccharides. These materials have gained wide usage in pharmaceutical, medical and food areas. The uses of biopolymer films depend on their structure and mechanical properties. This work is based on pectin and gelatin films. The films were prepared by casting. The casting technique used aqueous solutions in each case of sample preparation. The manufacturing process of the pectin and gelatin films was a single stage solving process.

From Commodity Polymers to Functional Polymers

PubMed Central

Xiang, Tao; Wang, Ling-Ren; Ma, Lang; Han, Zhi-Yuan; Wang, Rui; Cheng, Chong; Xia, Yi; Qin, Hui; Zhao, Chang-Sheng

2014-01-01

Functional polymers bear specified chemical groups, and have specified physical, chemical, biological, pharmacological, or other uses. To adjust the properties while keeping material usage low, a method for direct synthesis of functional polymers is indispensable. Here we show that various functional polymers can be synthesized by in situ cross-linked polymerization/copolymerization. We demonstrate that the polymers synthesized by the facile method using different functional monomers own outstanding pH-sensitivity and pH-reversibility, antifouling property, antibacterial, and anticoagulant property. Our study opens a route for the functionalization of commodity polymers, which lead to important advances in polymeric materials applications. PMID:24710333

[Characteristics of tenocyte adhesion to biologically-modified surface of polymer].

PubMed

Qin, Tingwu; Yang, Zhiming; Xie, Huiqi; Li, Hong; Qin, Jian; Wu, Zezhi; Xu, Shirong; Cai, Shaoxi

2002-12-01

In this study we examined the in vitro characteristics of tenocyte adhesion to biologically-modified surface of polymer. Polylactic-co-glycolic acid (PLGA) 85/15 films were prepared by a solvent-casting technique. Each film was adhered onto the bottom of a chamber. The film was precoated with poly-D-lysine (PDL), and then coated with serum-free F12 medium containing various concentrations of fibronectin (FN), type I collagen (CN I), and insulin-like growth factor1 (IGF-1). The monoclonal antibodies (to FN and to CN I) with various dilutions were used to inhibit attachment of tenocytes to surface precoated with FN or CN I. Human embryonic tendon cells (HETCs) and transformed human embryonic tendon cells (THETCs) were used as the seeding cells. The system used for the measurement of adhesion force was the micropipette aspiration experiment system. The micropipette was manipulated to aspirate a small portion of the tenocyte body by using a small aspiration pressure. Then the pipette was pulled away from the adhesion area by micromanipulation. The minimum force required to detach the tenocyte from the substrate was defined as the adhesion force. The results showed that modification of FN or CN I by precoating significantly enhanced attachment of tenocytes to surface of polymer (P < 0.05). As antibodies to FN or CN I were added to a polymer film precoated with FN or CN I, the adhesion force decreased significantly (P < 0.05). We concluded that the specific adhesion forces of tenocytes to extracellular matrix adhesion proteins (FN and CN I) had coordinated action and showed good dependence on their precoating concentrations, and were inhibited by the antibodies to these adhesion proteins. Films precoated with IGF-1 strongly accelerated the adhesion of tenocytes to polymer. These results indicate that the specific adhesion of tenocytes to polymer can be promoted by coating extracellular matrix adhesive proteins and insulin-like growth factor1. It is of great importance to

Biodegradable Polymers

PubMed Central

Vroman, Isabelle; Tighzert, Lan

2009-01-01

Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources) or from biological resources (renewable resources). In general natural polymers offer fewer advantages than synthetic polymers. The following review presents an overview of the different biodegradable polymers that are currently being used and their properties, as well as new developments in their synthesis and applications.

The constitutional protection of trade secrets and patents under the Biologics Price Competition and Innovation Act of 2009.

PubMed

Epstein, Richard A

2011-01-01

The Biologics Price Competition and Innovation Act of 2009 ("Biosimilars Act") is for the field of pharmaceutical products the single most important legislative development since passage of the Drug Price Competition and Patent Term Restoration Act of 1984 ("Hatch-Waxman Act"), on which portions of the Biosimilars Act are clearly patterned. Congress revised section 351 of the Public Health Service Act (PHSA) to create a pathway for FDA approval of "biosimilar" biological products. Each biosimilar applicant is required to cite in its application a "reference product" that was approved on the basis of a full application containing testing data and manufacturing information, which is owned and was submitted by another company and much of which constitutes trade secret information subject to constitutional protection. Because the Biosimilars Act authorizes biosimilar applicants to cite these previously approved applications, the implementation of the new legislative scheme raises critical issues under the Fifth Amendment of the Constitution, pursuant to which private property--trade secrets included--may not be taken for public use, without "just compensation." FDA must confront those issues as it implements the scheme set out in the Biosimilars Act. This article will discuss these issues, after providing a brief overview of the Biosimilars Act and a more detailed examination of the law of trade secrets.

Longitudinal relaxation of initially straight flexible and stiff polymers

NASA Astrophysics Data System (ADS)

Dimitrakopoulos, Panagiotis; Dissanayake, Inuka

2004-11-01

The present talk considers the relaxation of a single flexible or stiff polymer chain from an initial straight configuration in a viscous solvent. This problem commonly arises when strong flows are turned off in both industrial and biological applications. The problem is also motivated by recent experiments with single biopolymer molecules relaxing after being fully extended by applied forces as well as by the recent development of micro-devices involving stretched tethered biopolymers. Our results are applicable to a wide array of synthetic polymers such as polyacrylamides, Kevlar and polyesters as well as biopolymers such as DNA, actin filaments, microtubules and MTV. In this talk we discuss the mechanism of the polymer relaxation as was revealed through Brownian Dynamics simulations covering a broad range of time scales and chain stiffness. After the short-time free diffusion, the chain's longitudinal reduction at early intermediate times is shown to constitute a universal behavior for any chain stiffness caused by a quasi-steady relaxation of tensions associated with the deforming action of the Brownian forces. Stiff chains are shown to exhibit a late intermediate-time longitudinal reduction associated with a relaxation of tensions affected by the deforming Brownian and the restoring bending forces. The longitudinal and transverse relaxations are shown to obey different laws, i.e. the chain relaxation is anisotropic at all times. In the talk, we show how from the knowledge of the relaxation mechanism, we can predict and explain the polymer properties including the polymer stress and the solution birefringence. In addition, a generalized stress-optic law is derived valid for any time and chain stiffness. All polymer properties which depend on the polymer length are shown to exhibit two intermediate-time behaviors with the early one to constitute a universal behavior for any chain stiffness. This work was supported in part by the Minta Martin Research Fund. The

Biological preconcentrator

DOEpatents

Manginell, Ronald P [Albuquerque, NM; Bunker, Bruce C [Albuquerque, NM; Huber, Dale L [Albuquerque, NM

2008-09-09

A biological preconcentrator comprises a stimulus-responsive active film on a stimulus-producing microfabricated platform. The active film can comprise a thermally switchable polymer film that can be used to selectively absorb and desorb proteins from a protein mixture. The biological microfabricated platform can comprise a thin membrane suspended on a substrate with an integral resistive heater and/or thermoelectric cooler for thermal switching of the active polymer film disposed on the membrane. The active polymer film can comprise hydrogel-like polymers, such as poly(ethylene oxide) or poly(n-isopropylacrylamide), that are tethered to the membrane. The biological preconcentrator can be fabricated with semiconductor materials and technologies.

Polymer biomaterial constructs for regenerative medicine and functional biological systems

NASA Astrophysics Data System (ADS)

Meng, Linghui

The use of collagen as a biomaterial is currently undergoing a renaissance in the tissue engineering field. The excellent biocompatibility and safety due to its biological characteristics, such as biodegradability and weak antigenicity, make collagen a primary material resource in medical applications. Described herein is work towards the development of novel collagen-based matrices, with additional multi-functionality imparted through a novel in-situ crosslinking approach. The process of electrospinning has become a widely used technique for the creation of fibrous scaffolds for tissue engineering applications due to its ability to rapidly create structures composed of nano-scale polymer fibers closely resembling the architecture of the extracellular matrix (ECM). Collagen-PCL sheath-core bicomponent fibrous scaffolds were fabricated using a novel variation on traditional electrospinning, known as co-axial electrospinning. The results showed that the addition of a synthetic polymer core into collagen nanofibers remarkably increased the mechanical strength of collagen matrices spun from the benign solvent system. A novel single-step, in-situ collagen crosslink approach was developed in order to solve the problems dominating traditional collagen crosslinking methods, such as dimensional shrinking and loss of porous morphology, and to simplify the crosslinking procedure for electrospun collagen scaffolds. The excess amount of NHS present in the crosslinking mixture was found to delay the EDC/collagen coupling reaction in a controlled fashion. Fundamental investigations into the development and characterization of in-situ crosslinked collagen matrices such as fibrous scaffolds, gels and sponges, as well as their biomedical applications including cell culture substrates, wound dressings, drug delivery matrices and bone regeneration substitutes, were performed. The preliminary mice studies indicated that the in-situ crosslinked collagen matrices could be good candidates

Combined X-ray and neutron fibre diffraction studies of biological and synthetic polymers

NASA Astrophysics Data System (ADS)

Parrot, I. M.; Urban, V.; Gardner, K. H.; Forsyth, V. T.

2005-08-01

The fibrous state is a natural one for polymer molecules which tend to assume regular helical conformations rather than the globular structures characteristic of many proteins. Fibre diffraction therefore has broad application to the study of a wide range of biological and synthetic polymers. The purpose of this paper is to illustrate the general scope of the method and in particular to demonstrate the impact of a combined approach involving both X-ray and neutron diffraction methods. While the flux of modern X-ray synchrotron radiation sources allows high quality datasets to be recorded with good resolution within a very short space of time, neutron studies can provide unique information through the ability to locate hydrogen or deuterium atoms that are often difficult or impossible to locate using X-ray methods. Furthermore, neutron fibre diffraction methods can, through the ability to selectively label specific parts of a structure, be used to highlight novel aspects of polymer structure that can not be studied using X-rays. Two examples are given. The first describes X-ray and neutron diffraction studies of conformational transitions in DNA. The second describes structural studies of the synthetic high-performance polymer poly(p-phenylene terephthalamide) (PPTA), known commercially as Kevlar® or Twaron®.

Smart Polymer Surfaces

DTIC Science & Technology

2009-02-27

films: Inhibition of dewetting in thin polymer films”, Carroll, Gregory T., Sojka, Melissa E., Lei, Xuegong, Turro, Nicholas J., Koberstein, Jeffrey T...at Sandia was that the polymer films, designed to have specific interactions with particular warfare agents, would dewet the surface of a surface...crosslinking or dewetting . Patterned dewetting constitutes a completely new way of generating micro thin film structures that might be useful in

Polymer Electrolytes for Lithium/Sulfur Batteries

PubMed Central

Zhao, Yan; Zhang, Yongguang; Gosselink, Denise; Doan, The Nam Long; Sadhu, Mikhail; Cheang, Ho-Jae; Chen, Pu

2012-01-01

This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S) batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes. PMID:24958296

Star Polymers.

PubMed

Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G

2016-06-22

Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

Enhancement in biological response of Ag-nano composite polymer membranes using plasma treatment for fabrication of efficient bio materials

NASA Astrophysics Data System (ADS)

Agrawal, Narendra Kumar; Sharma, Tamanna Kumari; Chauhan, Manish; Agarwal, Ravi; Vijay, Y. K.; Swami, K. C.

2016-05-01

Biomaterials are nonviable material used in medical devices, intended to interact with biological systems, which are becoming necessary for the development of artificial material for biological systems such as artificial skin diaphragm, valves for heart and kidney, lenses for eye etc. Polymers having novel properties like antibacterial, antimicrobial, high adhesion, blood compatibility and wettability are most suitable for synthesis of biomaterial, but all of these properties does not exist in any natural or artificial polymeric material. Nano particles and plasma treatment can offer these properties to the polymers. Hence a new nano-biomaterial has been developed by modifying the surface and chemical properties of Ag nanocomposite polymer membranes (NCPM) by Argon ion plasma treatment. These membranes were characterized using different techniques for surface and chemical modifications occurred. Bacterial adhesion and wettability were also tested for these membranes, to show direct use of this new class of nano-biomaterial for biomedical applications.

Simulating the flow of entangled polymers.

PubMed

Masubuchi, Yuichi

2014-01-01

To optimize automation for polymer processing, attempts have been made to simulate the flow of entangled polymers. In industry, fluid dynamics simulations with phenomenological constitutive equations have been practically established. However, to account for molecular characteristics, a method to obtain the constitutive relationship from the molecular structure is required. Molecular dynamics simulations with atomic description are not practical for this purpose; accordingly, coarse-grained models with reduced degrees of freedom have been developed. Although the modeling of entanglement is still a challenge, mesoscopic models with a priori settings to reproduce entangled polymer dynamics, such as tube models, have achieved remarkable success. To use the mesoscopic models as staging posts between atomistic and fluid dynamics simulations, studies have been undertaken to establish links from the coarse-grained model to the atomistic and macroscopic simulations. Consequently, integrated simulations from materials chemistry to predict the macroscopic flow in polymer processing are forthcoming.

Synthetic (polymer) biology (membrane): functionalization of polymer scaffolds for membrane proteins.

PubMed

Hu, Zhaolong; Ho, James C S; Nallani, Madhavan

2017-08-01

A plethora of polymer-based scaffolds have been designed to facilitate biochemical and biophysical investigation of membrane proteins, with a common goal to stabilize and present them in a functional format. In this review, an up-to-date account of such polymer-based supports and incorporation methodologies are presented. Furthermore, conceptual and imminent technological advances, with associated technical challenges are proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of a Systems Computational Model to Investigate Early Biological Events in Hepatic Activation of Constitutive Androstane Receptor (CAR) by Phenobarbital

EPA Science Inventory

Activation of the nuclear receptor CAR (constitutive active/androstane receptor) is implicated in the control several key biological events such as metabolic pathways. Here, we combined data from literature with information obtained from in vitro assays in the US EPA ToxCast dat...

Conjugated Polymers in Bioelectronics.

PubMed

Inal, Sahika; Rivnay, Jonathan; Suiu, Andreea-Otilia; Malliaras, George G; McCulloch, Iain

2018-06-19

The emerging field of organic bioelectronics bridges the electronic world of organic-semiconductor-based devices with the soft, predominantly ionic world of biology. This crosstalk can occur in both directions. For example, a biochemical reaction may change the doping state of an organic material, generating an electronic readout. Conversely, an electronic signal from a device may stimulate a biological event. Cutting-edge research in this field results in the development of a broad variety of meaningful applications, from biosensors and drug delivery systems to health monitoring devices and brain-machine interfaces. Conjugated polymers share similarities in chemical "nature" with biological molecules and can be engineered on various forms, including hydrogels that have Young's moduli similar to those of soft tissues and are ionically conducting. The structure of organic materials can be tuned through synthetic chemistry, and their biological properties can be controlled using a variety of functionalization strategies. Finally, organic electronic materials can be integrated with a variety of mechanical supports, giving rise to devices with form factors that enable integration with biological systems. While these developments are innovative and promising, it is important to note that the field is still in its infancy, with many unknowns and immense scope for exploration and highly collaborative research. The first part of this Account details the unique properties that render conjugated polymers excellent biointerfacing materials. We then offer an overview of the most common conjugated polymers that have been used as active layers in various organic bioelectronics devices, highlighting the importance of developing new materials. These materials are the most popular ethylenedioxythiophene derivatives as well as conjugated polyelectrolytes and ion-free organic semiconductors functionalized for the biological interface. We then discuss several applications and

Path-Integration Computation of the Transport Properties of Polymers Nanoparticles and Complex Biological Structures

NASA Astrophysics Data System (ADS)

Douglas, Jack

2014-03-01

finite cross-section, DNA, nanoparticles with grafted chain layers and knotted polymers. The path-integration method, which grew up from research in Karl Freed's group, is evidently a powerful tool for computing basic transport properties of complex-shaped objects and should find increasing application in polymer science, nanotechnological applications and biology.

Modeling semiflexible polymer networks

NASA Astrophysics Data System (ADS)

Broedersz, C. P.; MacKintosh, F. C.

2014-07-01

This is an overview of theoretical approaches to semiflexible polymers and their networks. Such semiflexible polymers have large bending rigidities that can compete with the entropic tendency of a chain to crumple up into a random coil. Many studies on semiflexible polymers and their assemblies have been motivated by their importance in biology. Indeed, cross-linked networks of semiflexible polymers form a major structural component of tissue and living cells. Reconstituted networks of such biopolymers have emerged as a new class of biological soft matter systems with remarkable material properties, which have spurred many of the theoretical developments discussed here. Starting from the mechanics and dynamics of individual semiflexible polymers, the physics of semiflexible bundles, entangled solutions, and disordered cross-linked networks are reviewed. Finally, recent developments on marginally stable fibrous networks, which exhibit critical behavior similar to other marginal systems such as jammed soft matter, are discussed.

Combinatorial synthesis and screening of non-biological polymers

DOEpatents

Schultz, Peter G.; Xiang, Xiao-Dong; Goldwasser, Isy; Briceno, Gabriel; Sun, Xiao-Dong; Wang, Kai-An

2006-04-25

Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

Micro-processing of polymers and biological materials using high repetition rate femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Ding, Li

High repetition rate femtosecond laser micro-processing has been applied to ophthalmological hydrogel polymers and ocular tissues to create novel refractive and diffractive structures. Through the optimization of laser irradiation conditions and material properties, this technology has become feasible for future industrial applications and clinical practices. A femtosecond laser micro-processing workstation has been designed and developed. Different experimental parameters of the workstation such as laser pulse duration, focusing lens, and translational stages have been described and discussed. Diffractive gratings and three-dimensional waveguides have been fabricated and characterized in hydrogel polymers, and refractive index modifications as large as + 0.06 have been observed within the laser-irradiated region. Raman spectroscopic studies have shown that our femtosecond laser micro-processing induces significant thermal accumulation, resulting in a densification of the polymer network and increasing the localized refractive index of polymers within the laser irradiated region. Different kinds of dye chromophores have been doped in hydrogel polymers to enhance the two-photon absorption during femtosecond laser micro-processing. As the result, laser scanning speed can be greatly increased while the large refractive index modifications remain. Femtosecond laser wavelength and pulse energy as well as water and dye concentration of the hydrogels are optimized. Lightly fixed ocular tissues such as corneas and lenses have been micro-processed by focused femtosecond laser pulses, and refractive index modifications without any tissue-breakdown are observed within the stromal layer of the corneas and the cortex of the lenses. Living corneas are doped with Sodium Fluorescein to increase the two-photon absorption during the laser micro-processing, and laser scanning speed can be greatly increased while inducing large refractive index modifications. No evidence of cell death

Graphene-polymer hybrid nanostructure-based bioenergy storage device for real-time control of biological motor activity.

PubMed

Byun, Kyung-Eun; Choi, Dong Shin; Kim, Eunji; Seo, David H; Yang, Heejun; Seo, Sunae; Hong, Seunghun

2011-11-22

We report a graphene-polymer hybrid nanostructure-based bioenergy storage device to turn on and off biomotor activity in real-time. In this strategy, graphene was functionalized with amine groups and utilized as a transparent electrode supporting the motility of biomotors. Conducting polymer patterns doped with adenosine triphosphate (ATP) were fabricated on the graphene and utilized for the fast release of ATP by electrical stimuli through the graphene. The controlled release of biomotor fuel, ATP, allowed us to control the actin filament transportation propelled by the biomotor in real-time. This strategy should enable the integrated nanodevices for the real-time control of biological motors, which can be a significant stepping stone toward hybrid nanomechanical systems based on motor proteins. © 2011 American Chemical Society

Maximum drag reduction simulation using rodlike polymers.

PubMed

Gillissen, J J J

2012-10-01

Simulations of maximum drag reduction (MDR) in channel flow using constitutive equations for suspensions of noninteracting rods predict a few-fold larger turbulent kinetic energy than in experiments using rodlike polymers. These differences are attributed to the neglect of interactions between polymers in the simulations. Despite these inconsistencies the simulations correctly reproduce the essential features of MDR, with universal profiles of the mean flow and the shear stress budgets that do not depend on the polymer concentration.

Synthetic Polymers from Readily Available Monosaccharides

NASA Astrophysics Data System (ADS)

Galbis, J. A.; García-Martín, M. G.

The low degradability of petroleum-based polymers and the massive use of these materials constitute a serious problem because of the environmental pollution that they can cause. Thus, sustained efforts have been extensively devoted to produce new polymers based on natural renewing resources and with higher degradability. Of the different natural sources, carbohydrates stand out as highly convenient raw materials because they are inexpensive, readily available, and provide great stereochemical diversity. New polymers, analogous to the more accredited technical polymers, but based on chiral monomers, have been synthesized from natural and available sugars. This chapter describes the potential of sugar-based monomers as precursors to a wide variety of macromolecular materials.

Surface grafting of zwitterionic polymers onto dye doped AIE-active luminescent silica nanoparticles through surface-initiated ATRP for biological imaging applications

NASA Astrophysics Data System (ADS)

Mao, Liucheng; Liu, Xinhua; Liu, Meiying; Huang, Long; Xu, Dazhuang; Jiang, Ruming; Huang, Qiang; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-10-01

Aggregation-induced emission (AIE) dyes have recently been intensively explored for biological imaging applications owing to their outstanding optical feature as compared with conventional organic dyes. The AIE-active luminescent silica nanoparticles (LSNPs) are expected to combine the advantages both of silica nanoparticles and AIE-active dyes. Although the AIE-active LSNPs have been prepared previously, surface modification of these AIE-active LSNPs with functional polymers has not been reported thus far. In this work, we reported a rather facile and general strategy for preparation of polymers functionalized AIE-active LSNPs through the surface-initiated atom transfer radical polymerization (ATRP). The AIE-active LSNPs were fabricated via direct encapsulation of AIE-active dye into silica nanoparticles through a non-covalent modified Stöber method. The ATRP initiator was subsequently immobilized onto these AIE-active LSNPs through amidation reaction between 3-aminopropyl-triethoxy-silane and 2-bromoisobutyryl bromide. Finally, the zwitterionic 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) was selected as model monomer and grafted onto MSNs through ATRP. The characterization results suggested that LSNPs can be successfully modified with poly(MPC) through surface-initiated ATRP. The biological evaluation results demonstrated that the final SNPs-AIE-pMPC composites possess low cytotoxicity, desirable optical properties and great potential for biological imaging. Taken together, we demonstrated that AIE-active LSNPs can be fabricated and surface modified with functional polymers to endow novel functions and better performance for biomedical applications. More importantly, this strategy developed in this work could also be extended for fabrication of many other LSNPs polymer composites owing to the good monomer adoptability of ATRP.

Constitutive Behavior and Finite Element Analysis of FRP Composite and Concrete Members.

PubMed

Ann, Ki Yong; Cho, Chang-Geun

2013-09-10

The present study concerns compressive and flexural constitutive models incorporated into an isoparametric beam finite element scheme for fiber reinforced polymer (FRP) and concrete composites, using their multi-axial constitutive behavior. The constitutive behavior of concrete was treated in triaxial stress states as an orthotropic hypoelasticity-based formulation to determine the confinement effect of concrete from a three-dimensional failure surface in triaxial stress states. The constitutive behavior of the FRP composite was formulated from the two-dimensional classical lamination theory. To predict the flexural behavior of circular cross-section with FRP sheet and concrete composite, a layered discretization of cross-sections was incorporated into nonlinear isoparametric beam finite elements. The predicted constitutive behavior was validated by a comparison to available experimental results in the compressive and flexural beam loading test.

Constitutive Behavior and Finite Element Analysis of FRP Composite and Concrete Members

PubMed Central

Ann, Ki Yong; Cho, Chang-Geun

2013-01-01

The present study concerns compressive and flexural constitutive models incorporated into an isoparametric beam finite element scheme for fiber reinforced polymer (FRP) and concrete composites, using their multi-axial constitutive behavior. The constitutive behavior of concrete was treated in triaxial stress states as an orthotropic hypoelasticity-based formulation to determine the confinement effect of concrete from a three-dimensional failure surface in triaxial stress states. The constitutive behavior of the FRP composite was formulated from the two-dimensional classical lamination theory. To predict the flexural behavior of circular cross-section with FRP sheet and concrete composite, a layered discretization of cross-sections was incorporated into nonlinear isoparametric beam finite elements. The predicted constitutive behavior was validated by a comparison to available experimental results in the compressive and flexural beam loading test. PMID:28788312

Comparative experiments for in vivo fibroplasia and biological stability of four porous polymers intended for use in the Seoul-type keratoprosthesis

PubMed Central

Kim, M K; Lee, J L; Wee, W R; Lee, J H

2002-01-01

Aims: To evaluate in vivo fibroplasia and biological stability of porous polymers intended for use in the Seoul-type keratoprosthesis (S-KPro). Methods: Four porous polymers (polypropylene, two kinds of polyethylene terephthalate (PE70 and PE50), and polyurethane) were investigated. Discs of polymers were inserted into the corneal stroma of rabbits for a 2 and 5 month period. Corneal oedema and neovascularisation were evaluated. The fibroplasia and collagen deposition were examined under light and transmission electron microscopy. S-KPros, whose skirt was made of four types of polymer, were implanted into the rabbits' eyes. The retention time and complications were evaluated. Results: Neovascularisation and corneal oedema were found in all of the disc inserted eyes, but the corneal oedema subsided within 2 months in most of the eyes. The mean number of fibroblasts increased significantly in polypropylene and PE50 disc inserted eyes compared with polyurethane disc inserted eyes. Plentiful collagen deposition was also found in both polypropylene and PE50 disc inserted eyes. Mean retention time in the polypropylene SK-Pro implanted eyes was longer than that of the other eyes (20.7 weeks). The PE70 skirt induced corneal melting around the prosthesis. Conclusion: Polypropylene encourages fibroblast ingrowth and shows good biological stability when used as a skirt material in S-KPro. PMID:12084755

Physical properties of immiscible polymers

NASA Technical Reports Server (NTRS)

Harris, J. Milton

1987-01-01

The demixing of immiscible polymers in low gravity is discussed. Applications of knowledge gained in this research will provide a better understanding of the role of phase segregation in determining the properties of polymer blends made from immiscible polymers. Knowledge will also be gained regarding the purification of biological materials by partitioning between the two liquid phases formed by solution of the polymers polyethylene glycol and dextran in water. Testing of new apparatus for space flight, extension of affinity phase partitioning, refinement of polymer chemistry, and demixing of isopycnic polymer phases in a one gravity environment are discussed.

A nonlinear viscoelastic constitutive equation - Yield predictions in multiaxial deformations

NASA Technical Reports Server (NTRS)

Shay, R. M., Jr.; Caruthers, J. M.

1987-01-01

Yield stress predictions of a nonlinear viscoelastic constitutive equation for amorphous polymer solids have been obtained and are compared with the phenomenological von Mises yield criterion. Linear viscoelasticity theory has been extended to include finite strains and a material timescale that depends on the instantaneous temperature, volume, and pressure. Results are presented for yield and the correct temperature and strain-rate dependence in a variety of multiaxial deformations. The present nonlinear viscoelastic constitutive equation can be formulated in terms of either a Cauchy or second Piola-Kirchhoff stress tensor, and in terms of either atmospheric or hydrostatic pressure.

Multifunctional and biologically active matrices from multicomponent polymeric solutions

NASA Technical Reports Server (NTRS)

Kiick, Kristi L. (Inventor); Yamaguchi, Nori (Inventor)

2010-01-01

The present invention relates to a biologically active functionalized electrospun matrix to permit immobilization and long-term delivery of biologically active agents. In particular the invention relates to a functionalized polymer matrix comprising a matrix polymer, a compatibilizing polymer and a biomolecule or other small functioning molecule. In certain aspects the electrospun polymer fibers comprise at least one biologically active molecule functionalized with low molecular weight heparin. Examples of active molecules that may be used with the multicomponent polymer of the invention include, for example, a drug, a biopolymer, for example a growth factor, a protein, a peptide, a nucleotide, a polysaccharide, a biological macromolecule or the like. The invention is further directed to the formation of functionalized crosslinked matrices, such as hydrogels, that include at least one functionalized compatibilizing polymer capable of assembly.

Polymer flexibility and turbulent drag reduction.

PubMed

Gillissen, J J J

2008-10-01

Polymer-induced drag reduction is the phenomenon by which the friction factor of a turbulent flow is reduced by the addition of small amounts of high-molecular-weight linear polymers, which conformation in solution at rest can vary between randomly coiled and rodlike. It is well known that drag reduction is positively correlated to viscous stresses, which are generated by extended polymers. Rodlike polymers always assume this favorable conformation, while randomly coiling chains need to be unraveled by fluid strain rate in order to become effective. The coiling and stretching of flexible polymers in turbulent flow produce an additional elastic component in the polymer stress. The effect of the elastic stresses on drag reduction is unclear. To study this issue, we compare direct numerical simulations of turbulent drag reduction in channel flow using constitutive equations describing solutions of rigid and flexible polymers. When compared at constant phi r2, both simulations predict the same amount of drag reduction. Here phi is the polymer volume fraction and r is the polymer aspect ratio, which for flexible polymers is based on average polymer extension at the channel wall. This demonstrates that polymer elasticity plays a marginal role in the mechanism for drag reduction.

Functional Supramolecular Polymers*

PubMed Central

Aida, T.; Meijer, E.W.; Stupp, S.I.

2012-01-01

Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. PMID:22344437

Analytical Modeling of the High Strain Rate Deformation of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Roberts, Gary D.; Gilat, Amos

2003-01-01

The results presented here are part of an ongoing research program to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to high strain rate impact loads. State variable constitutive equations originally developed for metals have been modified in order to model the nonlinear, strain rate dependent deformation of polymeric matrix materials. To account for the effects of hydrostatic stresses, which are significant in polymers, the classical 5 plasticity theory definitions of effective stress and effective plastic strain are modified by applying variations of the Drucker-Prager yield criterion. To verify the revised formulation, the shear and tensile deformation of a representative toughened epoxy is analyzed across a wide range of strain rates (from quasi-static to high strain rates) and the results are compared to experimentally obtained values. For the analyzed polymers, both the tensile and shear stress-strain curves computed using the analytical model correlate well with values obtained through experimental tests. The polymer constitutive equations are implemented within a strength of materials based micromechanics method to predict the nonlinear, strain rate dependent deformation of polymer matrix composites. In the micromechanics, the unit cell is divided up into a number of independently analyzed slices, and laminate theory is then applied to obtain the effective deformation of the unit cell. The composite mechanics are verified by analyzing the deformation of a representative polymer matrix composite (composed using the representative polymer analyzed for the correlation of the polymer constitutive equations) for several fiber orientation angles across a variety of strain rates. The computed values compare favorably to experimentally obtained results.

Directed polymers versus directed percolation

NASA Astrophysics Data System (ADS)

Halpin-Healy, Timothy

1998-10-01

Universality plays a central role within the rubric of modern statistical mechanics, wherein an insightful continuum formulation rises above irrelevant microscopic details, capturing essential scaling behaviors. Nevertheless, occasions do arise where the lattice or another discrete aspect can constitute a formidable legacy. Directed polymers in random media, along with its close sibling, directed percolation, provide an intriguing case in point. Indeed, the deep blood relation between these two models may have sabotaged past efforts to fully characterize the Kardar-Parisi-Zhang universality class, to which the directed polymer belongs.

Predictive Modeling of Polymer Mechanical Behavior Coupled to Chemical Change/ Technique Development for Measuring Polymer Physical Aging.

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

Kropka, Jamie Michael; Stavig, Mark E.; Arechederra, Gabe Kenneth

Develop an understanding of the evolution of glassy polymer mechanical response during aging and the mechanisms associated with that evolution. That understanding will be used to develop constitutive models to assess the impact of stress evolution in encapsulants on NW designs.

Laser surface texturing of polymers for biomedical applications

NASA Astrophysics Data System (ADS)

Riveiro, Antonio; Maçon, Anthony L. B.; del Val, Jesus; Comesaña, Rafael; Pou, Juan

2018-02-01

Polymers are materials widely used in biomedical science because of their biocompatibility, and good mechanical properties (which, in some cases, are similar to those of human tissues); however, these materials are, in general, chemically and biologically inert. Surface characteristics, such as topography (at the macro-, micro, and nanoscale), surface chemistry, surface energy, charge or wettability are interrelated properties, and they cooperatively influence the biological performance of materials when used for biomedical applications. They regulate the biological response at the implant/tissue interface (e.g., influencing the cell adhesion, cell orientation, cell motility, etc.). Several surface processing techniques have been explored to modulate these properties for biomedical applications. Despite their potentials, these methods have limitations that prevent their applicability. In this regard, laser-based methods, in particular laser surface texturing (LST), can be an interesting alternative. Different works have showed the potentiality of this technique to control the surface properties of biomedical polymers and enhance their biological performance; however, more research is needed to obtain the desired biological response. This work provides a general overview of the basics and applications of LST for the surface modification of polymers currently used in the clinical practice (e.g. PEEK, UHMWPE, PP, etc.). The modification of roughness, wettability, and their impact on the biological response is addressed to offer new insights on the surface modification of biomedical polymers.

Exploring 'new' bioactivities of polymers at the nano-bio interface.

PubMed

Wang, Chunming; Dong, Lei

2015-01-01

A biological system is essentially an elegant assembly of polymeric nanostructures. The polymers in the body, biomacromolecules, are both building blocks and versatile messengers. We propose that non-biologically derived polymers can be potential therapeutic candidates with unique advantages. Emerging findings about polycations, polysaccharides, immobilised multivalent ligands, and biomolecular coronas provide evidence that polymers are activated at the nano-bio interface, while emphasising the current theoretical and practical challenges. Our increasing understanding of the nano-bio interface and evolving approaches to establish the therapeutic potential of polymers enable the development of polymer drugs with high specificities for broad applications. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermoelectric Polymers and their Elastic Aerogels.

PubMed

Khan, Zia Ullah; Edberg, Jesper; Hamedi, Mahiar Max; Gabrielsson, Roger; Granberg, Hjalmar; Wågberg, Lars; Engquist, Isak; Berggren, Magnus; Crispin, Xavier

2016-06-01

Electronically conducting polymers constitute an emerging class of materials for novel electronics, such as printed electronics and flexible electronics. Their properties have been further diversified to introduce elasticity, which has opened new possibility for "stretchable" electronics. Recent discoveries demonstrate that conducting polymers have thermoelectric properties with a low thermal conductivity, as well as tunable Seebeck coefficients - which is achieved by modulating their electrical conductivity via simple redox reactions. Using these thermoelectric properties, all-organic flexible thermoelectric devices, such as temperature sensors, heat flux sensors, and thermoelectric generators, are being developed. In this article we discuss the combination of the two emerging fields: stretchable electronics and polymer thermoelectrics. The combination of elastic and thermoelectric properties seems to be unique for conducting polymers, and difficult to achieve with inorganic thermoelectric materials. We introduce the basic concepts, and state of the art knowledge, about the thermoelectric properties of conducting polymers, and illustrate the use of elastic thermoelectric conducting polymer aerogels that could be employed as temperature and pressure sensors in an electronic-skin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Approach to Conjugated Polymers with Biomimetic Properties.

PubMed

Baek, Paul; Voorhaar, Lenny; Barker, David; Travas-Sejdic, Jadranka

2018-06-13

The field of bioelectronics involves the fascinating interplay between biology and human-made electronics. Applications such as tissue engineering, biosensing, drug delivery, and wearable electronics require biomimetic materials that can translate the physiological and chemical processes of biological systems, such as organs, tissues. and cells, into electrical signals and vice versa. However, the difference in the physical nature of soft biological elements and rigid electronic materials calls for new conductive or electroactive materials with added biomimetic properties that can bridge the gap. Soft electronics that utilize organic materials, such as conjugated polymers, can bring many important features to bioelectronics. Among the many advantages of conjugated polymers, the ability to modulate the biocompatibility, solubility, functionality, and mechanical properties through side chain engineering can alleviate the issues of mechanical mismatch and provide better interface between the electronics and biological elements. Additionally, conjugated polymers, being both ionically and electrically conductive through reversible doping processes provide means for direct sensing and stimulation of biological processes in cells, tissues, and organs. In this Account, we focus on our recent progress in molecular engineering of conjugated polymers with tunable biomimetic properties, such as biocompatibility, responsiveness, stretchability, self-healing, and adhesion. Our approach is general and versatile, which is based on functionalization of conjugated polymers with long side chains, commonly polymeric or biomolecules. Applications for such materials are wide-ranging, where we have demonstrated conductive, stimuli-responsive antifouling, and cell adhesive biointerfaces that can respond to external stimuli such as temperature, salt concentration, and redox reactions, the processes that in turn modify and reversibly switch the surface properties. Furthermore, utilizing the

Artificially Engineered Protein Polymers.

PubMed

Yang, Yun Jung; Holmberg, Angela L; Olsen, Bradley D

2017-06-07

Modern polymer science increasingly requires precise control over macromolecular structure and properties for engineering advanced materials and biomedical systems. The application of biological processes to design and synthesize artificial protein polymers offers a means for furthering macromolecular tunability, enabling polymers with dispersities of ∼1.0 and monomer-level sequence control. Taking inspiration from materials evolved in nature, scientists have created modular building blocks with simplified monomer sequences that replicate the function of natural systems. The corresponding protein engineering toolbox has enabled the systematic development of complex functional polymeric materials across areas as diverse as adhesives, responsive polymers, and medical materials. This review discusses the natural proteins that have inspired the development of key building blocks for protein polymer engineering and the function of these elements in material design. The prospects and progress for scalable commercialization of protein polymers are reviewed, discussing both technology needs and opportunities.

Improved Tumor Targeting of Polymer-based Nanovesicles Using Polymer-Lipid Blends

PubMed Central

Cheng, Zhiliang; Elias, Drew R.; Kamat, Neha P.; Johnston, Eric D.; Poloukhtine, Andrei; Popik, Vladimir; Hammer, Daniel A.; Tsourkas, Andrew

2011-01-01

Block copolymer-based vesicles have recently garnered a great deal of interest as nanoplatforms for drug delivery and molecular imaging applications due to their unique structural properties. These nanovesicles have been shown to direct their cargo to disease sites either through enhanced permeability and retention or even more efficiently via active targeting. Here we show that the efficacy of nanovesicle targeting can be significantly improved when prepared from polymer-lipid blends compared with block copolymer alone. Polymer-lipid hybrid nanovesicles were produced from the aqueous co-assembly of the diblock copolymer, poly(ethylene oxide)-block-polybutadiene (PEO-PBD), and the phospholipid, hydrogenated soy phosphatidylcholine (HSPC). The PEG-based vesicles, 117 nm in diameter, were functionalized with either folic acid or anti-HER2/neu affibodies as targeting ligands to confer specificity for cancer cells. Our results revealed that nanovesicles prepared from polymer-lipid blends led to significant improvement in cell binding compared to nanovesicles prepared from block copolymer alone in both in vitro cell studies and murine tumor models. Therefore, it is envisioned that nanovesicles composed of polymer-lipid blends may constitute a preferred embodiment for targeted drug delivery and molecular imaging applications. PMID:21899335

Hybrid protein-synthetic polymer nanoparticles for drug delivery.

PubMed

Koseva, Neli S; Rydz, Joanna; Stoyanova, Ekaterina V; Mitova, Violeta A

2015-01-01

Among the most common nanoparticulate systems, the polymeric nanocarriers have a number of key benefits, which give a great choice of delivery platforms. Nevertheless, polymeric nanoparticles possess some limitations that include use of toxic solvents in the production process, polymer degradation, drug leakage outside the diseased tissue, and polymer cytotoxicity. The combination of polymers of biological and synthetic origin is an appealing modern strategy for the production of novel nanocarriers with unprecedented properties. Proteins' interface can play an important role in determining bioactivity and toxicity and gives perspective for future development of the polymer-based nanoparticles. The design of hybrid constructs composed of synthetic polymer and biological molecules such as proteins can be considered as a straightforward tool to integrate a broad spectrum of properties and biofunctions into a single device. This review discusses hybrid protein-synthetic polymer nanoparticles with different structures and levels in complexity and functionality, in view of their applications as drug delivery systems. © 2015 Elsevier Inc. All rights reserved.

Cognition research and constitutional classification in Chinese medicine.

PubMed

Wang, Ji; Li, Yingshuai; Ni, Cheng; Zhang, Huimin; Li, Lingru; Wang, Qi

2011-01-01

In the Western medicine system, scholars have explained individual differences in terms of behaviour and thinking, leading to the emergence of various classification theories on individual differences. Traditional Chinese medicine has long observed human constitutions. Modern Chinese medicine studies have also involved study of human constitutions; however, differences exist in the ways traditional and modern Chinese medicine explore individual constitutions. In the late 1970s, the constitutional theory of Chinese medicine was proposed. This theory takes a global and dynamic view of human differences (e.g., the shape of the human body, function, psychology, and other characteristics) based on arguments from traditional Chinese medicine. The establishment of a standard for classifying constitutions into nine modules was critical for clinical application of this theory. In this review, we describe the history and recent research progress of this theory, and compare it with related studies in the western medicine system. Several research methods, including philology, informatics, epidemiology, and molecular biology, in classifying constitutions used in the constitutional theory of Chinese medicine were discussed. In summary, this constitutional theory of Chinese medicine can be used in clinical practice and would contribute to health control of patients.

Polymer therapeutics: concepts and applications.

PubMed

Haag, Rainer; Kratz, Felix

2006-02-13

Polymer therapeutics encompass polymer-protein conjugates, drug-polymer conjugates, and supramolecular drug-delivery systems. Numerous polymer-protein conjugates with improved stability and pharmacokinetic properties have been developed, for example, by anchoring enzymes or biologically relevant proteins to polyethylene glycol components (PEGylation). Several polymer-protein conjugates have received market approval, for example the PEGylated form of adenosine deaminase. Coupling low-molecular-weight anticancer drugs to high-molecular-weight polymers through a cleavable linker is an effective method for improving the therapeutic index of clinically established agents, and the first candidates have been evaluated in clinical trials, including, N-(2-hydroxypropyl)methacrylamide conjugates of doxorubicin, camptothecin, paclitaxel, and platinum(II) complexes. Another class of polymer therapeutics are drug-delivery systems based on well-defined multivalent and dendritic polymers. These include polyanionic polymers for the inhibition of virus attachment, polycationic complexes with DNA or RNA (polyplexes), and dendritic core-shell architectures for the encapsulation of drugs. In this Review an overview of polymer therapeutics is presented with a focus on concepts and examples that characterize the salient features of the drug-delivery systems.

Separation and enrichment of trace ractopamine in biological samples by uniformly-sized molecularly imprinted polymers

PubMed Central

Li, Ya; Fu, Qiang; Liu, Meng; Jiao, Yuan-Yuan; Du, Wei; Yu, Chong; Liu, Jing; Chang, Chun; Lu, Jian

2012-01-01

In order to prepare a high capacity packing material for solid-phase extraction with specific recognition ability of trace ractopamine in biological samples, uniformly-sized, molecularly imprinted polymers (MIPs) were prepared by a multi-step swelling and polymerization method using methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and toluene as a porogen respectively. Scanning electron microscope and specific surface area were employed to identify the characteristics of MIPs. Ultraviolet spectroscopy, Fourier transform infrared spectroscopy, Scatchard analysis and kinetic study were performed to interpret the specific recognition ability and the binding process of MIPs. The results showed that, compared with other reports, MIPs synthetized in this study showed high adsorption capacity besides specific recognition ability. The adsorption capacity of MIPs was 0.063 mmol/g at 1 mmol/L ractopamine concentration with the distribution coefficient 1.70. The resulting MIPs could be used as solid-phase extraction materials for separation and enrichment of trace ractopamine in biological samples. PMID:29403774

pH-responsive fluorescence chemical sensor constituted by conjugated polymers containing pyridine rings.

PubMed

Adachi, Naoya; Kaneko, Yuki; Sekiguchi, Kazuki; Sugiyama, Hiroki; Sugeno, Masafumi

2015-12-01

Poly(p-pyridinium phenylene ethynylene)s (PPyPE) functionalized with alternating donor-acceptor repeat units were synthesized by a Pd-catalyzed Sonogashira coupling reaction between diethynyl monomer and di-iodopyridine for use as a pH-responsive fluorescence chemical sensor. The synthesized PPyPE, containing pyridine units, was characterized by FT-IR, (1)H and (13)C NMR, UV-visible and fluorescence spectroscopies. We investigated the relationship between changes of optical properties and protonation/deprotonation of PPyPE containing pyridine units in solution. Addition of HCl decreased and red-shifted the fluorescence intensity of the conjugated polymers that contained pyridine rings; fluorescence intensity of the polymers increased upon addition of NaOH solution. The synthesized PPyPE was found to be an effective and reusable chemical sensor for pH sensing. Copyright © 2015 John Wiley & Sons, Ltd.

Extension of in vivo half-life of biologically active peptides via chemical conjugation to XTEN protein polymer.

PubMed

Podust, Vladimir N; Sim, Bee-Cheng; Kothari, Dharti; Henthorn, Lana; Gu, Chen; Wang, Chia-wei; McLaughlin, Bryant; Schellenberger, Volker

2013-11-01

XTEN, unstructured biodegradable proteins, have been used to extend the in vivo half-life of genetically fused therapeutic proteins and peptides. To expand the applications of XTEN technology to half-life extension of other classes of molecules, XTEN protein polymers and methods for chemical XTENylation were developed. Two XTEN precursors were engineered to contain enzymatically removable purification tags. The proteins were readily expressed in bacteria and purified to homogeneity by chromatography techniques. As proof-of-principle, GLP2-2G peptide was chemically conjugated to each of the two XTEN protein polymers using maleimide-thiol chemistry. The monodisperse nature of XTEN protein polymer enabled reaction monitoring as well as the detection of peptide modifications in the conjugated state using reverse phase-high performance liquid chromatography (RP-HPLC) and electrospray ionization mass spectrometry. The resulting GLP2-2G-XTEN conjugates were purified by preparative RP-HPLC to homogeneity. In comparison with recombinantly fused GLP2-2G-XTEN, chemically conjugated GLP2-2G-XTEN molecules exhibited comparable in vitro activity, in vitro plasma stability and pharmacokinetics in rats. These data suggest that chemical XTENylation could effectively extend the half-life of a wide spectrum of biologically active molecules, therefore broadening its applicability.

Multifunctional and biologically active matrices from multicomponent polymeric solutions

NASA Technical Reports Server (NTRS)

Kiick, Kristi L. (Inventor); Yamaguchi, Nori (Inventor); Rabolt, John (Inventor); Casper, Cheryl (Inventor)

2012-01-01

A functionalized electrospun matrix for the controlled-release of biologically active agents, such as growth factors, is presented. The functionalized matrix comprises a matrix polymer, a compatibilizing polymer and a biomolecule or other small functioning molecule. In certain aspects the electrospun polymer fibers comprise at least one biologically active molecule functionalized with low molecular weight heparin.

On the Constitutive Response Characterization for Composite Materials Via Data-Driven Design Optimization

Treesearch

John G. Michopoulos; John G. Hermanson; Athanasios lliopoulos; Samuel Lambrakos; Tomonari Furukawa

2011-01-01

In the present paper we focus on demonstrating the use of design optimization for the constitutive characterization of anisotropic material systems such as polymer matrix composites, with or without damage. All approaches are based on the availability of experimental data originating from mechatronic material testing systems that can expose specimens to...

Constitutional multicenter bank linked to Sasang constitutional phenotypic data.

PubMed

Jin, Hee-Jeong; Baek, Younghwa; Kim, Ho-Seok; Ryu, Jonghyang; Lee, Siwoo

2015-03-10

Biobanks are more important in medical area because they can give researchers data for demonstrating and validating their research. In this study, we developed a biobank called the Korea Constitutional Multicenter Bank (KCMB) based on Sasang Constitutional Medicine (SCM). The aim of the KCMB was a foundation to providing the scientific basis of SCM. The KCMB has been constructed since 2006 in 24 Korean medical clinics with collection of questionnaire data, physical measurements and biological information comprised the results from blood test and DNA analyses. All participants were prescribed Sasang Constitution (SC)-specific herbal remedies for the treatment, and showed improvement of original symptoms as confirmed by Korean medicine doctor. Collected data went through de-identification process using the electronic case report form system. For calculation of several SC type specific tendencies, we used the direct standardization and Chi-square tests. The KCMB collected clinical information from 3,711 study participants (1,353 men and 2,358 women) aged more than 10 years. The mean age (± standard deviation) was 47.1 (±16.6) and 47.7 (±15.8) years for men and women respectively. After applying the direct standardization, the estimated constitutional distributions for the SC types were as follows: 39.2% for Tae-eumin(TE), 27.1% for Soeumin(SE), 33.7% for Soyangyin(SY), and non-zero but below 0.1% for Taeyangyin(TY). The estimated distribution of TE was about 10% less, while that of SY and SE were slightly more than the distribution reported by Jema Lee established the SCM. Based on the participants' medical history within the KCMB, each SC type had notably different frequencies for some diseases such as hypertension, diabetes, hyperlipidemia, stroke, and obesity (P < 0.001). The KCMB may serve to verify and validate SCM theories and practices. It may also provide new insights into SCM mechanisms. The results from many studies using the KCMB data are of great

Polymers for Drug Delivery Systems

PubMed Central

Liechty, William B.; Kryscio, David R.; Slaughter, Brandon V.; Peppas, Nicholas A.

2012-01-01

Polymers have played an integral role in the advancement of drug delivery technology by providing controlled release of therapeutic agents in constant doses over long periods, cyclic dosage, and tunable release of both hydrophilic and hydrophobic drugs. From early beginnings using off-the-shelf materials, the field has grown tremendously, driven in part by the innovations of chemical engineers. Modern advances in drug delivery are now predicated upon the rational design of polymers tailored for specific cargo and engineered to exert distinct biological functions. In this review, we highlight the fundamental drug delivery systems and their mathematical foundations and discuss the physiological barriers to drug delivery. We review the origins and applications of stimuli-responsive polymer systems and polymer therapeutics such as polymer-protein and polymer-drug conjugates. The latest developments in polymers capable of molecular recognition or directing intracellular delivery are surveyed to illustrate areas of research advancing the frontiers of drug delivery. PMID:22432577

Functional polymers as therapeutic agents: concept to market place.

PubMed

Dhal, Pradeep K; Polomoscanik, Steven C; Avila, Louis Z; Holmes-Farley, S Randall; Miller, Robert J

2009-11-12

Biologically active synthetic polymers have received considerable scientific interest and attention in recent years for their potential as promising novel therapeutic agents to treat human diseases. Although a significant amount of research has been carried out involving polymer-linked drugs as targeted and sustained release drug delivery systems and prodrugs, examples on bioactive polymers that exhibit intrinsic therapeutic properties are relatively less. Several appealing characteristics of synthetic polymers including high molecular weight, molecular architecture, and controlled polydispersity can all be utilized to discover a new generation of therapies. For example, high molecular weight bioactive polymers can be restricted to gastrointestinal tract, where they can selectively recognize, bind, and remove target disease causing substances from the body. The appealing features of GI tract restriction and stability in biological environment render these polymeric drugs to be devoid of systemic toxicity that are generally associated with small molecule systemic drugs. The present article highlights recent developments in the rational design and synthesis of appropriate functional polymers that have resulted in a number of promising polymer based therapies and biomaterials, including some marketed products.

Nucleation in Polymers and Soft Matter

NASA Astrophysics Data System (ADS)

Xu, Xiaofei; Ting, Christina L.; Kusaka, Isamu; Wang, Zhen-Gang

2014-04-01

Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer-small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.

Conformational assembly and biological properties of collagen mimetic peptides and their thermally responsive polymer conjugates

NASA Astrophysics Data System (ADS)

Krishna, Ohm Divyam

2011-12-01

Collagens are one of the most abundant proteins found in body tissues and organs, endowing structural integrity, mechanical strength, and multiple biological functions. Destabilized collagen inside human body leads to various degenerative diseases (ex. osteoarthritis) and ageing. This has continued to motivate the design of synthetic peptides and bio-synthetic polypeptides to closely mimic the native collagens in terms of triple helix structure and stability, potential for higher order assembly, and biological properties. However, the widespread application of de novo collagens has been limited in part by the need for hydroxylated proline in the formation of stable triple helical structures. To address this continued need, a hydroxyproline-free, thermally stable collagen-mimetic peptide (CLP-Cys) was rationally designed via the incorporation of electrostatically stabilized amino acid triplets. CLP-Cys was synthesized via solid phase peptide synthesis. The formation and stability of the triple helical structure were indicated via circular dichroism (CD) experiments and confirmed via differential scanning calorimetry (DSC) results. CLP-Cys also self-assembled into nano-rods and micro-fibrils, as evidenced via a combination of dynamic light scattering and transmission electron microscopy. Given the high thermal stability and its propensity for higher-order assembly, CLP-Cys was further functionalized at both the ends with a thermally responsive polymer, poly(diethylene glycol methyl ether methacrylate), (PDEGMEMA) to synthesize a biohybrid triblock copolymer. The CD results indicated that the triple helical form is retained, the thermal unfolding is sustained and helix to coil transition is reversible in the triblock hybrid context. The LCST of PDEGMEMA homopolymer (26 °C) is increased (to 35 °C) upon conjugation to the hydrophilic collagen peptide domain. Further, a combination of static light scattering, Cryo-SEM, TEM and confocal microscopy elucidated that the

Molecularly Engineered Polymer-Based Systems in Drug Delivery and Regenerative Medicine.

PubMed

Piluso, Susanna; Soultan, Al Halifa; Patterson, Jennifer

2017-01-01

Polymer-based systems are attractive in drug delivery and regenerative medicine due to the possibility of tailoring their properties and functions to a specific application. The present review provides several examples of molecularly engineered polymer systems, including stimuli responsive polymers and supramolecular polymers. The advent of controlled polymerization techniques has enabled the preparation of polymers with controlled molecular weight and well-defined architecture. By using these techniques coupled to orthogonal chemical modification reactions, polymers can be molecularly engineered to incorporate functional groups able to respond to small changes in the local environment or to a specific biological signal. This review highlights the properties and applications of stimuli-responsive systems and polymer therapeutics, such as polymer-drug conjugates, polymer-protein conjugates, polymersomes, and hyperbranched systems. The applications of polymeric membranes in regenerative medicine are also discussed. The examples presented in this review suggest that the combination of membranes with polymers that are molecularly engineered to respond to specific biological functions could be relevant in the field of regenerative medicine. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Electrically switchable polymer liquid crystal and polymer birefringent flake in fluid host systems and optical devices utilizing same

DOEpatents

Marshall, Kenneth L.; Kosc, Tanya Z.; Jacobs, Stephen D.; Faris, Sadeg M.; Li, Le

2003-12-16

Flakes or platelets of polymer liquid crystals (PLC) or other birefringent polymers (BP) suspended in a fluid host medium constitute a system that can function as the active element in an electrically switchable optical device when the suspension is either contained between a pair of rigid substrates bearing transparent conductive coatings or dispersed as microcapsules within the body of a flexible host polymer. Optical properties of these flake materials include large effective optical path length, different polarization states and high angular sensitivity in their selective reflection or birefringence. The flakes or platelets of these devices need only a 3-20.degree. rotation about the normal to the cell surface to achieve switching characteristics obtainable with prior devices using particle rotation or translation.

Microbial production of building block chemicals and polymers.

PubMed

Lee, Jeong Wook; Kim, Hyun Uk; Choi, Sol; Yi, Jongho; Lee, Sang Yup

2011-12-01

Owing to our increasing concerns on the environment, climate change, and limited natural resources, there has recently been considerable effort exerted to produce chemicals and materials from renewable biomass. Polymers we use everyday can also be produced either by direct fermentation or by polymerization of monomers that are produced by fermentation. Recent advances in metabolic engineering combined with systems biology and synthetic biology are allowing us to more systematically develop superior strains and bioprocesses for the efficient production of polymers and monomers. Here, we review recent trends in microbial production of building block chemicals that can be subsequently used for the synthesis of polymers. Also, recent successful cases of direct one-step production of polymers are reviewed. General strategies for the production of natural and unnatural platform chemicals are described together with representative examples. Copyright © 2011 Elsevier Ltd. All rights reserved.

Investigation on vascular cytotoxicity and extravascular transport of cationic polymer nanoparticles using perfusable 3D microvessel model.

PubMed

Ahn, Jungho; Cho, Chong-Su; Cho, Seong Woo; Kang, Joo H; Kim, Sung-Yon; Min, Dal-Hee; Song, Joon Myong; Park, Tae-Eun; Jeon, Noo Li

2018-05-25

Vascular networks are the first sites exposed to cationic polymer nanoparticles (NPs) administered intravenously, and thus function as a barrier for NPs reaching the target organ. While cationic polymer NPs have been intensively studied as non-viral delivery systems, their biological effects in human microvessels have been poorly investigated due to a lack of appropriate in vitro systems. Here, we employed a three-dimensional microvessel on a chip, which accurately models in vivo conditions. An open and perfused microvessel surrounded by pericytes was shown to reproduce the important features of living vasculature, including barrier function and biomarkers. Using this microvessel chip, we observed contraction of the microvascular lumen induced by perfused polyethylenimine (PEI)/DNA NPs. We demonstrated that the oxidative stress present when microvessels were exposed to PEI NPs led to rearrangement of microtubules resulting in microvessel contraction. Furthermore, the transcytotic behavior of PEI NPs was analyzed in the microvessel by monitoring the escape of PEI NPs from the microvascular lumen into the perivascular region, which was not possible in two-dimensional culture systems. With our new understanding of the different behaviors of cationic polymer NPs depending on their transcytotic route, we suggest that caveolae-mediated transcytosis is a powerful route for efficient extravascular transport. Microvascular networks are not only biological system constituting largest surface area in the body and but also first site exposed to nanoparticle in vivo. While cationic polymer NPs have been intensively studied as non-viral delivery systems, its biological effects in human microvessel have been poorly investigated due to lack of appropriate in vitro systems. Here, we microengineered an open and perfused 3D pericyte incorporated microvessel model which possesses same morphological characteristic of in vivo. Using the microengineered model, this study represents the

Implementation of an Associative Flow Rule Including Hydrostatic Stress Effects Into the High Strain Rate Deformation Analysis of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Roberts, Gary D.; Gilat, Amos

2003-01-01

A previously developed analytical formulation has been modified in order to more accurately account for the effects of hydrostatic stresses on the nonlinear, strain rate dependent deformation of polymer matrix composites. State variable constitutive equations originally developed for metals have been modified in order to model the nonlinear, strain rate dependent deformation of polymeric materials. To account for the effects of hydrostatic stresses, which are significant in polymers, the classical J2 plasticity theory definitions of effective stress and effective inelastic strain, along with the equations used to compute the components of the inelastic strain rate tensor, are appropriately modified. To verify the revised formulation, the shear and tensile deformation of two representative polymers are computed across a wide range of strain rates. Results computed using the developed constitutive equations correlate well with experimental data. The polymer constitutive equations are implemented within a strength of materials based micromechanics method to predict the nonlinear, strain rate dependent deformation of polymer matrix composites. The composite mechanics are verified by analyzing the deformation of a representative polymer matrix composite for several fiber orientation angles across a variety of strain rates. The computed values compare well to experimentally obtained results.

Unexpected power-law stress relaxation of entangled ring polymers

PubMed Central

KAPNISTOS, M.; LANG, M.; PYCKHOUT-HINTZEN, W.; RICHTER, D.; CHO, D.; CHANG, T.

2016-01-01

After many years of intense research, most aspects of the motion of entangled polymers have been understood. Long linear and branched polymers have a characteristic entanglement plateau and their stress relaxes by chain reptation or branch retraction, respectively. In both mechanisms, the presence of chain ends is essential. But how do entangled polymers without ends relax their stress? Using properly purified high-molar-mass ring polymers, we demonstrate that these materials exhibit self-similar dynamics, yielding a power-law stress relaxation. However, trace amounts of linear chains at a concentration almost two decades below their overlap cause an enhanced mechanical response. An entanglement plateau is recovered at higher concentrations of linear chains. These results constitute an important step towards solving an outstanding problem of polymer science and are useful for manipulating properties of materials ranging from DNA to polycarbonate. They also provide possible directions for tuning the rheology of entangled polymers. PMID:18953345

Pathways Involved in Sasang Constitution from Genome-Wide Analysis in a Korean Population

PubMed Central

Yu, Sung-Gon; Kim, Jong-Yeol; Song, Kwang Hoon

2012-01-01

Abstract Objective Sasang constitution (SC) medicine, a branch of Korean traditional medicine, classifies the individual into one of four constitutional types (Taeum, TE; Soeum, SE; Soyang, SY; and Taeyang, TY) based on physiologic characteristics. The authors of the current article recently reported individual genetic elements associated with SC types via genome-wide association (GWA) analysis. However, to understand the biologic mechanisms underlying constitution, a comprehensive approach that combines individual genetic effects was applied. Design Genotypes of 1222 subjects of defined constitution types were measured for 341,998 genetic loci across the entire genome. The biologic pathways associated with SC types were identified via GWA analysis using three different algorithms—namely, the Z-static method, a restandardized gene set assay, and a gene set enrichment assay. Results Distinct pathways were associated (p<0.05) with each constitution type. The TE type was significantly associated with cytoskeleton-related pathways. The SE type was significantly associated with cardio- and amino-acid metabolism–related pathways. The SY type was associated with enriched melanoma-related pathways. TY subjects were excluded because of the small size of that sample. Among these functionally related pathways, core-node genes regulating multiple pathways were identified. TJP1, PTK2, and SRC were selected as core-nodes for TE; RHOA, and MAOA/MAOB for SE; and GNAO1 for SY (p<0.05), respectively. Conclusions The current authors systematically identified the biologic pathways and core-node genes associated with SC types from the GWA study; this information should provide insights regarding the molecular mechanisms inherent in constitutional pathophysiology. PMID:22889377

Analytical theory of polymer-network-mediated interaction between colloidal particles

PubMed Central

Di Michele, Lorenzo; Zaccone, Alessio; Eiser, Erika

2012-01-01

Nanostructured materials based on colloidal particles embedded in a polymer network are used in a variety of applications ranging from nanocomposite rubbers to organic-inorganic hybrid solar cells. Further, polymer-network-mediated colloidal interactions are highly relevant to biological studies whereby polymer hydrogels are commonly employed to probe the mechanical response of living cells, which can determine their biological function in physiological environments. The performance of nanomaterials crucially relies upon the spatial organization of the colloidal particles within the polymer network that depends, in turn, on the effective interactions between the particles in the medium. Existing models based on nonlocal equilibrium thermodynamics fail to clarify the nature of these interactions, precluding the way toward the rational design of polymer-composite materials. In this article, we present a predictive analytical theory of these interactions based on a coarse-grained model for polymer networks. We apply the theory to the case of colloids partially embedded in cross-linked polymer substrates and clarify the origin of attractive interactions recently observed experimentally. Monte Carlo simulation results that quantitatively confirm the theoretical predictions are also presented. PMID:22679289

Strain Rate Dependent Deformation and Strength Modeling of a Polymer Matrix Composite Utilizing a Micromechanics Approach. Degree awarded by Cincinnati Univ.

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

1999-01-01

Potential gas turbine applications will expose polymer matrix composites to very high strain rate loading conditions, requiring an ability to understand and predict the material behavior under extreme conditions. Specifically, analytical methods designed for these applications must have the capability of properly capturing the strain rate sensitivities and nonlinearities that are present in the material response. The Ramaswamy-Stouffer constitutive equations, originally developed to analyze the viscoplastic deformation of metals, have been modified to simulate the nonlinear deformation response of ductile, crystalline polymers. The constitutive model is characterized and correlated for two representative ductile polymers. Fiberite 977-2 and PEEK, and the computed results correlate well with experimental values. The polymer constitutive equations are implemented in a mechanics of materials based composite micromechanics model to predict the nonlinear, rate dependent deformation response of a composite ply. Uniform stress and uniform strain assumptions are applied to compute the effective stresses of a composite unit cell from the applied strains. The micromechanics equations are successfully verified for two polymer matrix composites. IM7/977-2 and AS4/PEEK. The ultimate strength of a composite ply is predicted with the Hashin failure criteria that were implemented in the composite micromechanics model. The failure stresses of the two composite material systems are accurately predicted for a variety of fiber orientations and strain rates. The composite deformation model is implemented in LS-DYNA, a commercially available transient dynamic explicit finite element code. The matrix constitutive equations are converted into an incremental form, and the model is implemented into LS-DYNA through the use of a user defined material subroutine. The deformation response of a bulk polymer and a polymer matrix composite are predicted by finite element analyses. The results

Incorporation of Mean Stress Effects into the Micromechanical Analysis of the High Strain Rate Response of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Roberts, Gary D.; Gilat, Amos

2002-01-01

The results presented here are part of an ongoing research program, to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to high strain rate impact loads. A micromechanics approach is employed in this work, in which state variable constitutive equations originally developed for metals have been modified to model the deformation of the polymer matrix, and a strength of materials based micromechanics method is used to predict the effective response of the composite. In the analysis of the inelastic deformation of the polymer matrix, the definitions of the effective stress and effective inelastic strain have been modified in order to account for the effect of hydrostatic stresses, which are significant in polymers. Two representative polymers, a toughened epoxy and a brittle epoxy, are characterized through the use of data from tensile and shear tests across a variety of strain rates. Results computed by using the developed constitutive equations correlate well with data generated via experiments. The procedure used to incorporate the constitutive equations within a micromechanics method is presented, and sample calculations of the deformation response of a composite for various fiber orientations and strain rates are discussed.

Polymer physics experiments with single DNA molecules

NASA Astrophysics Data System (ADS)

Smith, Douglas E.

1999-11-01

Bacteriophage DNA molecules were taken as a model flexible polymer chain for the experimental study of polymer dynamics at the single molecule level. Video fluorescence microscopy was used to directly observe the conformational dynamics of fluorescently labeled molecules, optical tweezers were used to manipulate individual molecules, and micro-fabricated flow cells were used to apply controlled hydrodynamic strain to molecules. These techniques constitute a powerful new experimental approach in the study of basic polymer physics questions. I have used these techniques to study the diffusion and relaxation of isolated and entangled polymer molecules and the hydrodynamic deformation of polymers in elongational and shear flows. These studies revealed a rich, and previously unobserved, ``molecular individualism'' in the dynamical behavior of single molecules. Individual measurements on ensembles of identical molecules allowed the average conformation to be determined as well as the underlying probability distributions for molecular conformation. Scaling laws, that predict the dependence of properties on chain length and concentration, were also tested. The basic assumptions of the reptation model were directly confirmed by visualizing the dynamics of entangled chains.

Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

NASA Astrophysics Data System (ADS)

Rosenthal-Kim, Emily Quinn

The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight

Influence of macromolecular architecture on necking in polymer extrusion film casting process

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

Pol, Harshawardhan; Banik, Sourya; Azad, Lal Busher

2015-05-22

Extrusion film casting (EFC) is an important polymer processing technique that is used to produce several thousand tons of polymer films/coatings on an industrial scale. In this research, we are interested in understanding quantitatively how macromolecular chain architecture (for example long chain branching (LCB) or molecular weight distribution (MWD or PDI)) influences the necking and thickness distribution of extrusion cast films. We have used different polymer resins of linear and branched molecular architecture to produce extrusion cast films under controlled experimental conditions. The necking profiles of the films were imaged and the velocity profiles during EFC were monitored using particlemore » tracking velocimetry (PTV) technique. Additionally, the temperature profiles were captured using an IR thermography and thickness profiles were calculated. The experimental results are compared with predictions of one-dimensional flow model of Silagy et al{sup 1} wherein the polymer resin rheology is modeled using molecular constitutive equations such as the Rolie-Poly (RP) and extended Pom Pom (XPP). We demonstrate that the 1-D flow model containing the molecular constitutive equations provides new insights into the role of macromolecular chain architecture on film necking.{sup 1}D. Silagy, Y. Demay, and J-F. Agassant, Polym. Eng. Sci., 36, 2614 (1996)« less

Optically responsive supramolecular polymer glasses

NASA Astrophysics Data System (ADS)

Balkenende, Diederik W. R.; Monnier, Christophe A.; Fiore, Gina L.; Weder, Christoph

2016-03-01

The reversible and dynamic nature of non-covalent interactions between the constituting building blocks renders many supramolecular polymers stimuli-responsive. This was previously exploited to create thermally and optically healable polymers, but it proved challenging to achieve high stiffness and good healability. Here we present a glass-forming supramolecular material that is based on a trifunctional low-molecular-weight monomer ((UPyU)3TMP). Carrying three ureido-4-pyrimidinone (UPy) groups, (UPyU)3TMP forms a dynamic supramolecular polymer network, whose properties are governed by its cross-linked architecture and the large content of the binding motif. This design promotes the formation of a disordered glass, which, in spite of the low molecular weight of the building block, displays typical polymeric behaviour. The material exhibits a high stiffness and offers excellent coating and adhesive properties. On account of reversible dissociation and the formation of a low-viscosity liquid upon irradiation with ultraviolet light, rapid optical healing as well as (de)bonding on demand is possible.

Polymers in the gut compress the colonic mucus hydrogel.

PubMed

Datta, Sujit S; Preska Steinberg, Asher; Ismagilov, Rustem F

2016-06-28

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host-microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer-mucus interactions can be described using a thermodynamic model based on Flory-Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice-whose microbiota degrade gut polymers-did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes.

Biologically active LIL proteins built with minimal chemical diversity

PubMed Central

Heim, Erin N.; Marston, Jez L.; Federman, Ross S.; Edwards, Anne P. B.; Karabadzhak, Alexander G.; Petti, Lisa M.; Engelman, Donald M.; DiMaio, Daniel

2015-01-01

We have constructed 26-amino acid transmembrane proteins that specifically transform cells but consist of only two different amino acids. Most proteins are long polymers of amino acids with 20 or more chemically distinct side-chains. The artificial transmembrane proteins reported here are the simplest known proteins with specific biological activity, consisting solely of an initiating methionine followed by specific sequences of leucines and isoleucines, two hydrophobic amino acids that differ only by the position of a methyl group. We designate these proteins containing leucine (L) and isoleucine (I) as LIL proteins. These proteins functionally interact with the transmembrane domain of the platelet-derived growth factor β-receptor and specifically activate the receptor to transform cells. Complete mutagenesis of these proteins identified individual amino acids required for activity, and a protein consisting solely of leucines, except for a single isoleucine at a particular position, transformed cells. These surprisingly simple proteins define the minimal chemical diversity sufficient to construct proteins with specific biological activity and change our view of what can constitute an active protein in a cellular context. PMID:26261320

Application of Eyring's thermal activation theory to constitutive equations for polymers

NASA Astrophysics Data System (ADS)

Zerilli, Frank J.; Armstrong, Ronald W.

2000-04-01

The application of a constitutive model based on the thermal activation theory of Eyring to the yield stress of polymethylmethacrylate at various temperatures and strain rates, as measured by Bauwens-Crowet, shows that the yield stress may reasonably well be described by a thermal activation equation in which the volume of activation is inversely proportional to the yield stress. It is found that, to obtain an accurate model, the dependence of the cold (T=0 K) yield stress on the shear modulus must be taken into account.

DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP.

PubMed

Aied, Ahmed; Zheng, Yu; Pandit, Abhay; Wang, Wenxin

2012-02-01

Cationic polymers with various structures have been widely investigated in the areas of medical diagnostics and molecular biology because of their unique binding properties and capability to interact with biological molecules in complex biological environments. In this work, we report the grafting of a linear cationic polymer from an atom transfer radical polymerization (ATRP) initiator bound to cellulose paper surface. We show successful binding of ATRP initiator onto cellulose paper and grafting of polymer chains from the immobilized initiator with ATRP. The cellulose paper grafted polymer was used in combination with PicoGreen (PG) to demonstrate detection of nucleic acids in the nanogram range in homogeneous solution and in a biological sample (serum). The results showed specific identification of hybridized DNA after addition of PG in both solutions.

Polymer translocation under time-dependent driving forces: resonant activation induced by attractive polymer-pore interactions.

PubMed

Ikonen, Timo; Shin, Jaeoh; Sung, Wokyung; Ala-Nissila, Tapio

2012-05-28

We study the driven translocation of polymers under time-dependent driving forces using N-particle Langevin dynamics simulations. We consider the force to be either sinusoidally oscillating in time or dichotomic noise with exponential correlation time, to mimic both plausible experimental setups and naturally occurring biological conditions. In addition, we consider both the case of purely repulsive polymer-pore interactions and the case with additional attractive polymer-pore interactions, typically occurring inside biological pores. We find that the nature of the interaction fundamentally affects the translocation dynamics. For the non-attractive pore, the translocation time crosses over to a fast translocation regime as the frequency of the driving force decreases. In the attractive pore case, because of a free energy well induced inside the pore, the translocation time can be a minimum at the optimal frequency of the force, the so-called resonant activation. In the latter case, we examine the effect of various physical parameters on the resonant activation, and explain our observations using simple theoretical arguments.

Polymer Brushes: Synthesis, Characterization, Applications

NASA Astrophysics Data System (ADS)

Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

2004-09-01

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Physics of the gut: How polymers dynamically structure the gut environment

NASA Astrophysics Data System (ADS)

Preska Steinberg, Asher; Datta, Sujit; Bogatyrev, Said; Ismagilov, Rustem

While the gut microbiome and biological regulation of the gut environment is being exhaustively studied by the microbiology community, little is known about the rich physics that governs the macro- and microstructure of the gut environment. The mammalian gut abounds in soft materials; ranging from soluble polymers (e.g. dietary fibers, therapeutic polymers and mucins) to colloidal matter (e.g. bacteria, viruses and nanoparticles carrying drugs). We have found experimentally that soluble polymers can dynamically re-structure the colonic mucus hydrogel by modulating its degree of swelling. We implemented a mean-field Flory-Huggins model to reveal that these polymer-mucus interactions can be captured using a simple, first principles thermodynamics model. In this model, the amount of deswelling increases with polymer concentration and size. We then used these physical principles to make predictions about how different polymer solutions affect the structure of mucus. Lastly, we explore applying this framework and similar physical principles to a variety of biological problems in the gut.

More Than Just a Polymer

NASA Technical Reports Server (NTRS)

2001-01-01

Triton atomic Oxygen Resistant polymers TOR(TM), were developed by Chelmsford, Massachusetts-based Triton Systems, Inc., through a Small Business Innovation Research (SBIR) contract from NASA's Langley Research Center. The new family of polymers comes from a Langley-developed polymer technology, which marks a new class of aerospace materials that resist the extreme effects of low Earth orbit (LEO). When applied to spacecraft surfaces, TOR polymers protect against erosion caused by the atomic oxygen and radiation present in space. Other polymers, such as Teflon(R) and Kapton(R), are subject to degradation from atomic oxygen and ultraviolet radiation, but TOR polymers use atomic oxygen to their advantage. A long-lasting protective barrier means major savings in the cost of spacecraft maintenance and the time spent performing repairs. While the obvious application of this material lies with the aerospace industry, an underlying benefit is found in the field of electronics. TOR polymers can be made electrically conductive, and then utilized in the creation of sensors that react to the presence of chemical and biological agents by exhibiting a detectable change in electrical conductivity. These sensors have applications in the defense, medical, and industrial sectors.

Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

NASA Astrophysics Data System (ADS)

Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

2015-03-01

Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

Localized Enzymatic Degradation of Polymers: Physics and Scaling Laws

NASA Astrophysics Data System (ADS)

Lalitha Sridhar, Shankar; Vernerey, Franck

2018-03-01

Biodegradable polymers are naturally abundant in living matter and have led to great advances in controlling environmental pollution due to synthetic polymer products, harnessing renewable energy from biofuels, and in the field of biomedicine. One of the most prevalent mechanisms of biodegradation involves enzyme-catalyzed depolymerization by biological agents. Despite numerous studies dedicated to understanding polymer biodegradation in different environments, a simple model that predicts the macroscopic behavior (mass and structural loss) in terms of microphysical processes (enzyme transport and reaction) is lacking. An interesting phenomenon occurs when an enzyme source (released by a biological agent) attacks a tight polymer mesh that restricts free diffusion. A fuzzy interface separating the intact and fully degraded polymer propagates away from the source and into the polymer as the enzymes diffuse and react in time. Understanding the characteristics of this interface will provide crucial insight into the biodegradation process and potential ways to precisely control it. In this work, we present a centrosymmetric model of biodegradation by characterizing the moving fuzzy interface in terms of its speed and width. The model predicts that the characteristics of this interface are governed by two time scales, namely the polymer degradation and enzyme transport times, which in turn depend on four main polymer and enzyme properties. A key finding of this work is simple scaling laws that can be used to guide biodegradation of polymers in different applications.

General Multimechanism Reversible-Irreversible Time-Dependent Constitutive Deformation Model Being Developed

NASA Technical Reports Server (NTRS)

Saleeb, A. F.; Arnold, Steven M.

2001-01-01

Since most advanced material systems (for example metallic-, polymer-, and ceramic-based systems) being currently researched and evaluated are for high-temperature airframe and propulsion system applications, the required constitutive models must account for both reversible and irreversible time-dependent deformations. Furthermore, since an integral part of continuum-based computational methodologies (be they microscale- or macroscale-based) is an accurate and computationally efficient constitutive model to describe the deformation behavior of the materials of interest, extensive research efforts have been made over the years on the phenomenological representations of constitutive material behavior in the inelastic analysis of structures. From a more recent and comprehensive perspective, the NASA Glenn Research Center in conjunction with the University of Akron has emphasized concurrently addressing three important and related areas: that is, 1) Mathematical formulation; 2) Algorithmic developments for updating (integrating) the external (e.g., stress) and internal state variables; 3) Parameter estimation for characterizing the model. This concurrent perspective to constitutive modeling has enabled the overcoming of the two major obstacles to fully utilizing these sophisticated time-dependent (hereditary) constitutive models in practical engineering analysis. These obstacles are: 1) Lack of efficient and robust integration algorithms; 2) Difficulties associated with characterizing the large number of required material parameters, particularly when many of these parameters lack obvious or direct physical interpretations.

Coating carbon nanotubes with a polystyrene-based polymer protects against pulmonary toxicity

PubMed Central

2011-01-01

Background carbon nanotubes (CNT) can have adverse effects on health. Therefore, minimizing the risk associated with CNT exposure is of crucial importance. The aim of this work was to evaluate if coating multi-walled CNT (MWCNT) with polymers could modify their toxicity, thus representing a useful strategy to decrease adverse health effects of CNT. We used industrially-produced MWCNT uncoated (NT1) or coated (50/50 wt%) with acid-based (NT2) or polystyrene-based (NT3) polymer, and exposed murine macrophages (RAW 264.7 cell line) or Balb/c mice by intratracheal administration. Biological experiments were performed both in vitro and in vivo, examining time- and dose-dependent effects of CNT, in terms of cytotoxicity, expression of genes and proteins related to oxidative stress, inflammation and tissue remodeling, cell and lung tissue morphology (optical and transmission electron microscopy), and bronchoalveolar lavage fluid content analysis. Results extensive physico-chemical characterization of MWCNT was performed, and showed, although similar dimensions for the 3 MWCNT, a much smaller specific surface area for NT2 and NT3 as compared to NT1 (54.1, 34 and 227.54 m2/g respectively), along with different surface characteristics. MWCNT-induced cytotoxicity, oxidative stress, and inflammation were increased by acid-based and decreased by polystyrene-based polymer coating both in vitro in murine macrophages and in vivo in lung of mice monitored for 6 months. Conclusions these results demonstrate that coating CNT with polymers, without affecting their intrinsic structure, may constitute a useful strategy for decreasing CNT toxicity, and may hold promise for improving occupational safety and that of general the user. PMID:21255417

Coating carbon nanotubes with a polystyrene-based polymer protects against pulmonary toxicity.

PubMed

Tabet, Lyes; Bussy, Cyrill; Setyan, Ari; Simon-Deckers, Angélique; Rossi, Michel J; Boczkowski, Jorge; Lanone, Sophie

2011-01-21

carbon nanotubes (CNT) can have adverse effects on health. Therefore, minimizing the risk associated with CNT exposure is of crucial importance. The aim of this work was to evaluate if coating multi-walled CNT (MWCNT) with polymers could modify their toxicity, thus representing a useful strategy to decrease adverse health effects of CNT. We used industrially-produced MWCNT uncoated (NT1) or coated (50/50 wt%) with acid-based (NT2) or polystyrene-based (NT3) polymer, and exposed murine macrophages (RAW 264.7 cell line) or Balb/c mice by intratracheal administration. Biological experiments were performed both in vitro and in vivo, examining time- and dose-dependent effects of CNT, in terms of cytotoxicity, expression of genes and proteins related to oxidative stress, inflammation and tissue remodeling, cell and lung tissue morphology (optical and transmission electron microscopy), and bronchoalveolar lavage fluid content analysis. extensive physico-chemical characterization of MWCNT was performed, and showed, although similar dimensions for the 3 MWCNT, a much smaller specific surface area for NT2 and NT3 as compared to NT1 (54.1, 34 and 227.54 m(2)/g respectively), along with different surface characteristics. MWCNT-induced cytotoxicity, oxidative stress, and inflammation were increased by acid-based and decreased by polystyrene-based polymer coating both in vitro in murine macrophages and in vivo in lung of mice monitored for 6 months. these results demonstrate that coating CNT with polymers, without affecting their intrinsic structure, may constitute a useful strategy for decreasing CNT toxicity, and may hold promise for improving occupational safety and that of general the user.

Near-infrared (NIR) emitting conjugated polymers for biomedical applications (Presentation Recording)

NASA Astrophysics Data System (ADS)

Repenko, Tatjana; Kuehne, Alexander J. C.

2015-10-01

Fluorescent biomedical markers of today such as dye-infiltrated colloids, microgels and quantum dots suffer from fast bleaching, lack surface functionality (for targets or pharmaceutical agents) and potentially leach heavy metals in case of quantum dots (e.g. Cd). By contrast, conjugated polymer particles are non-cytotoxic, exhibit reduced bleaching, as the entire particle consists of fluorophore, they are hydrophobic and show high quantum yields. Consequently, conjugated polymer particles represent ideal materials for biological applications and imaging. However currently, conjugated polymer particles for biomedical imaging usually lack near-infrared (NIR) emission and are polydisperse. Fluorescent agents with emission in the NIR spectrum are interesting for biomedical applications due to their low photo-damage towards biological species and the ability of NIR radiation to penetrate deep into biological tissue.. I will present the development and synthesis of new conjugated polymers particles with fluorescence in the NIR spectral region for bio-imaging and clinical diagnosis. The particle synthesis proceeds in a one-step Pd or Ni-catalyzed dispersion polymerization of functional NIR emitters. The resulting monodisperse conjugated polymer particles are obtained as a dispersion in a non-hazardous solvent. Different sizes in the sub-micrometer range with a narrow size distribution can be produced. Furthermore biological recognition motifs can be easily attached to the conjugated polymers via thiol-yne click-chemistry providing specific tumor targeting without quenching of the fluorescence. References [1] Kuehne AJC, Gather MC, Sprakel J., Nature Commun. 2012, 3, 1088. [2] Repenko T, Fokong S, De Laporte L, Go D, Kiessling F, Lammers T, Kuehne AJC.,Chem Commun 2015, accepted.

Conjugated Polymers Atypically Prepared in Water

PubMed Central

Invernale, Michael A.; Pendergraph, Samuel A.; Yavuz, Mustafa S.; Ombaba, Matthew; Sotzing, Gregory A.

2010-01-01

Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties. PMID:20959869

Nanotribology of charged polymer brushes

NASA Astrophysics Data System (ADS)

Klein, Jacob

Polymers at surfaces, whose modern understanding may be traced back to early work by Sam Edwards1, have become a paradigm for modification of surface properties, both as steric stabilizers and as remarkable boundary lubricants2. Charged polymer brushes are of particular interest, with both technological implications and especially biological relevance where most macromolecules are charged. In the context of biolubrication, relevant in areas from dry eye syndrome to osteoarthritis, charged polymer surface phases and their complexes with other macromolecules may play a central role. The hydration lubrication paradigm, where tenaciously-held yet fluid hydration shells surrounding ions or zwitterions serve as highly-efficient friction-reducing elements, has been invoked to understand the excellent lubrication provided both by ionized3 and by zwitterionic4 brushes. In this talk we describe recent advances in our understanding of the nanotribology of such charged brush systems. We consider interactions between charged end-grafted polymers, and how one may disentangle the steric from the electrostatic surface forces5. We examine the limits of lubrication by ionized brushes, both synthetic and of biological origins, and how highly-hydrated zwitterionic chains may provide extremely effective boundary lubrication6. Finally we describe how the lubrication of articular cartilage in the major joints, a tribosystem presenting some of the greatest challenges and opportunities, may be understood in terms of a supramolecular synergy between charged surface-attached polymers and zwitterionic groups7. Work supported by European Research Council (HydrationLube), Israel Science Foundation (ISF), Petroleum Research Fund of the American Chemical Society, ISF-NSF China Joint Program.

Polymers for 3D Printing and Customized Additive Manufacturing.

PubMed

Ligon, Samuel Clark; Liska, Robert; Stampfl, Jürgen; Gurr, Matthias; Mülhaupt, Rolf

2017-08-09

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems.

Polymers for 3D Printing and Customized Additive Manufacturing

PubMed Central

2017-01-01

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems. PMID:28756658

Polymer-mediated growth of crystals and mesocrystals.

PubMed

Cölfen, Helmut

2013-01-01

Polymers are important additives for the control of mineralization reactions in both biological and bioinspired mineralization. The reason is that they allow for a number of interactions with the growing crystals and even amorphous minerals. These can substantially influence the way the mineral grows on several levels. Already in the prenucleation phase, polymers can control the formation of prenucleation clusters and subsequently the nucleation event. Also, polymers can control whether the further crystallization follows a classical or nonclassical particle-mediated growth path. In this chapter, the main ways in which polymers can be used to control a crystallization reaction will be highlighted. In addition, polymers that are useful for this purpose and the experimental conditions suitable for directing a crystallization reaction into the desired direction through the use of polymers will be described. © 2013 Elsevier Inc. All rights reserved.

Sasang Constitutional Medicine as a Holistic Tailored Medicine

PubMed Central

Pham, Duong Duc

2009-01-01

Sasang constitutional medicine (SCM) is a unique traditional Korean therapeutic alternative form of medicine. Based on the Yin and Yang theory and on Confucianism, humans are classified into four constitutions. These differ in terms of (i) sensitivity to certain groups of herbs and medicines, (ii) equilibrium among internal organic functions, (iii) physical features and (iv) psychological characteristics. We propose that two main axes in the physiopathology of SCM (food intake/waste discharge and consuming/storing Qi and body fluids) are equivalent to the process of internal–external exchange and catabolism/anabolism in modern physiology, respectively. We then used this hypothesis to discuss the physiological and pathological principles of SCM. Constitution-based medicine is based on the theory that some medicinal herbs and remedies are only appropriate for certain constitutions and can cause adverse effects in others. The constitutional approach of SCM share the same vision as tailored medicine; an individualized therapy that can minimize the risk of adverse reaction while increasing the efficacy and an individualized self-regulation that can help prevent specific susceptible chronic disease and live healthily. There is still a long way to this goal for both SCM and tailored medicine, but we may benefit from systems approaches such as systems biology. We suggest that constitutional perspective of SCM and our hypothesis of two main processes may provide a novel insight for further studies. PMID:19745007

Sasang constitutional medicine as a holistic tailored medicine.

PubMed

Kim, Jong Yeol; Pham, Duong Duc

2009-09-01

Sasang constitutional medicine (SCM) is a unique traditional Korean therapeutic alternative form of medicine. Based on the Yin and Yang theory and on Confucianism, humans are classified into four constitutions. These differ in terms of (i) sensitivity to certain groups of herbs and medicines, (ii) equilibrium among internal organic functions, (iii) physical features and (iv) psychological characteristics. We propose that two main axes in the physiopathology of SCM (food intake/waste discharge and consuming/storing Qi and body fluids) are equivalent to the process of internal-external exchange and catabolism/anabolism in modern physiology, respectively. We then used this hypothesis to discuss the physiological and pathological principles of SCM. Constitution-based medicine is based on the theory that some medicinal herbs and remedies are only appropriate for certain constitutions and can cause adverse effects in others. The constitutional approach of SCM share the same vision as tailored medicine; an individualized therapy that can minimize the risk of adverse reaction while increasing the efficacy and an individualized self-regulation that can help prevent specific susceptible chronic disease and live healthily. There is still a long way to this goal for both SCM and tailored medicine, but we may benefit from systems approaches such as systems biology. We suggest that constitutional perspective of SCM and our hypothesis of two main processes may provide a novel insight for further studies.

Computational modeling of in vitro biological responses on polymethacrylate surfaces

PubMed Central

Ghosh, Jayeeta; Lewitus, Dan Y; Chandra, Prafulla; Joy, Abraham; Bushman, Jared; Knight, Doyle; Kohn, Joachim

2011-01-01

The objective of this research was to examine the capabilities of QSPR (Quantitative Structure Property Relationship) modeling to predict specific biological responses (fibrinogen adsorption, cell attachment and cell proliferation index) on thin films of different polymethacrylates. Using 33 commercially available monomers it is theoretically possible to construct a library of over 40,000 distinct polymer compositions. A subset of these polymers were synthesized and solvent cast surfaces were prepared in 96 well plates for the measurement of fibrinogen adsorption. NIH 3T3 cell attachment and proliferation index were measured on spin coated thin films of these polymers. Based on the experimental results of these polymers, separate models were built for homo-, co-, and terpolymers in the library with good correlation between experiment and predicted values. The ability to predict biological responses by simple QSPR models for large numbers of polymers has important implications in designing biomaterials for specific biological or medical applications. PMID:21779132

Composites comprising biologically-synthesized nanomaterials

DOEpatents

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

2013-04-30

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

Electroactive polymers for healthcare and biomedical applications

NASA Astrophysics Data System (ADS)

Bauer, Siegfried

2017-04-01

Electroactivity was noticed early in biological substances, including proteins, polynucleotides and enzymes, even piezoand pyroelectricity were found in wool, hair, wood, bone and tendon. Recently, ferroelectricity has been identified in a surprisingly large number of biologically relevant materials, including hydroxyapatite, aortic walls and elastin. Inspired by the variety of natural electroactive materials, a wealth of new elastomers and polymers were designed recently, including an all organic elastomer electret and self-healing dielectric elastomers. Let's further draw inspiration from nature and widen the utilization of electroactive polymers towards (mobile) healthcare and biomedical applications. Ferroelectrets, internally charged polymer foams with a strong piezoelectric thickness coefficient are employed in biomedical sensing, for example as blood pressure and pulse sensor, as vital signs monitor or for the detection of tonicclonic seizures. Piezo- and pyroelectric polymers are booming in printed electronics research. They provide electronic skin the ability to "feel" pressure and temperature changes, or to generate electrical energy from vibrations and motions, even from contractile and relaxation motions of the heart and lung. Dielectric elastomers are pioneered by StretchSense as wearable motion capture sensors, monitoring pressure, stretch, bend and shear, quantifying comfort in sports and healthcare. On the cellular level, electroactive polymer arrays are used to study mechanotransduction of individual cells. Ionic electroactive polymers show potential to be used in implantable electroactive biomedical devices. Already with the currently available science and technology, we are at the verge of witnessing the demonstration of truly complex bionic systems.

Biological and protein-binding studies of newly synthesized polymer-cobalt(III) complexes.

PubMed

Vignesh, G; Pradeep, I; Arunachalam, S; Vignesh, S; Arthur James, R; Arun, R; Premkumar, K

2016-03-01

The polymer-cobalt(III) complexes, [Co(bpy)(dien)BPEI]Cl3 · 4H2O (bpy = 2,2'-bipyridine, dien = diethylentriamine, BPEI = branched polyethyleneimine) were synthesized and characterized. The interaction of these complexes with human serum albumin (HSA) and bovine serum albumin (BSA) was investigated under physiological conditions using various physico-chemical techniques. The results reveal that the fluorescence quenching of serum albumins by polymer-cobalt(III) complexes took place through static quenching. The binding of these complexes changed the molecular conformation of the protein considerably. The polymer-cobalt(III) complex with x = 0.365 shows antimicrobial activity against several human pathogens. This complex also induces cytotoxicity against MCF-7 through apoptotic induction. However, further studies are needed to decipher the molecular mode of action of polymer-cobalt(III) complex and for its possible utilization in anticancer therapy. Copyright © 2015 John Wiley & Sons, Ltd.

Constitutive gene expression and specification of tissue identity in adult planarian biology

PubMed Central

Reddien, Peter W.

2011-01-01

Planarians are flatworms that constitutively maintain adult tissues through cell turnover and can regenerate entire organisms from tiny body fragments. In addition to requiring new cells (from neoblasts), these feats require mechanisms that specify tissue identity in the adult. Critical roles for Wnt and BMP signaling in regeneration and maintenance of the body axes have been uncovered, among other regulatory factors. Available data indicate that genes involved in positional identity regulation at key embryonic stages in other animals display persisting regionalized expression in adult planarians. These expression patterns suggest that a constitutively active gene expression map exists for maintenance of the planarian body. Planarians therefore present a fertile ground for identification of factors regulating regionalization of the metazoan body plan and for study of the attributes of these factors that can lead to maintenance and regeneration of adult tissues. PMID:21680047

Polymers as directing agents for motions of chemical and biological species

NASA Astrophysics Data System (ADS)

Tanyeri, Nihan Yonet

This thesis involves descriptions of solid surface modifications with various polymeric materials which were used as a guiding agent for motion of chemical and biological species. Quasi-two dimensional poly(oligoethylene glycol) acrylate polymer brush based molecular conduits have been designed with the goal of regulating and controlling the diffusive transport of molecular, e.g. organic dyes, and ionic species, e.g. AuCl4-, and Cu2+ ions, along predefined 2-D pathways. The transport of these chemical species has been examined by both fluorescence and dark field microscopy. The polymer brushes were formed through microcontact printing of an initiator, followed by surface-initiated Atom Transfer Radical Polymerization (SI-ATRP). SI-ATRP enables both 2-D patterning with a resolution of about 1 micrometer, and control over the resultant polymer brush thickness (which was varied from 10-100 nm). A hydrophilic poly(oligoethylene glycol) acrylate brushe was selected because of its potential to dissolve a wide range of hydrophilic species. The transport of fluorescent species can be directly followed. A non-lithographic fabrication method was developed for mufluidic devices used in the diffusion studies. Singular channel mufluidic device was utilized to study the directed organic dye diffusion. The AuCl4-, and Cu 2+ ion transport was studied by designing molecular devices with two mufluidic channels. We have demonstrated that the various species of interest diffuse much more rapidly along the predefined pathway than along the bare (polymer brush free) regions of the substrate, demonstrating that diffusive conduits for molecular transport can indeed be formed. The protein resistance of poly(N-isopropylacrylamide) (PNIPAM) brushes grafted from silicon wafers was investigated as a function of the chain molecular weight, grafting density, and temperature. Above the lower critical solution temperature (LCST) of 32°C, the collapse of the water swollen chains, determined by

Molecularly Imprinted Polymers: Present and Future Prospective

PubMed Central

Vasapollo, Giuseppe; Sole, Roberta Del; Mergola, Lucia; Lazzoi, Maria Rosaria; Scardino, Anna; Scorrano, Sonia; Mele, Giuseppe

2011-01-01

Molecular Imprinting Technology (MIT) is a technique to design artificial receptors with a predetermined selectivity and specificity for a given analyte, which can be used as ideal materials in various application fields. Molecularly Imprinted Polymers (MIPs), the polymeric matrices obtained using the imprinting technology, are robust molecular recognition elements able to mimic natural recognition entities, such as antibodies and biological receptors, useful to separate and analyze complicated samples such as biological fluids and environmental samples. The scope of this review is to provide a general overview on MIPs field discussing first general aspects in MIP preparation and then dealing with various application aspects. This review aims to outline the molecularly imprinted process and present a summary of principal application fields of molecularly imprinted polymers, focusing on chemical sensing, separation science, drug delivery and catalysis. Some significant aspects about preparation and application of the molecular imprinting polymers with examples taken from the recent literature will be discussed. Theoretical and experimental parameters for MIPs design in terms of the interaction between template and polymer functionalities will be considered and synthesis methods for the improvement of MIP recognition properties will also be presented. PMID:22016636

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Harris, J. M.

1985-01-01

Partition of biological cells in two phase aqueous polymer systems is recognized as a powerful separation technique which is limited by gravity. The synthesis of new, selective polymer ligand conjugates to be used in affinity partition separations is of interest. The two most commonly used polymers in two phase partitioning are dextran and polyethylene glycol. A thorough review of the chemistry of these polymers was begun, particularly in the area of protein attachment. Preliminary studies indicate the importance in affinity partitioning of minimizing gravity induced randomizing forces in the phase separation process. The PEG-protein conjugates that were prepared appear to be ideally suited for achieving high quality purifications in a microgravity environment. An interesting spin-off of this synthetic work was the observation of catalytic activity for certain of our polymer derivatives.

Research Programs Constituting U.S. Participation in the International Biological Program.

ERIC Educational Resources Information Center

National Academy of Sciences--National Research Council, Washington, DC. Div. of Biology and Agriculture.

The United States contribution to the International Biological Program, which aims to understand more clearly the interrelationships within ecosystems, is centered on multidisciplinary research programs investigating the biological basis of ecological productivity and human welfare. Integrated research programs have been established for the…

Effects of Adiabatic Heating on the High Strain Rate Deformation of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Sorini, Chris; Chattopadhyay, Aditi; Goldberg, Robert K.

2017-01-01

Polymer matrix composites (PMCs) are increasingly being used in aerospace structures that are expected to experience complex dynamic loading conditions throughout their lifetime. As such, a detailed understanding of the high strain rate behavior of the constituents, particularly the strain rate, temperature, and pressure dependent polymer matrix, is paramount. In this paper, preliminary efforts in modeling experimentally observed temperature rises due to plastic deformation in PMCs subjected to dynamic loading are presented. To this end, an existing isothermal viscoplastic polymer constitutive formulation is extended to model adiabatic conditions by incorporating temperature dependent elastic properties and modifying the components of the inelastic strain rate tensor to explicitly depend on temperature. It is demonstrated that the modified polymer constitutive model is capable of capturing strain rate and temperature dependent yield as well as thermal softening associated with the conversion of plastic work to heat at high rates of strain. The modified constitutive model is then embedded within a strength of materials based micromechanics framework to investigate the manifestation of matrix thermal softening, due to the conversion of plastic work to heat, on the high strain rate response of a T700Epon 862 (T700E862) unidirectional composite. Adiabatic model predictions for high strain rate composite longitudinal tensile, transverse tensile, and in-plane shear loading are presented. Results show a substantial deviation from isothermal conditions; significant thermal softening is observed for matrix dominated deformation modes (transverse tension and in-plane shear), highlighting the importance of accounting for the conversion of plastic work to heat in the polymer matrix in the high strain rate analysis of PMC structures.

Metal-containing and related polymers for biomedical applications.

PubMed

Yan, Yi; Zhang, Jiuyang; Ren, Lixia; Tang, Chuanbing

2016-10-07

A survey of the most recent progress in the biomedical applications of metal-containing polymers is given. Due to the unique optical, electrochemical, and magnetic properties, at least 30 different metal elements, most of them transition metals, are introduced into polymeric frameworks for interactions with biology-relevant substrates via various means. Inspired by the advance of metal-containing small molecular drugs and promoted by the great progress in polymer chemistry, metal-containing polymers have gained momentum during recent decades. According to their different applications, this review summarizes the following biomedical applications: (1) metal-containing polymers as drug delivery vehicles; (2) metal-containing polymeric drugs and biocides, including antimicrobial and antiviral agents, anticancer drugs, photodynamic therapy agents, radiotherapy agents and biocides; (3) metal-containing polymers as biosensors, and (4) metal-containing polymers in bioimaging.

Impact of HydroPolymers on the soil biological components in mediterranean drylands

NASA Astrophysics Data System (ADS)

Dvořáčková, Helena; Hueso González, Paloma; Záhora, Jaroslav; Mikajlo, Irina; Damián Ruiz Sinoga, Jose

2016-04-01

Soil degradation affects more than 52 million ha of land in counties of the European Union. This problem is particularly serious in Mediterranean areas, where the effects of anthropogenic activities (tillage on slopes, deforestation, and pasture production) add to problems caused by prolonged periods of drought and intense and irregular rainfall. Soil microbiota can be used as an indicator of the soil healthy in degraded areas. This is because soil microbiota participates in the cycle elements and in the organic matter decomposition. All this helps to the young plants establishment and in long term protect the soils against the erosion. During dry periods in the Mediterranean areas, the lack of water entering the soil matrix leads to a loss of soil microbiological activity and it turns into a lower soil production capabilities. Under these conditions, the aim of this study was to evaluate the positive effect on soil biological components produced by an hydro absorbent polymer (Terracottem). The aim of the experiment was to evaluate the impact assessment of an hydropolymer (Terracottem) on the soil biological components. An experimental flowerpot layout was established in June 2015 and 12 variants with different amount of Terracottem were applied as follow: i) 3.0 kg.m3 ; ii) 1.5 kg.m3 and; iii) 0 kg.m3. In all the variants were tested the further additives: a) 1% of glucose, b) 50 kg N.ha-1 of Mineral nitrogen, c) 1% of Glucose + 50 kg N.ha-1 of Mineral nitrogen d) control (no additive). According to natural conditions, humidity have been kept at 15% in all the variants. During four weeks, mineral nitrogen leaching and soil respiration have been measured in each flowerplot. Respiration has been quantified four times every time while moistening containers and alkaline soda lime has been used as a sorbent. The amount of CO2 increase has been measured with the sorbent. Leaching of mineral nitrogen has been quantified by ion exchange resins (IER). IER pouches have been

Phospholipid Polymer Biointerfaces for Lab-on-a-Chip Devices.

PubMed

Xu, Yan; Takai, Madoka; Ishihara, Kazuhiko

2010-06-01

This review summarizes recent achievements and progress in the development of various functional 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer biointerfaces for lab-on-a-chip devices and applications. As phospholipid polymers, MPC polymers can form cell-membrane-like surfaces by surface chemistry and physics and thereby provide biointerfaces capable of suppressing protein adsorption and many subsequent biological responses. In order to enable application to microfluidic devices, a number of MPC polymers with diverse functions have been specially designed and synthesized by incorporating functional units such as charge and active ester for generating the microfluidic flow and conjugating biomolecules, respectively. Furthermore, these polymers were incorporated with silane or hydrophobic moiety to construct stable interfaces on various substrate materials such as glass, quartz, poly(methyl methacrylate), and poly(dimethylsiloxane), via a silane-coupling reaction or hydrophobic interactions. The basic interfacial properties of these interfaces have been characterized from multiple aspects of chemistry, physics, and biology, and the suppression of nonspecific bioadsorption and control of microfluidic flow have been successfully achieved using these biointerfaces on a chip. Further, many chip-based biomedical applications such as immunoassays and DNA separation have been accomplished by integrating these biointerfaces on a chip. Therefore, functional phospholipid polymer interfaces are promising and useful for application to lab-on-a-chip devices in biomedicine.

Polymer scaffold degradation control via chemical control

DOEpatents

Hedberg-Dirk, Elizabeth L.; Dirk, Shawn; Cicotte, Kirsten

2016-01-05

A variety of polymers and copolymers suitable for use as biologically compatible constructs and, as a non-limiting specific example, in the formation of degradable tissue scaffolds as well methods for synthesizing these polymers and copolymers are described. The polymers and copolymers have degradation rates that are substantially faster than those of previously described polymers suitable for the same uses. Copolymers having a synthesis route which enables one to fine tune the degradation rate by selecting the specific stoichiometry of the monomers in the resulting copolymer are also described. The disclosure also provides a novel synthesis route for maleoyl chloride which yields monomers suitable for use in the copolymer synthesis methods described herein.

Conducting polymer actuators: From basic concepts to proprioceptive systems

NASA Astrophysics Data System (ADS)

Martinez Gil, Jose Gabriel

Designers and engineers have been dreaming for decades of motors sensing, by themselves, working and surrounding conditions, as biological muscles do originating proprioception. Here bilayer full polymeric artificial muscles were checked up to very high cathodic potential limits (-2.5 V) in aqueous solution by cyclic voltammetry. The electrochemical driven exchange of ions from the conducting polymer film, and the concomitant Faradaic bending movement of the muscle, takes place in the full studied potential range. The presence of trapped counterion after deep reduction was corroborated by EDX determinations giving quite high electronic conductivity to the device. The large bending movement was used as a tool to quantify the amount of water exchanged per reaction unit (exchanged electron or ion). The potential evolutions of self-supported films of conducting polymers or conducting polymers (polypyrrole, polyaniline) coating different microfibers, during its oxidation/reduction senses working mechanical, thermal, chemical or electrical variables. The evolution of the muscle potential from electrochemical artificial muscles based on electroactive materials such as intrinsically conducting polymers and driven by constant currents senses, while working, any variation of the mechanical (trailed mass, obstacles, pressure, strain or stress), thermal or chemical conditions of work. One physically uniform artificial muscle includes one electrochemical motor and several sensors working simultaneously under the same driving reaction. Actuating (current and charge) and sensing (potential and energy) magnitudes are present, simultaneously, in the only two connecting wires and can be read by the computer at any time. From basic polymeric, mechanical and electrochemical principles a physicochemical equation describing artificial proprioception has been developed. It includes and describes, simultaneously, the evolution of the muscle potential during actuation as a function of the

Fetal pain, abortion, viability, and the Constitution.

PubMed

Cohen, I Glenn; Sayeed, Sadath

2011-01-01

In early 2010, the Nebraska state legislature passed a new abortion restricting law asserting a new, compelling state interest in preventing fetal pain. In this article, we review existing constitutional abortion doctrine and note difficulties presented by persistent legal attention to a socially derived viability construct. We then offer a substantive biological, ethical, and legal critique of the new fetal pain rationale. © 2011 American Society of Law, Medicine & Ethics, Inc.

Polymer Composites Corrosive Degradation: A Computational Simulation

NASA Technical Reports Server (NTRS)

Chamis, Christos C.; Minnetyan, Levon

2007-01-01

A computational simulation of polymer composites corrosive durability is presented. The corrosive environment is assumed to manage the polymer composite degradation on a ply-by-ply basis. The degradation is correlated with a measured pH factor and is represented by voids, temperature and moisture which vary parabolically for voids and linearly for temperature and moisture through the laminate thickness. The simulation is performed by a computational composite mechanics computer code which includes micro, macro, combined stress failure and laminate theories. This accounts for starting the simulation from constitutive material properties and up to the laminate scale which exposes the laminate to the corrosive environment. Results obtained for one laminate indicate that the ply-by-ply degradation degrades the laminate to the last one or the last several plies. Results also demonstrate that the simulation is applicable to other polymer composite systems as well.

Nature's Mechanisms for Tough, Self-healing Polymers and Polymer Adhesives

NASA Astrophysics Data System (ADS)

Hansma, Paul

2007-03-01

Spider silk^2 and the natural polymer adhesives in abalone shells^3 and bone^4,5 can give us insights into nature's mechanisms for tough, self-healing polymers and polymer adhesives. The natural polymer adhesives in biomaterials have been optimized by evolution. An optimized polymer adhesive has five characteristics. 1) It holds together the strong elements of the composite. 2) It yields just before the strong elements would otherwise break. 3) It dissipates large amounts of energy as it yields. 4) It self heals after it yields. 5) It takes just a few percent by weight. Both natural polymer adhesives and silk rely on sacrificial bonds and hidden length for toughness and self-healing.^6 A relatively large energy, of order 100eV, is required to stretch a polymer molecule after a weak bond, a sacrificial bond, breaks and liberates hidden length, which was previously hidden, typically in a loop or folded domain, from whatever was stretching the polymer. The bond is called sacrificial if it breaks at forces well below the forces that could otherwise break the polymer backbone, typically greater than 1nN. In many biological cases, the breaking of sacrificial bonds has been found to be reversible, thereby also providing a ``self-healing'' property to the material.^2-4 Individual polymer adhesive molecules based on sacrificial bonds and hidden length can supply forces of order 300pN over distances of 100s of nanometers. Model calculations show that a few percent by weight of adhesives based on these principles could be optimized adhesives for high performance composite materials including nanotube and graphene sheet composites. ^2N. Becker, E. Oroudjev, S. Mutz et al., Nature Materials 2 (4), 278 (2003). ^3B. L. Smith, T. E. Schaffer, M. Viani et al., Nature 399 (6738), 761 (1999). ^4J. B. Thompson, J. H. Kindt, B. Drake et al., Nature 414 (6865), 773 (2001). ^5G. E. Fantner, T. Hassenkam, J. H. Kindt et al., Nature Materials 4, 612 (2005). ^6G. E. Fantner, E. Oroudjev, G

[Biogeography: geography or biology?].

PubMed

Kafanov, A I

2009-01-01

General biogeography is an interdisciplinary science, which combines geographic and biological aspects constituting two distinct research fields: biological geography and geographic biology. These fields differ in the nature of their objects of study, employ different methods and represent Earth sciences and biological sciences, respectively. It is suggested therefore that the classification codes for research fields and the state professional education standard should be revised.

From Biological Cilia to Artificial Flow Sensors: Biomimetic Soft Polymer Nanosensors with High Sensing Performance

NASA Astrophysics Data System (ADS)

Asadnia, Mohsen; Kottapalli, Ajay Giri Prakash; Karavitaki, K. Domenica; Warkiani, Majid Ebrahimi; Miao, Jianmin; Corey, David P.; Triantafyllou, Michael

2016-09-01

We report the development of a new class of miniature all-polymer flow sensors that closely mimic the intricate morphology of the mechanosensory ciliary bundles in biological hair cells. An artificial ciliary bundle is achieved by fabricating bundled polydimethylsiloxane (PDMS) micro-pillars with graded heights and electrospinning polyvinylidenefluoride (PVDF) piezoelectric nanofiber tip links. The piezoelectric nature of a single nanofiber tip link is confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Rheology and nanoindentation experiments are used to ensure that the viscous properties of the hyaluronic acid (HA)-based hydrogel are close to the biological cupula. A dome-shaped HA hydrogel cupula that encapsulates the artificial hair cell bundle is formed through precision drop-casting and swelling processes. Fluid drag force actuates the hydrogel cupula and deflects the micro-pillar bundle, stretching the nanofibers and generating electric charges. Functioning with principles analogous to the hair bundles, the sensors achieve a sensitivity and threshold detection limit of 300 mV/(m/s) and 8 μm/s, respectively. These self-powered, sensitive, flexible, biocompatibale and miniaturized sensors can find extensive applications in navigation and maneuvering of underwater robots, artificial hearing systems, biomedical and microfluidic devices.

From Biological Cilia to Artificial Flow Sensors: Biomimetic Soft Polymer Nanosensors with High Sensing Performance.

PubMed

Asadnia, Mohsen; Kottapalli, Ajay Giri Prakash; Karavitaki, K Domenica; Warkiani, Majid Ebrahimi; Miao, Jianmin; Corey, David P; Triantafyllou, Michael

2016-09-13

We report the development of a new class of miniature all-polymer flow sensors that closely mimic the intricate morphology of the mechanosensory ciliary bundles in biological hair cells. An artificial ciliary bundle is achieved by fabricating bundled polydimethylsiloxane (PDMS) micro-pillars with graded heights and electrospinning polyvinylidenefluoride (PVDF) piezoelectric nanofiber tip links. The piezoelectric nature of a single nanofiber tip link is confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Rheology and nanoindentation experiments are used to ensure that the viscous properties of the hyaluronic acid (HA)-based hydrogel are close to the biological cupula. A dome-shaped HA hydrogel cupula that encapsulates the artificial hair cell bundle is formed through precision drop-casting and swelling processes. Fluid drag force actuates the hydrogel cupula and deflects the micro-pillar bundle, stretching the nanofibers and generating electric charges. Functioning with principles analogous to the hair bundles, the sensors achieve a sensitivity and threshold detection limit of 300 mV/(m/s) and 8 μm/s, respectively. These self-powered, sensitive, flexible, biocompatibale and miniaturized sensors can find extensive applications in navigation and maneuvering of underwater robots, artificial hearing systems, biomedical and microfluidic devices.

From Biological Cilia to Artificial Flow Sensors: Biomimetic Soft Polymer Nanosensors with High Sensing Performance

PubMed Central

Asadnia, Mohsen; Kottapalli, Ajay Giri Prakash; Karavitaki, K. Domenica; Warkiani, Majid Ebrahimi; Miao, Jianmin; Corey, David P.; Triantafyllou, Michael

2016-01-01

We report the development of a new class of miniature all-polymer flow sensors that closely mimic the intricate morphology of the mechanosensory ciliary bundles in biological hair cells. An artificial ciliary bundle is achieved by fabricating bundled polydimethylsiloxane (PDMS) micro-pillars with graded heights and electrospinning polyvinylidenefluoride (PVDF) piezoelectric nanofiber tip links. The piezoelectric nature of a single nanofiber tip link is confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Rheology and nanoindentation experiments are used to ensure that the viscous properties of the hyaluronic acid (HA)-based hydrogel are close to the biological cupula. A dome-shaped HA hydrogel cupula that encapsulates the artificial hair cell bundle is formed through precision drop-casting and swelling processes. Fluid drag force actuates the hydrogel cupula and deflects the micro-pillar bundle, stretching the nanofibers and generating electric charges. Functioning with principles analogous to the hair bundles, the sensors achieve a sensitivity and threshold detection limit of 300 mV/(m/s) and 8 μm/s, respectively. These self-powered, sensitive, flexible, biocompatibale and miniaturized sensors can find extensive applications in navigation and maneuvering of underwater robots, artificial hearing systems, biomedical and microfluidic devices. PMID:27622466

Polymers in the gut compress the colonic mucus hydrogel

PubMed Central

Datta, Sujit S.; Preska Steinberg, Asher

2016-01-01

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host–microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer–mucus interactions can be described using a thermodynamic model based on Flory–Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice—whose microbiota degrade gut polymers—did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes. PMID:27303035

Quantum Mechanics predicts evolutionary biology.

PubMed

Torday, J S

2018-07-01

Nowhere are the shortcomings of conventional descriptive biology more evident than in the literature on Quantum Biology. In the on-going effort to apply Quantum Mechanics to evolutionary biology, merging Quantum Mechanics with the fundamentals of evolution as the First Principles of Physiology-namely negentropy, chemiosmosis and homeostasis-offers an authentic opportunity to understand how and why physics constitutes the basic principles of biology. Negentropy and chemiosmosis confer determinism on the unicell, whereas homeostasis constitutes Free Will because it offers a probabilistic range of physiologic set points. Similarly, on this basis several principles of Quantum Mechanics also apply directly to biology. The Pauli Exclusion Principle is both deterministic and probabilistic, whereas non-localization and the Heisenberg Uncertainty Principle are both probabilistic, providing the long-sought after ontologic and causal continuum from physics to biology and evolution as the holistic integration recognized as consciousness for the first time. Copyright © 2018 Elsevier Ltd. All rights reserved.

LS-DYNA Implementation of Polymer Matrix Composite Model Under High Strain Rate Impact

NASA Technical Reports Server (NTRS)

Zheng, Xia-Hua; Goldberg, Robert K.; Binienda, Wieslaw K.; Roberts, Gary D.

2003-01-01

A recently developed constitutive model is implemented into LS-DYNA as a user defined material model (UMAT) to characterize the nonlinear strain rate dependent behavior of polymers. By utilizing this model within a micromechanics technique based on a laminate analogy, an algorithm to analyze the strain rate dependent, nonlinear deformation of a fiber reinforced polymer matrix composite is then developed as a UMAT to simulate the response of these composites under high strain rate impact. The models are designed for shell elements in order to ensure computational efficiency. Experimental and numerical stress-strain curves are compared for two representative polymers and a representative polymer matrix composite, with the analytical model predicting the experimental response reasonably well.

Rapid Polymer Transport in a Single Nanometer-Scale Pore

NASA Astrophysics Data System (ADS)

Kasianowicz, J. J.

1998-03-01

Protein ion channels are nanometer-scale pores that control the transport of ions and polymers across cell membranes. We compared the ability of charged and nonelectrolyte linear polymers to partition into a single channel reconstituted into a planar lipid bilayer membrane. The entry of each polymer (e.g. monodisperse length single-stranded homopolymeric RNA1 or poly(ethylene glycol)2,3) into the pore caused characteristic transient decreases in the channel's ionic conductance. The ionic current blockades yield detailed information about the physical properties of the polymers and the pore. The biological and technological significance of the results will be discussed.

The influence of polymer topology on pharmacokinetics: differences between cyclic and linear PEGylated poly(acrylic acid) comb polymers.

PubMed

Chen, Bo; Jerger, Katherine; Fréchet, Jean M J; Szoka, Francis C

2009-12-16

Water-soluble polymers for the delivery of chemotherapeutic drugs passively target solid tumors as a consequence of reduced renal clearance and the enhanced permeation and retention (EPR) effect. Elimination of the polymers in the kidney occurs due to filtration through biological nanopores with a hydrodynamic diameter comparable to the polymer. Therefore we have investigated chemical features that may broadly be grouped as "molecular architecture" such as: molecular weight, chain flexibility, number of chain ends and branching, to learn how they impact polymer elimination. In this report we describe the synthesis of four pairs of similar molecular weight cyclic and linear polyacrylic acid polymers grafted with polyethylene glycol (23, 32, 65, 114 kDa) with low polydispersities using ATRP and "click" chemistry. The polymers were radiolabeled with (125)I and their pharmacokinetics and tissue distribution after intravenous injection were determined in normal and C26 adenocarcinoma tumored BALB/c mice. Cyclic polymers above the renal threshold of 30 kDa had a significantly longer elimination time (between 10 and 33% longer) than did the comparable linear polymer (for the 66 kDa cyclic polymer, t(1/2,beta)=35+/-2 h) and a greater area under the serum concentration versus time curve. This resulted in a greater tumor accumulation of the cyclic polymer than the linear polymer counterpart. Thus water-soluble cyclic comb polymers join a growing list of polymer topologies that show greatly extended circulation times compared to their linear counterparts and provide alternative polymer architecture for use as drug carriers.

The Influence of Polymer Topology on Pharmacokinetics: Differences Between Cyclic and Linear PEGylated Poly(acrylic Acid) Comb Polymers

PubMed Central

Chen, Bo; Jerger, Katherine; Fréchet, Jean M. J.; Szoka, Francis C.

2009-01-01

Water-soluble polymers for the delivery of chemotherapeutic drugs passively target solid tumors as a consequence of reduced renal clearance and the enhanced permeation and retention (EPR) effect. Elimination of the polymers in the kidney occurs due to filtration through biological nanopores with a hydrodynamic diameter comparable to the polymer. Therefore we have investigated chemical features that may broadly be grouped as “molecular architecture” such as: molecular weight, chain flexibility, number of chain ends and branching, to learn how they impact polymer elimination. In this report we describe the synthesis of four pairs of similar molecular weight cyclic and linear polyacrylic acid polymers grafted with polyethylene glycol (23, 32, 65, 114 kDa) with low polydispersities using ATRP and “click” chemistry. The polymers were radiolabeled with 125I and their pharmacokinetics and tissue distribution after intravenous injection were determined in normal and C26 adenocarcinoma tumored BALB/c mice. Cyclic polymers above the renal threshold of 30kDa had a significantly longer elimination time (between 10 to 33 % longer) than did the comparable linear polymer (for the 66 kDa cyclic polymer, t1/2, β= 35 ± 2 h) and a greater area under the serum concentration time curve. This resulted in a greater tumor accumulation of the cyclic polymer than the linear polymer counterpart. Thus water-soluble cyclic comb polymers join a growing list of polymer topologies that show greatly extended circulation times compared to their linear counterparts and provide alternative polymer architecture for use as drug carriers. PMID:19465070

Damage evolution in viscoelastic polymers

NASA Astrophysics Data System (ADS)

Clements, B. E.

2000-04-01

Constitutive relations are derived for viscoelastic polymers. These relations are applicable to polymers for temperatures above their glass transition temperature and strain rates ranging from quasistatic up to shock regimes. Linear viscoelasticity is assumed for small tensile deformations but nonlinear effects, arising from void growth, become important at larger strains. Our void growth model is based on a generalization of Eshelby's Green's function solution to the problem of an ellipsoidal void in an elastic material. We apply our analysis to study the mechanical properties of polyvinyl acetate under dynamic loading conditions. Void concentration and aspect ratio considerations are found to be important in general deformation events. Uniaxial tension tends to favor aspect ratio change, while non-spherical voids are observed to evolve into spherical ones as tensile strain approaches triaxiality. [Research supported by the USDOE under contract W-7405-ENG-36

Radiation-resistant composite for biological shield of personnel

NASA Astrophysics Data System (ADS)

Barabash, D. E.; Barabash, A. D.; Potapov, Yu B.; Panfilov, D. V.; Perekalskiy, O. E.

2017-10-01

This article presents the results of theoretical and practical justification for the use of polymer concrete based on nonisocyanate polyurethanes in biological shield structures. We have identified the impact of ratio: polymer - radiation-resistant filling compound on the durability and protection properties of polymer concrete. The article expounds regression dependence of the change of basic properties of the aforementioned polymer concrete on the absorbed radiation dose rate. Synergy effect in attenuation of radioactivity release in case of conjoint use of hydrogenous polymer base and radiation-resistant powder is also addressed herein.

Dynamic stiffness of chemically and physically ageing rubber vibration isolators in the audible frequency range. Part 1: constitutive equations

NASA Astrophysics Data System (ADS)

Kari, Leif

2017-09-01

The constitutive equations of chemically and physically ageing rubber in the audible frequency range are modelled as a function of ageing temperature, ageing time, actual temperature, time and frequency. The constitutive equations are derived by assuming nearly incompressible material with elastic spherical response and viscoelastic deviatoric response, using Mittag-Leffler relaxation function of fractional derivative type, the main advantage being the minimum material parameters needed to successfully fit experimental data over a broad frequency range. The material is furthermore assumed essentially entropic and thermo-mechanically simple while using a modified William-Landel-Ferry shift function to take into account temperature dependence and physical ageing, with fractional free volume evolution modelled by a nonlinear, fractional differential equation with relaxation time identical to that of the stress response and related to the fractional free volume by Doolittle equation. Physical ageing is a reversible ageing process, including trapping and freeing of polymer chain ends, polymer chain reorganizations and free volume changes. In contrast, chemical ageing is an irreversible process, mainly attributed to oxygen reaction with polymer network either damaging the network by scission or reformation of new polymer links. The chemical ageing is modelled by inner variables that are determined by inner fractional evolution equations. Finally, the model parameters are fitted to measurements results of natural rubber over a broad audible frequency range, and various parameter studies are performed including comparison with results obtained by ordinary, non-fractional ageing evolution differential equations.

Polymer-Based Protein Engineering: Synthesis and Characterization of Armored, High Graft Density Polymer-Protein Conjugates.

PubMed

Carmali, Sheiliza; Murata, Hironobu; Cummings, Chad; Matyjaszewski, Krzysztof; Russell, Alan J

2017-01-01

Atom transfer radical polymerization (ATRP) from the surface of a protein can generate remarkably dense polymer shells that serve as armor and rationally tune protein function. Using straightforward chemistry, it is possible to covalently couple or display multiple small molecule initiators onto a protein surface. The chemistry is fine-tuned to be sequence specific (if one desires a single targeted site) at controlled density. Once the initiator is anchored on the protein surface, ATRP is used to grow polymers on protein surface, in situ. The technique is so powerful that a single-protein polymer conjugate molecule can contain more than 90% polymer coating by weight. If desired, stimuli-responsive polymers can be "grown" from the initiated sites to prepare enzyme conjugates that respond to external triggers such as temperature or pH, while still maintaining enzyme activity and stability. Herein, we focus mainly on the synthesis of chymotrypsin-polymer conjugates. Control of the number of covalently coupled initiator sites by changing the stoichiometric ratio between enzyme and the initiator during the synthesis of protein-initiator complexes allowed fine-tuning of the grafting density. For example, very high grafting density chymotrypsin conjugates were prepared from protein-initiator complexes to grow the temperature-responsive polymers, poly(N-isopropylacrylamide), and poly[N,N'-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate]. Controlled growth of polymers from protein surfaces enables one to predictably manipulate enzyme kinetics and stability without the need for molecular biology-dependent mutagenesis. © 2017 Elsevier Inc. All rights reserved.

Polymer Brushes as Functional, Patterned Surfaces for Nanobiotechnology.

PubMed

Welch, M Elizabeth; Xu, Youyong; Chen, Hongjun; Smith, Norah; Tague, Michele E; Abruña, Héctor D; Baird, Barbara; Ober, Christopher K

2013-01-01

Polymer brushes have many desirable characteristics such as the ability to tether molecules to a substrate or change the properties of a surface. Patterning of polymer films has been an area of great interest due to the broad range of applications including bio-related and medicinal research. Consequently, we have investigated patterning techniques for polymer brushes which allow for two different functionalities on the same surface. This method has been applied to a biosensor device which requires both polymer brushes and a photosensitizer to be polymerized on a patterned gold substrate. Additionally, the nature of patterned polymer brushes as removable thin films was explored. An etching process has enabled us to lift off very thin membranes for further characterization with the potential of using them as Janus membranes for biological applications.

Kant on biological teleology: Towards a two-level interpretation.

PubMed

Quarfood, Marcel

2006-12-01

According to Kant's Critique of the power of judgment, teleological considerations are unavoidable for conceptualizing organisms. Does this mean that teleology is more than merely heuristic? Kant stresses the regulative status of teleological attributions, but sometimes he seems to treat teleology as a constitutive condition for biology. To clarify this issue, the concept of natural purpose and its role for biology are examined. I suggest that the concept serves an identificatory function: it singles out objects as natural purposes, whereby the special science of biology is constituted. This relative constitutivity of teleology is explicated by means of a distinction of levels: on the object level of biological science, teleology is taken as constitutive, though it is merely regulative on the philosophical meta level. This distinction also concerns the place of Aristotelian teleology in Kant: on the object level, the Aristotelian view is accepted, whereas on the meta level, an agnostic stance is taken concerning teleology.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion

Biologically inspired artificial compound eyes.

PubMed

Jeong, Ki-Hun; Kim, Jaeyoun; Lee, Luke P

2006-04-28

This work presents the fabrication of biologically inspired artificial compound eyes. The artificial ommatidium, like that of an insect's compound eyes, consists of a refractive polymer microlens, a light-guiding polymer cone, and a self-aligned waveguide to collect light with a small angular acceptance. The ommatidia are omnidirectionally arranged along a hemispherical polymer dome such that they provide a wide field of view similar to that of a natural compound eye. The spherical configuration of the microlenses is accomplished by reconfigurable microtemplating, that is, polymer replication using the deformed elastomer membrane with microlens patterns. The formation of polymer waveguides self-aligned with microlenses is also realized by a self-writing process in a photosensitive polymer resin. The angular acceptance is directly measured by three-dimensional optical sectioning with a confocal microscope, and the detailed optical characteristics are studied in comparison with a natural compound eye.

Nonlinearity and Strain-Rate Dependence in the Deformation Response of Polymer Matrix Composites Modeled

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

2000-01-01

There has been no accurate procedure for modeling the high-speed impact of composite materials, but such an analytical capability will be required in designing reliable lightweight engine-containment systems. The majority of the models in use assume a linear elastic material response that does not vary with strain rate. However, for containment systems, polymer matrix composites incorporating ductile polymers are likely to be used. For such a material, the deformation response is likely to be nonlinear and to vary with strain rate. An analytical model has been developed at the NASA Glenn Research Center at Lewis Field that incorporates both of these features. A set of constitutive equations that was originally developed to analyze the viscoplastic deformation of metals (Ramaswamy-Stouffer equations) was modified to simulate the nonlinear, rate-dependent deformation of polymers. Specifically, the effects of hydrostatic stresses on the inelastic response, which can be significant in polymers, were accounted for by a modification of the definition of the effective stress. The constitutive equations were then incorporated into a composite micromechanics model based on the mechanics of materials theory. This theory predicts the deformation response of a composite material from the properties and behavior of the individual constituents. In this manner, the nonlinear, rate-dependent deformation response of a polymer matrix composite can be predicted.

New constitutionalism and the social reproduction of caring institutions.

PubMed

Gill, Stephen; Bakker, Isabella

2006-01-01

This essay analyzes neo-liberal economic agreements and legal and political frameworks or what has been called the "new constitutionalism," a governance framework that empowers market forces to reshape economic and social development worldwide. The article highlights some consequences of new constitutionalism for caring institutions specifically, and for what feminists call social reproduction more generally: the biological reproduction of the species; the reproduction of labor power; and the reproduction of social institutions and processes associated with the creation and maintenance of communities. New constitutional governance frameworks fundamentally reshape conditions under which the care of human beings takes place. Caring institutions once governed by enabling professions geared to universal care are now determined increasingly by market values and private forces, and driven directly by the profit motive. This is one of the reasons why neo-liberalism is increasingly contested in both the North and the global South.

Dynamic nanoplatforms in biosensor and membrane constitutional systems.

PubMed

Mahon, Eugene; Aastrup, Teodor; Barboiu, Mihail

2012-01-01

Molecular recognition in biological systems occurs mainly at interfacial environments such as membrane surfaces, enzyme active sites, or the interior of the DNA double helix. At the cell membrane surface, carbohydrate-protein recognition principles apply to a range of specific non-covalent interactions including immune response, cell proliferation, adhesion and death, cell-cell interaction and communication. Protein-protein recognition meanwhile accounts for signalling processes and ion channel structure. In this chapter we aim to describe such constitutional dynamic interfaces for biosensing and membrane transport applications. Constitutionally adaptive interfaces may mimic the recognition capabilities intrinsic to natural recognition processes. We present some recent examples of 2D and 3D constructed sensors and membranes of this type and describe their sensing and transport capabilities.

Chemomechanical Polymers as Sensors and Actuators for Biological and Medicinal Applications

PubMed Central

Schneider, Hans-Jörg; Kato, Kazuaki; Strongin, Robert M.

2007-01-01

Changes in the chemical environment can trigger large motions in chemomechanical polymers. The unique feature of such intelligent materials, mostly in the form of hydrogels, is therefore, that they serve as sensors and actuators at the same time, and do not require any measuring devices, transducers or power supplies. Until recently the most often used of these materials responded to changes in pH. Chemists are now increasingly using supramolecular recognition sites in materials, which are covalently bound to the polymer backbone. This allows one to use a nearly unlimited variety of guest (or effector) compounds in the environment for a selective response by automatically triggered size changes. This is illustrated with non-covalent interactions of effectors comprising of metal ions, isomeric organic compounds, including enantiomers, nucleotides, aminoacids, and peptides. Two different effector molecules can induce motions as functions of their concentration, thus representing a logical AND gate. This concept is particularly fruitful with effector compounds such as peptides, which only trigger size changes if, e.g. copper ions are present in the surroundings. Another principle relies on the fast formation of covalent bonds between an effector and the chemomechanical polymer. The most promising application is the selective interaction of covalently fixed boronic acid residues with glucose, which renders itself not only for sensing, but eventually also for delivery of drugs such as insulin. The speed of the responses can significantly increase by increasing the surface to volume ratio of the polymer particles. Of particular interest is the sensitivity increase which can be reached by downsizing the particle volume. PMID:19606275

Materials comprising polydienes and hydrophilic polymers and related methods

DOEpatents

Mays, Jimmy W [Knoxville, TN; Deng, Suxiang [Knoxville, TN; Mauritz, Kenneth A [Hattiesburg, MS; Hassan, Mohammad K [Hattiesburg, MS; Gido, Samuel P [Hadley, MA

2011-11-22

Materials prepared from polydienes, such as poly(cyclohexadiene), and hydrophilic polymers, such as poly(alkylene oxide), are described. Methods of making the materials and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization are also provided. The materials can be crosslinked and sulfonated, and can include copolymers and polymer blends.

Quantitative fabrication of functional polymer surfaces

NASA Astrophysics Data System (ADS)

Rengifo, Hernan R.

areal density. The approach is based upon synthesis of an alkyne-end-functional diblock copolymer alpha-alkyne-o-Br-poly(tBA- b-MMA). The block copolymer self-assembles to form a bilayer on the substrate and directs alkyne groups to the surface. Azido-functionalized DNA is immobilized on alkyne functionalized substrates by a "click" reaction. The density of immobilized DNA can be quantitatively controlled by varying the parameters used for spin-coating the polymer film or by adjusting the hydrophilicity of the polymer surface underlying the reactive alkyne functional groups. In Chapter 5, Layer by layer (LbL) assembly techniques construct multilayer thin films by sequential deposition of monomolecular layers of organic molecules. One of the drawbacks associated with their use is that monomolecular layers are usually held together by relatively weak forces such as Van der Waals, electrostatic and hydrogen bonding interactions, and can therefore be lacking in mechanical integrity. In this chapter, it is demonstrated that heterobifunctional polymers, functionalized with one azide chain terminus and a protected alkyne group as the other chain terminus, constitute a powerful and versatile means for the covalent layer-by-layer (CLbL) assembly of thin polymer films. Each monomolecular polymer layer is covalently bound to both the preceding and following layers to produce a robust multilayer structure. Because the coupling chemistry used, "click" chemistry, is highly chemoselective, the layering process is virtually independent of the chemical nature of the polymer so that the constitution of each layer can be selected at will. Unlike other layer-by-layer deposition techniques, the layer thickness in CLbL is not equivalent to the diameter of the polymer chain, but is related to the polymer chain length and can be controlled by adjustment of either the polymer molecular weight or the areal density of surface alkyne groups.

Generalized theory of semiflexible polymers.

PubMed

Wiggins, Paul A; Nelson, Philip C

2006-03-01

DNA bending on length scales shorter than a persistence length plays an integral role in the translation of genetic information from DNA to cellular function. Quantitative experimental studies of these biological systems have led to a renewed interest in the polymer mechanics relevant for describing the conformational free energy of DNA bending induced by protein-DNA complexes. Recent experimental results from DNA cyclization studies have cast doubt on the applicability of the canonical semiflexible polymer theory, the wormlike chain (WLC) model, to DNA bending on biologically relevant length scales. This paper develops a theory of the chain statistics of a class of generalized semiflexible polymer models. Our focus is on the theoretical development of these models and the calculation of experimental observables. To illustrate our methods, we focus on a specific, illustrative model of DNA bending. We show that the WLC model generically describes the long-length-scale chain statistics of semiflexible polymers, as predicted by renormalization group arguments. In particular, we show that either the WLC or our present model adequately describes force-extension, solution scattering, and long-contour-length cyclization experiments, regardless of the details of DNA bend elasticity. In contrast, experiments sensitive to short-length-scale chain behavior can in principle reveal dramatic departures from the linear elastic behavior assumed in the WLC model. We demonstrate this explicitly by showing that our toy model can reproduce the anomalously large short-contour-length cyclization factors recently measured by Cloutier and Widom. Finally, we discuss the applicability of these models to DNA chain statistics in the context of future experiments.

Smart Polymers with Special Wettability.

PubMed

Chang, Baisong; Zhang, Bei; Sun, Taolei

2017-01-01

Surface wettability plays a key role in addressing issues ranging from basic life activities to our daily life, and thus being able to control it is an attractive goal. Learning from nature, both of its structure and function, brings us much inspiration in designing smart polymers to tackle this major challenge. Life functions particularly depend on biomolecular recognition-induced interfacial properties from the aqueous phase onto either "soft" cell and tissue or "hard" inorganic bone and tooth surfaces. The driving force is noncovalent weak interactions rather than strong covalent combinations. An overview is provided of the weak interactions that perform vital actions in mediating biological processes, which serve as a basis for elaborating multi-component polymers with special wettabilities. The role of smart polymers from molecular recognitions to macroscopic properties are highlighted. The rationale is that highly selective weak interactions are capable of creating a dynamic synergetic communication in the building components of polymers. Biomolecules could selectively induce conformational transitions of polymer chains, and then drive a switching of physicochemical properties, e.g., roughness, stiffness and compositions, which are an integrated embodiment of macroscopic surface wettabilities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional supramolecular polymers for biomedical applications.

PubMed

Dong, Ruijiao; Zhou, Yongfeng; Huang, Xiaohua; Zhu, Xinyuan; Lu, Yunfeng; Shen, Jian

2015-01-21

As a novel class of dynamic and non-covalent polymers, supramolecular polymers not only display specific structural and physicochemical properties, but also have the ability to undergo reversible changes of structure, shape, and function in response to diverse external stimuli, making them promising candidates for widespread applications ranging from academic research to industrial fields. By an elegant combination of dynamic/reversible structures with exceptional functions, functional supramolecular polymers are attracting increasing attention in various fields. In particular, functional supramolecular polymers offer several unique advantages, including inherent degradable polymer backbones, smart responsiveness to various biological stimuli, and the ease for the incorporation of multiple biofunctionalities (e.g., targeting and bioactivity), thereby showing great potential for a wide range of applications in the biomedical field. In this Review, the trends and representative achievements in the design and synthesis of supramolecular polymers with specific functions are summarized, as well as their wide-ranging biomedical applications such as drug delivery, gene transfection, protein delivery, bio-imaging and diagnosis, tissue engineering, and biomimetic chemistry. These achievements further inspire persistent efforts in an emerging interdisciplin-ary research area of supramolecular chemistry, polymer science, material science, biomedical engineering, and nanotechnology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modelling Polymer Deformation during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

Three-dimensional printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The fused deposition modelling technique involves melting a thermoplastic, followed by layer-by-layer extrusion to fabricate an object. The key to ensuring strength at the weld between layers is successful inter-diffusion. However, prior to welding, both the extrusion process and the cooling temperature profile can significantly deform the polymer micro-structure and, consequently, how well the polymers are able to ``re-entangle'' across the weld. In particular, polymer alignment in the flow can cause de-bonding of the layers and create defects. We have developed a simple model of the non-isothermal extrusion process to explore the effects that typical printing conditions and material rheology have on the conformation of a polymer melt. In particular, we incorporate both stretch and orientation using the Rolie-Poly constitutive equation to examine the melt structure as it flows through the nozzle, the subsequent alignment with the build plate and the resulting deformation due to the fixed nozzle height, which is typically less than the nozzle radius.

Molecular dynamics modeling the synthetic and biological polymers interactions pre-studied via docking

NASA Astrophysics Data System (ADS)

Tsvetkov, Vladimir B.; Serbin, Alexander V.

2014-06-01

In previous works we reported the design, synthesis and in vitro evaluations of synthetic anionic polymers modified by alicyclic pendant groups (hydrophobic anchors), as a novel class of inhibitors of the human immunodeficiency virus type 1 ( HIV-1) entry into human cells. Recently, these synthetic polymers interactions with key mediator of HIV-1 entry-fusion, the tri-helix core of the first heptad repeat regions [ HR1]3 of viral envelope protein gp41, were pre-studied via docking in terms of newly formulated algorithm for stepwise approximation from fragments of polymeric backbone and side-group models toward real polymeric chains. In the present article the docking results were verified under molecular dynamics ( MD) modeling. In contrast with limited capabilities of the docking, the MD allowed of using much more large models of the polymeric ligands, considering flexibility of both ligand and target simultaneously. Among the synthesized polymers the dinorbornen anchors containing alternating copolymers of maleic acid were selected as the most representative ligands (possessing the top anti-HIV activity in vitro in correlation with the highest binding energy in the docking). To verify the probability of binding of the polymers with the [HR1]3 in the sites defined via docking, various starting positions of polymer chains were tried. The MD simulations confirmed the main docking-predicted priority for binding sites, and possibilities for axial and belting modes of the ligands-target interactions. Some newly MD-discovered aspects of the ligand's backbone and anchor units dynamic cooperation in binding the viral target clarify mechanisms of the synthetic polymers anti-HIV activity and drug resistance prevention.

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.

Synthetic biology, inspired by synthetic chemistry.

PubMed

Malinova, V; Nallani, M; Meier, W P; Sinner, E K

2012-07-16

The topic synthetic biology appears still as an 'empty basket to be filled'. However, there is already plenty of claims and visions, as well as convincing research strategies about the theme of synthetic biology. First of all, synthetic biology seems to be about the engineering of biology - about bottom-up and top-down approaches, compromising complexity versus stability of artificial architectures, relevant in biology. Synthetic biology accounts for heterogeneous approaches towards minimal and even artificial life, the engineering of biochemical pathways on the organismic level, the modelling of molecular processes and finally, the combination of synthetic with nature-derived materials and architectural concepts, such as a cellular membrane. Still, synthetic biology is a discipline, which embraces interdisciplinary attempts in order to have a profound, scientific base to enable the re-design of nature and to compose architectures and processes with man-made matter. We like to give an overview about the developments in the field of synthetic biology, regarding polymer-based analogs of cellular membranes and what questions can be answered by applying synthetic polymer science towards the smallest unit in life, namely a cell. Copyright © 2012 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Thermal-Responsive Polymers for Enhancing Safety of Electrochemical Storage Devices.

PubMed

Yang, Hui; Leow, Wan Ru; Chen, Xiaodong

2018-03-01

Thermal runway constitutes the most pressing safety issue in lithium-ion batteries and supercapacitors of large-scale and high-power density due to risks of fire or explosion. However, traditional strategies for averting thermal runaway do not enable the charging-discharging rate to change according to temperature or the original performance to resume when the device is cooled to room temperature. To efficiently control thermal runaway, thermal-responsive polymers provide a feasible and reversible strategy due to their ability to sense and subsequently act according to a predetermined sequence when triggered by heat. Herein, recent research progress on the use of thermal-responsive polymers to enhance the thermal safety of electrochemical storage devices is reviewed. First, a brief discussion is provided on the methods of preventing thermal runaway in electrochemical storage devices. Subsequently, a short review is provided on the different types of thermal-responsive polymers that can efficiently avoid thermal runaway, such as phase change polymers, polymers with sol-gel transitions, and polymers with positive temperature coefficients. The results represent the important development of thermal-responsive polymers toward the prevention of thermal runaway in next-generation smart electrochemical storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of semicrystalline polymer morphologies by imaging-SANS

NASA Astrophysics Data System (ADS)

Radulescu, A.; Fetters, L. J.; Richter, D.

2012-02-01

Control and optimization of polymer properties require the global knowledge of the constitutive microstructures of polymer morphologies in various conditions. The microstructural features can be typically explored over a wide length scale by combining pinhole-, focusing- and ultra-small-angle neutron scattering (SANS) techniques. Though it proved to be a successful approach, this involves major efforts related to the use of various scattering instruments and large amount of samples and the need to ensure the same crystallization kinetics for the samples investigated at various facilities, in different sample cell geometries and at different time intervals. With the installation and commissioning of the MgF2 neutron lenses at the KWS-2 SANS diffractometer installed at the Heinz Maier-Leibnitz neutron source (FRMII reactor) in Garching, a wide Q-range, between 10-4Å-1 and 0.5Å-1, can be covered at a single instrument. This enables investigation of polymer microstructures over a length scale from lnm up to 1μm, while the overall polymer morphology can be further examined up to 100μm by optical microscopy (including crossed polarizers). The study of different semi-crystalline polypropylene-based polymers in solution is discussed and the new imaging-SANS approach allowing for an unambiguous and complete structural characterization of polymer morphologies is presented.

Hopping Diffusion of Nanoparticles in Polymer Matrices

PubMed Central

2016-01-01

We propose a hopping mechanism for diffusion of large nonsticky nanoparticles subjected to topological constraints in both unentangled and entangled polymer solids (networks and gels) and entangled polymer liquids (melts and solutions). Probe particles with size larger than the mesh size ax of unentangled polymer networks or tube diameter ae of entangled polymer liquids are trapped by the network or entanglement cells. At long time scales, however, these particles can diffuse by overcoming free energy barrier between neighboring confinement cells. The terminal particle diffusion coefficient dominated by this hopping diffusion is appreciable for particles with size moderately larger than the network mesh size ax or tube diameter ae. Much larger particles in polymer solids will be permanently trapped by local network cells, whereas they can still move in polymer liquids by waiting for entanglement cells to rearrange on the relaxation time scales of these liquids. Hopping diffusion in entangled polymer liquids and networks has a weaker dependence on particle size than that in unentangled networks as entanglements can slide along chains under polymer deformation. The proposed novel hopping model enables understanding the motion of large nanoparticles in polymeric nanocomposites and the transport of nano drug carriers in complex biological gels such as mucus. PMID:25691803

An elasto-viscoplastic interface model for investigating the constitutive behavior of nacre

NASA Astrophysics Data System (ADS)

Tang, H.; Barthelat, F.; Espinosa, H. D.

2007-07-01

In order to better understand the strengthening mechanism observed in nacre, we have developed an interface computational model to simulate the behavior of the organic present at the interface between aragonite tablets. In the model, the single polymer-chain behavior is characterized by the worm-like-chain (WLC) model, which is in turn incorporated into the eight-chain cell model developed by Arruda and Boyce [Arruda, E.M., Boyce, M.C., 1993a. A three-dimensional constitutive model for the large stretches, with application to polymeric glasses. Int. J. Solids Struct. 40, 389-412] to achieve a continuum interface constitutive description. The interface model is formulated within a finite-deformation framework. A fully implicit time-integration algorithm is used for solving the discretized governing equations. Finite element simulations were performed on a representative volume element (RVE) to investigate the tensile response of nacre. The staggered arrangement of tablets and interface waviness obtained experimentally by Barthelat et al. [Barthelat, F., Tang, H., Zavattieri, P.D., Li, C.-M., Espinosa, H.D., 2007. On the mechanics of mother-of-pearl: a key feature in the material hierarchical structure. J. Mech. Phys. Solids 55 (2), 306-337] was included in the RVE simulations. The simulations showed that both the rate-dependence of the tensile response and hysteresis loops during loading, unloading and reloading cycles were captured by the model. Through a parametric study, the effect of the polymer constitutive response during tablet-climbing and its relation to interface hardening was investigated. It is shown that stiffening of the organic material is not required to achieve the experimentally observed strain hardening of nacre during tension. In fact, when ratios of contour length/persistent length experimentally identified are employed in the simulations, the predicted stress-strain behavior exhibits a deformation hardening consistent with the one measured

A review of the fundamentals of polymer-modified asphalts: Asphalt/polymer interactions and principles of compatibility.

PubMed

Polacco, Giovanni; Filippi, Sara; Merusi, Filippo; Stastna, George

2015-10-01

the specification and techniques proposed to quantify the storage stability, state-of-the-art knowledge about the internal structure and morphology of polymer-modified asphalts is presented. Moreover, the chemical, physical, and processing solutions suggested in the scientific and patent literature to improve storage stability are extensively discussed, with particular attention to an emerging class of asphalt binders in which the technologies of polymer-modified asphalts and polymer nanocomposites are combined. These polymer-modified asphalt nanocomposites have been introduced less than ten years ago and still do not meet the requirements of industrial practice, but they may constitute a solution for both the performance and storage requirements. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, Characterization and Biological Studies of New Linear Thermally Stable Schiff Base Polymers with Flexible Spacers.

PubMed

Qureshi, Farah; Khuhawar, Muhammad Yar; Jahangir, Taj Muhammad; Channar, Abdul Hamid

2016-01-01

Five new linear Schiff base polymers having azomethine structures, ether linkages and extended aliphatic chain lengths with flexible spacers were synthesized by polycondensation of dialdehyde (monomer) with aliphatic and aromatic diamines. The formation yields of monomer and polymers were obtained within 75-92%. The polymers with flexible spacers of n-hexane were somewhat soluble in acetone, chloroform, THF, DMF and DMSO on heating. The monomer and polymers were characterized by melting point, elemental microanalysis, FT-IR, (1)HNMR, UV-Vis spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), fluorescence emission, scanning electron microscopy (SEM) and viscosities and thermodynamic parameters measurements of their dilute solutions. The studies supported formation of the monomer and polymers and on the basis of these studies their structures have been assigned. The synthesized polymers were tested for their antibacterial and antifungal activities.

Process For Cutting Polymers Electrolyte Multi-Layer Batteries And Batteries Obtained Thereby

DOEpatents

Gauthier, Michel; Lessard, Ginette; Dussault, Gaston; Rouillard, Roger; Simoneau, Martin; Miller, Alan Paul

2003-09-09

A stacking of battery laminate is prepared, each battery consisting of anode, polymer electrolyte, cathode films and possibly an insulating film, under conditions suitable to constitute a rigid monoblock assembly, in which the films are unitary with one another. The assembly obtained is thereafter cut in predetermined shape by using a mechanical device without macroscopic deformation of the films constituting the assembly and without inducing permanent short circuits. The battery which is obtained after cutting includes at least one end which appears as a uniform cut, the various films constituting the assembly having undergone no macroscopic deformation, the edges of the films of the anode including an electronically insulating passivation film.

Fracture simulation of elastomer blended polypropylene based on elastoviscoplastic constitutive equation with craze and tensile softening law

NASA Astrophysics Data System (ADS)

Mae, H.

2006-08-01

The strong strain-rate dependence, neck propagation and craze evolution characterize the large plastic deformation and fracture behavior of polymer. In the latest study, Kobayashi, Tomii and Shizawa suggested the elastoviscoplastic constitutive equation based on craze evolution and annihilation and then applied it to the plane strain issue of polymer. In the previous study, the author applied their suggested elastoviscoplastic constitutive equation with craze effect to the three dimensional shell and then showed that the load displacement history was in good agreement with the experimental result including only microscopic crack such as crazes. For the future industrial applications, the macroscopic crack has to be taken into account. Thus, the main objective of this study is to propose the tensile softening equation and then add it to the elastoviscoplastic constitutive equation with craze effect so that the load displacement history can be roughly simulated during the macroscopic crack propagation. The tested material in this study is the elastomer blended polypropylene used in the interior and exterior of automobiles. First, the material properties are obtained based on the tensile test results at wide range of strain rates: 10 - 4-102 (1/sec). Next, the compact tension test is conducted and then the tensile softening parameters are fixed. Then, the dart impact test is carried out in order to obtain the load displacement history and also observe the macroscopic crack propagation at high strain rate. Finally, the fracture behavior is simulated and then compared with the experimental results. It is shown that the predictions of the constitutive equation with the proposed tensile softening equation are in good agreement with the experimental results for the future industrial applications.

Isogeometric Kirchhoff-Love shell formulations for biological membranes

PubMed Central

Tepole, Adrián Buganza; Kabaria, Hardik; Bletzinger, Kai-Uwe; Kuhl, Ellen

2015-01-01

Computational modeling of thin biological membranes can aid the design of better medical devices. Remarkable biological membranes include skin, alveoli, blood vessels, and heart valves. Isogeometric analysis is ideally suited for biological membranes since it inherently satisfies the C1-requirement for Kirchhoff-Love kinematics. Yet, current isogeometric shell formulations are mainly focused on linear isotropic materials, while biological tissues are characterized by a nonlinear anisotropic stress-strain response. Here we present a thin shell formulation for thin biological membranes. We derive the equilibrium equations using curvilinear convective coordinates on NURBS tensor product surface patches. We linearize the weak form of the generic linear momentum balance without a particular choice of a constitutive law. We then incorporate the constitutive equations that have been designed specifically for collagenous tissues. We explore three common anisotropic material models: Mooney-Rivlin, May Newmann-Yin, and Gasser-Ogden-Holzapfel. Our work will allow scientists in biomechanics and mechanobiology to adopt the constitutive equations that have been developed for solid three-dimensional soft tissues within the framework of isogeometric thin shell analysis. PMID:26251556

Occurrence, degradation, and effect of polymer-based materials in the environment.

PubMed

Lambert, Scott; Sinclair, Chris; Boxall, Alistair

2014-01-01

There is now a plethora of polymer-based materials (PBMs) on the market, because of the increasing demand for cheaper consumable goods, and light-weight industrial materials. Each PBM constitutes a mixture of their representative polymer/sand their various chemical additives. The major polymer types are polyethylene, polypropylene,and polyvinyl chloride, with natural rubber and biodegradable polymers becoming increasingly more important. The most important additives are those that are biologically active, because to be effective such chemicals often have properties that make them resistant to photo-degradation and biodegradation. During their lifecycle,PBMs can be released into the environment form a variety of sources. The principal introduction routes being general littering, dumping of unwanted waste materials,migration from landfills and emission during refuse collection. Once in the environment,PBMs are primarily broken down by photo-degradation processes, but due to the complex chemical makeup of PBMs, receiving environments are potentially exposed to a mixture of macro-, meso-, and micro-size polymer fragments, leached additives, and subsequent degradation products. In environments where sunlight is absent (i.e., soils and the deep sea) degradation for most PBMs is minimal .The majority of literature to date that has addressed the environmental contamination or disposition of PBMs has focused on the marine environment. This is because the oceans are identified as the major sink for macro PBMs, where they are known to present a hazard to wildlife via entanglement and ingestion. The published literature has established the occurrence of microplastics in marine environment and beach sediments, but is inadequate as regards contamination of soils and freshwater sediments. The uptake of microplastics for a limited range of aquatic organisms has also been established, but there is a lack of information regarding soil organisms, and the long-term effects of

A Minimal Polymer Model Integrates an Inverted Nuclear Geometry with Conventional Hi-C Compartmentalization

NASA Astrophysics Data System (ADS)

Falk, Martin; Naumova, Natasha; Fudenberg, Geoffrey; Feodorova, Yana; Imakaev, Maxim; Dekker, Job; Solovei, Irina; Mirny, Leonid

The organization of interphase nuclei differs dramatically across cell types in a functionally-relevant fashion. A striking example is found in the rod photoreceptors of nocturnal mammals, where the conventional nuclear organization is inverted. In particular, in murine rods, constitutive heterochromatin is packed into a single chromocenter in the nuclear center, which is encircled by a shell of facultative heterochromatin and then by an outermost shell of euchromatin. Surprisingly, Hi-C maps of conventional and inverted nuclei display remarkably similar compartmentalization between heterochromatin and euchromatin. Here, we simulate a de novo polymer model that is capable of replicating both conventional and inverted geometries while preserving the patterns of compartmentalization as observed by Hi-C. In this model, chromatin is a polymer composed of three classes of monomers arranged in blocks representing constitutive heterochromatin, facultative heterochromatin, and euchromatin. Different classes of monomers have different levels of attraction to each other and to the nuclear lamina. Our results indicate that preferential interactions between facultative heterochromatin and constitutive heterochromatin provide a possible mechanism to explain nuclear inversion when association with the lamina is lost.

Large-eddy simulations of a forced homogeneous isotropic turbulence with polymer additives

NASA Astrophysics Data System (ADS)

Wang, Lu; Cai, Wei-Hua; Li, Feng-Chen

2014-03-01

Large-eddy simulations (LES) based on the temporal approximate deconvolution model were performed for a forced homogeneous isotropic turbulence (FHIT) with polymer additives at moderate Taylor Reynolds number. Finitely extensible nonlinear elastic in the Peterlin approximation model was adopted as the constitutive equation for the filtered conformation tensor of the polymer molecules. The LES results were verified through comparisons with the direct numerical simulation results. Using the LES database of the FHIT in the Newtonian fluid and the polymer solution flows, the polymer effects on some important parameters such as strain, vorticity, drag reduction, and so forth were studied. By extracting the vortex structures and exploring the flatness factor through a high-order correlation function of velocity derivative and wavelet analysis, it can be found that the small-scale vortex structures and small-scale intermittency in the FHIT are all inhibited due to the existence of the polymers. The extended self-similarity scaling law in the polymer solution flow shows no apparent difference from that in the Newtonian fluid flow at the currently simulated ranges of Reynolds and Weissenberg numbers.

A high brightness probe of polymer nanoparticles for biological imaging

NASA Astrophysics Data System (ADS)

Zhou, Sirong; Zhu, Jiarong; Li, Yaping; Feng, Liheng

2018-03-01

Conjugated polymer nanoparticles (CPNs) with high brightness in long wavelength region were prepared by the nano-precipitation method. Based on fluorescence resonance energy transfer (FRET) mechanism, the high brightness property of the CPNs was realized by four different emission polymers. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) displayed that the CPNs possessed a spherical structure and an average diameter of 75 nm. Analysis assays showed that the CPNs had excellent biocompatibility, good photostability and low cytotoxicity. The CPNs were bio-modified with a cell penetrating peptide (Tat, a targeted element) through covalent link. Based on the entire wave fluorescence emission, the functionalized CPNs1-4 can meet multichannel and high throughput assays in cell and organ imaging. The contribution of the work lies in not only providing a new way to obtain a high brightness imaging probe in long wavelength region, but also using targeted cell and organ imaging.

Augmenting Primary and Secondary Education with Polymer Science and Engineering

ERIC Educational Resources Information Center

Cersonsky, Rose K.; Foster, Leanna L.; Ahn, Taeyong; Hall, Ryan J.; van der Laan, Harry L.; Scott, Timothy F.

2017-01-01

Despite the prevalence of polymers in modern everyday life, there is little introduction to the topic in science education throughout primary or secondary schooling in the United States. Of the few states that do include polymer education, this is only found at the high school level, primarily in biology or chemistry. Over the past year, we have…

Current Trends in Sensors Based on Conducting Polymer Nanomaterials

PubMed Central

Yoon, Hyeonseok

2013-01-01

Conducting polymers represent an important class of functional organic materials for next-generation electronic and optical devices. Advances in nanotechnology allow for the fabrication of various conducting polymer nanomaterials through synthesis methods such as solid-phase template synthesis, molecular template synthesis, and template-free synthesis. Nanostructured conducting polymers featuring high surface area, small dimensions, and unique physical properties have been widely used to build various sensor devices. Many remarkable examples have been reported over the past decade. The enhanced sensitivity of conducting polymer nanomaterials toward various chemical/biological species and external stimuli has made them ideal candidates for incorporation into the design of sensors. However, the selectivity and stability still leave room for improvement. PMID:28348348

Advanced functional polymers for regenerative and therapeutic dentistry.

PubMed

Lai, W-F; Oka, K; Jung, H-S

2015-07-01

Use of ceramics and polymers continues to dominate clinical procedures in modern dentistry. Polymers have provided the basis for adhesives, tissue void fillers, and artificial replacements for whole teeth. They have been remarkably effective in the clinic at restoration of major dental functions after damage or loss of teeth. With the rapid development of polymer science, dental materials science has significantly lagged behind in harnessing these advanced polymer products. What they offer is new and unique properties superior to traditional polymers and crucially a range of properties that more closely match natural biomaterials. Therefore, we should pursue more vigorously the benefits of advanced polymers in dentistry. In this review, we highlight how the latest generation of advanced polymers will enhance the application of materials in the dental clinic using numerous promising examples. Polymers have a broad range of applications in modern dentistry. Some major applications are to construct frameworks that mimic the precise structure of tissues, to restore tooth organ function, and to deliver bioactive agents to influence cell behavior from the inside. The future of polymers in dentistry must include all these new enhancements to increase biological and clinical effectiveness beyond what can be achieved with traditional biomaterials. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Characterization of Nonlinear Rate Dependent Response of Shape Memory Polymers

NASA Technical Reports Server (NTRS)

Volk, Brent; Lagoudas, Dimitris C.; Chen, Yi-Chao; Whitley, Karen S.

2007-01-01

Shape Memory Polymers (SMPs) are a class of polymers, which can undergo deformation in a flexible state at elevated temperatures, and when cooled below the glass transition temperature, while retaining their deformed shape, will enter and remain in a rigid state. Upon heating above the glass transition temperature, the shape memory polymer will return to its original, unaltered shape. SMPs have been reported to recover strains of over 400%. It is important to understand the stress and strain recovery behavior of SMPs to better develop constitutive models which predict material behavior. Initial modeling efforts did not account for large deformations beyond 25% strain. However, a model under current development is capable of describing large deformations of the material. This model considers the coexisting active (rubber) and frozen (glass) phases of the polymer, as well as the transitions between the material phases. The constitutive equations at the continuum level are established with internal state variables to describe the microstructural changes associated with the phase transitions. For small deformations, the model reduces to a linear model that agrees with those reported in the literature. Thermomechanical characterization is necessary for the development, calibration, and validation of a constitutive model. The experimental data reported in this paper will assist in model development by providing a better understanding of the stress and strain recovery behavior of the material. This paper presents the testing techniques used to characterize the thermomechanical material properties of a shape memory polymer (SMP) and also presents the resulting data. An innovative visual-photographic apparatus, known as a Vision Image Correlation (VIC) system was used to measure the strain. The details of this technique will also be presented in this paper. A series of tensile tests were performed on specimens such that strain levels of 10, 25, 50, and 100% were applied to

Genome-Wide Association Analysis of Sasang Constitution in the Korean Population

PubMed Central

Kim, Bu-Yeo; Jin, Hee-Jeong

2012-01-01

Abstract Objectives Sasang constitutional medicine is a traditional Korean medicine in which an individual is classified into one of four types of constitution: Taeum (TE), Soeum (SE) Soyang (SY), and Taeyang (TY). These constitution types are determined with biologic and physiologic characteristics, so it has been assumed that genetic factors are associated with each constitution type. Identifying the genetic elements underlying each constitution is necessary for the elucidation of the molecular mechanism of Sasang constitutional medicine. Design A total of 341,998 genetic loci across the whole genome were genotyped for 1222 subjects of defined constitution type. The genetic loci associated with each constitution type were identified and the functional connectivity of genes within these loci was analyzed using statistical text mining. Results From the difference in allele frequencies between constitution types, significant genetic loci associated with each type were identified. Chromosomes 3q27.3 (rs10937331, p=2.71×10−6), 15q22.2 (rs7180547, p=1.58×10−6), and 14q22.3 (rs12431592, p=1.31×10−6) were most significantly associated with TE, SE, and SY constitution types, respectively. From the functional relationship analysis using all loci with a p-value≤10−4, genes associated with each constitution type were identified. Fifteen (15) genes, including GPM6A, SYT4, and GRIK1, were significantly associated with the TE constitution type (p<0.05); 12 genes, including DRGX and AKAP11, were significantly associated with the SE constitution type (p<0.05); and 17 genes, including ZFP42, CDH22, ALDH1A2, OTX2, and EN2, were significantly associated with the SY constitution type (p<0.05). Conclusions Genetic loci and genes associated with Sasang constitution types were systematically identified from a genome-wide association study using a large number of subjects. PMID:22394158

Active learning of constitutive relation from mesoscopic dynamics for macroscopic modeling of non-Newtonian flows

NASA Astrophysics Data System (ADS)

Zhao, Lifei; Li, Zhen; Caswell, Bruce; Ouyang, Jie; Karniadakis, George Em

2018-06-01

We simulate complex fluids by means of an on-the-fly coupling of the bulk rheology to the underlying microstructure dynamics. In particular, a continuum model of polymeric fluids is constructed without a pre-specified constitutive relation, but instead it is actively learned from mesoscopic simulations where the dynamics of polymer chains is explicitly computed. To couple the bulk rheology of polymeric fluids and the microscale dynamics of polymer chains, the continuum approach (based on the finite volume method) provides the transient flow field as inputs for the (mesoscopic) dissipative particle dynamics (DPD), and in turn DPD returns an effective constitutive relation to close the continuum equations. In this multiscale modeling procedure, we employ an active learning strategy based on Gaussian process regression (GPR) to minimize the number of expensive DPD simulations, where adaptively selected DPD simulations are performed only as necessary. Numerical experiments are carried out for flow past a circular cylinder of a non-Newtonian fluid, modeled at the mesoscopic level by bead-spring chains. The results show that only five DPD simulations are required to achieve an effective closure of the continuum equations at Reynolds number Re = 10. Furthermore, when Re is increased to 100, only one additional DPD simulation is required for constructing an extended GPR-informed model closure. Compared to traditional message-passing multiscale approaches, applying an active learning scheme to multiscale modeling of non-Newtonian fluids can significantly increase the computational efficiency. Although the method demonstrated here obtains only a local viscosity from the polymer dynamics, it can be extended to other multiscale models of complex fluids whose macro-rheology is unknown.

Cell-free biology: exploiting the interface between synthetic biology and synthetic chemistry

PubMed Central

Harris, D. Calvin; Jewett, Michael C.

2014-01-01

Just as synthetic organic chemistry once revolutionized the ability of chemists to build molecules (including those that did not exist in nature) following a basic set of design rules, cell-free synthetic biology is beginning to provide an improved toolbox and faster process for not only harnessing but also expanding the chemistry of life. At the interface between chemistry and biology, research in cell-free synthetic systems is proceeding in two different directions: using synthetic biology for synthetic chemistry and using synthetic chemistry to reprogram or mimic biology. In the coming years, the impact of advances inspired by these approaches will make possible the synthesis of non-biological polymers having new backbone compositions, new chemical properties, new structures, and new functions. PMID:22483202

The Juxtaposition of Ribose Hydroxyl Groups: The Root of Biological Catalysis and the RNA World?

NASA Astrophysics Data System (ADS)

Bernhardt, Harold S.

2015-06-01

We normally think of enzymes as being proteins; however, the RNA world hypothesis suggests that the earliest biological catalysts may have been composed of RNA. One of the oldest surviving RNA enzymes we are aware of is the peptidyl transferase centre (PTC) of the large ribosomal RNA, which joins amino acids together to form proteins. Recent evidence indicates that the enzymatic activity of the PTC is principally due to ribose 2 '-OHs. Many other reactions catalyzed by RNA and/or in which RNA is a substrate similarly utilize ribose 2 '-OHs, including phosphoryl transfer reactions that involve the cleavage and/or ligation of the ribose-phosphate backbone. It has recently been proposed by Yakhnin (2013) that phosphoryl transfer reactions were important in the prebiotic chemical evolution of RNA, by enabling macromolecules composed of polyols joined by phosphodiester linkages to undergo recombination reactions, with the reaction energy supplied by the phosphodiester bond itself. The almost unique juxtaposition of the ribose 2'-hydroxyl and 3'-oxygen in ribose-containing polymers such as RNA, which gives ribose the ability to catalyze such reactions, may have been an important factor in the selection of ribose as a component of the first biopolymer. In addition, the juxtaposition of hydroxyl groups in free ribose: (i) allows coordination of borate ions, which could have provided significant and preferential stabilization of ribose in a prebiotic environment; and (ii) enhances the rate of permeation by ribose into a variety of lipid membrane systems, possibly favouring its incorporation into early metabolic pathways and an ancestral ribose-phosphate polymer. Somewhat more speculatively, hydrogen bonds formed by juxtaposed ribose hydroxyl groups may have stabilized an ancestral ribose-phosphate polymer against degradation (Bernhardt and Sandwick 2014). I propose that the almost unique juxtaposition of ribose hydroxyl groups constitutes the root of both biological

The viscoelastic characterization of polymer materials exposed to the low-Earth orbit environment

NASA Technical Reports Server (NTRS)

Strganac, Thomas; Letton, Alan

1992-01-01

Recent accomplishments in our research efforts have included the successful measurement of the thermal mechanical properties of polymer materials exposed to the low-earth orbit environment. In particular, viscoelastic properties were recorded using the Rheometrics Solids Analyzer (RSA 2). Dynamic moduli (E', the storage component of the elastic modulus, and E'', the loss component of the elastic modulus) were recorded over three decades of frequency (0.1 to 100 rad/sec) for temperatures ranging from -150 to 150 C. Although this temperature range extends beyond the typical use range of the materials, measurements in this region are necessary in the development of complete viscoelastic constitutive models. The experimental results were used to provide the stress relaxation and creep compliance performance characteristics through viscoelastic correspondence principles. Our results quantify the differences between exposed and control polymer specimens. The characterization is specifically designed to elucidate a constitutive model that accurately predicts the change in behavior of these materials due to exposure. The constitutive model for viscoelastic behavior reflects the level of strain, the rate of strain, and the history of strain as well as the thermal history of the material.

Modular-based multiscale modeling on viscoelasticity of polymer nanocomposites

NASA Astrophysics Data System (ADS)

Li, Ying; Liu, Zeliang; Jia, Zheng; Liu, Wing Kam; Aldousari, Saad M.; Hedia, Hassan S.; Asiri, Saeed A.

2017-02-01

Polymer nanocomposites have been envisioned as advanced materials for improving the mechanical performance of neat polymers used in aerospace, petrochemical, environment and energy industries. With the filler size approaching the nanoscale, composite materials tend to demonstrate remarkable thermomechanical properties, even with addition of a small amount of fillers. These observations confront the classical composite theories and are usually attributed to the high surface-area-to-volume-ratio of the fillers, which can introduce strong nanoscale interfacial effect and relevant long-range perturbation on polymer chain dynamics. Despite decades of research aimed at understanding interfacial effect and improving the mechanical performance of composite materials, it is not currently possible to accurately predict the mechanical properties of polymer nanocomposites directly from their molecular constituents. To overcome this challenge, different theoretical, experimental and computational schemes will be used to uncover the key physical mechanisms at the relevant spatial and temporal scales for predicting and tuning constitutive behaviors in silico, thereby establishing a bottom-up virtual design principle to achieve unprecedented mechanical performance of nanocomposites. A modular-based multiscale modeling approach for viscoelasticity of polymer nanocomposites has been proposed and discussed in this study, including four modules: (A) neat polymer toolbox; (B) interphase toolbox; (C) microstructural toolbox and (D) homogenization toolbox. Integrating these modules together, macroscopic viscoelasticity of polymer nanocomposites could be directly predicted from their molecular constituents. This will maximize the computational ability to design novel polymer composites with advanced performance. More importantly, elucidating the viscoelasticity of polymer nanocomposites through fundamental studies is a critical step to generate an integrated computational material

Microbial conversion of biomass into bio-based polymers.

PubMed

Kawaguchi, Hideo; Ogino, Chiaki; Kondo, Akihiko

2017-12-01

The worldwide market for plastics is rapidly growing, and plastics polymers are typically produced from petroleum-based chemicals. The overdependence on petroleum-based chemicals for polymer production raises economic and environmental sustainability concerns. Recent progress in metabolic engineering has expanded fermentation products from existing aliphatic acids or alcohols to include aromatic compounds. This diversity provides an opportunity to expand the development and industrial uses of high-performance bio-based polymers. However, most of the biomonomers are produced from edible sugars or starches that compete directly with food and feed uses. The present review focuses on recent progress in the microbial conversion of biomass into bio-based polymers, in which fermentative products from renewable feedstocks serve as biomonomers for the synthesis of bio-based polymers. In particular, the production of biomonomers from inedible lignocellulosic feedstocks by metabolically engineered microorganisms and the synthesis of bio-based engineered plastics from the biological resources are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Implementation of Laminate Theory Into Strain Rate Dependent Micromechanics Analysis of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

2000-01-01

A research program is in progress to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to impact loads. Previously, strain rate dependent inelastic constitutive equations developed to model the polymer matrix were implemented into a mechanics of materials based micromechanics method. In the current work, the computation of the effective inelastic strain in the micromechanics model was modified to fully incorporate the Poisson effect. The micromechanics equations were also combined with classical laminate theory to enable the analysis of symmetric multilayered laminates subject to in-plane loading. A quasi-incremental trapezoidal integration method was implemented to integrate the constitutive equations within the laminate theory. Verification studies were conducted using an AS4/PEEK composite using a variety of laminate configurations and strain rates. The predicted results compared well with experimentally obtained values.

Polymer dual ring resonators for label-free optical biosensing using microfluidics.

PubMed

Salleh, Muhammad H M; Glidle, Andrew; Sorel, Marc; Reboud, Julien; Cooper, Jonathan M

2013-04-18

We demonstrate a polymer resonator microfluidic biosensor that overcomes the complex manufacturing procedures required to fabricate traditional devices. In this new format, we show that a gapless light coupling photonic configuration, fabricated in SU8 polymer, can achieve high sensitivity, label-free chemical sensing in solution and high sensitivity biological sensing, at visible wavelengths.

Blood Clotting Inspired Polymer Physics

NASA Astrophysics Data System (ADS)

Sing, Charles Edward

The blood clotting process is one of the human body's masterpieces in targeted molecular manipulation, as it requires the activation of the clotting cascade at a specific place and a specific time. Recent research in the biological sciences have discovered that one of the protein molecules involved in the initial stages of the clotting response, von Willebrand Factor (vWF), exhibits counterintuitive and technologically useful properties that are driven in part by the physical environment in the bloodstream at the site of a wound. In this thesis, we take inspiration from initial observations of the vWF in experiments, and aim to describe the behaviors observed in this process within the context of polymer physics. By understanding these physical principles, we hope to harness nature's ability to both direct molecules in both spatial and conformational coordinates. This thesis is presented in three complementary sections. After an initial introduction describing the systems of interest, we first describe the behavior of collapsed Lennard-Jones polymers in the presence of an infinite medium. It has been shown that simple bead-spring homopolymer models describe vWF quite well in vitro. We build upon this previous work to first describe the behavior of a collapsed homopolymer in an elongational fluid flow. Through a nucleation-protrusion mechanism, scaling relationships can be developed to provide a clear picture of a first-order globule-stretch transition and its ramifications in dilute-solution rheology. The implications of this behavior and its relation to the current literature provides qualitative explanations for the physiological process of vasoconstriction. In an effort to generalize these observations, we present an entire theory on the behavior of polymer globules under influence of any local fluid flow. Finally, we investigate the internal dynamics of these globules by probing their pulling response in an analogous fashion to force spectroscopy. We elucidate

Bio- and chemocatalysis cascades as a bridge between biology and chemistry for green polymer synthesis.

PubMed

Marszałek-Harych, Aleksandra; Jędrzkiewicz, Dawid; Ejfler, Jolanta

2017-01-01

The development and integration of bio- and chemocatalytic processes to convert renewable or biomass feedstocks into polymers is a vibrant field of research with enormous potential for environmental protection and the mitigation of global warming. Here, we review the biotechnological and chemical synthetic strategies for producing platform monomers from bio-based sources and transforming them into eco-polymers. We also discuss their advanced bio-application using the example of polylactide (PLA), the most valuable green polymer on the market.

Constitutional and Non-Constitutional Governments...Similarities and Differences throughout History. Resource Packet.

ERIC Educational Resources Information Center

Pallasch, Brian Thomas

This civic education resource packet is designed to provide teachers, community leaders, and other civic educators with an understanding of the differences between constitutional and non-constitutional governments. Six papers discussing the topic are included: "The Differences bewteen Constitutional and Non-Constitutional Governments" (John…

A micro-macro constitutive model for finite-deformation viscoelasticity of elastomers with nonlinear viscosity

NASA Astrophysics Data System (ADS)

Zhou, Jianyou; Jiang, Liying; Khayat, Roger E.

2018-01-01

Elastomers are known to exhibit viscoelastic behavior under deformation, which is linked to the diffusion processes of the highly mobile and flexible polymer chains. Inspired by the theories of polymer dynamics, a micro-macro constitutive model is developed to study the viscoelastic behaviors and the relaxation process of elastomeric materials under large deformation, in which the material parameters all have a microscopic foundation or a microstructural justification. The proposed model incorporates the nonlinear material viscosity into the continuum finite-deformation viscoelasticity theories which represent the polymer networks of elastomers with an elastic ground network and a few viscous subnetworks. The developed modeling framework is capable of adopting most of strain energy density functions for hyperelastic materials and thermodynamics evolution laws of viscoelastic solids. The modeling capacity of the framework is outlined by comparing the simulation results with the experimental data of three commonly used elastomeric materials, namely, VHB4910, HNBR50 and carbon black (CB) filled elastomers. The comparison shows that the stress responses and some typical behaviors of filled and unfilled elastomers can be quantitatively predicted by the model with suitable strain energy density functions. Particularly, the strain-softening effect of elastomers could be explained by the deformation-dependent (nonlinear) viscosity of the polymer chains. The presented modeling framework is expected to be useful as a modeling platform for further study on the performance of different type of elastomeric materials.

A Non-Biological Method for Screening Active Components against Influenza Virus from Traditional Chinese Medicine by Coupling a LC Column with Oseltamivir Molecularly Imprinted Polymers

PubMed Central

Yang, Ya-Jun; Li, Jian-Yong; Liu, Xi-Wang; Zhang, Ji-Yu; Liu, Yu-Rong; Li, Bing

2013-01-01

To develop a non-biological method for screening active components against influenza virus from traditional Chinese medicine (TCM) extraction, a liquid chromatography (LC) column prepared with oseltamivir molecularly imprinted polymer (OSMIP) was employed with LC-mass spectrometry (LC-MS). From chloroform extracts of compound TCM liquid preparation, we observed an affinitive component m/z 249, which was identified to be matrine following analysis of phytochemical literatures, OSMIP-LC column on-line of control compounds and MS/MS off-line. The results showed that matrine had similar bioactivities with OS against avian influenza virus H9N2 in vitro for both alleviating cytopathic effect and hemagglutination inhibition and that the stereostructures of these two compounds are similar while their two-dimensional structures were different. In addition, our results suggested that the bioactivities of those affinitive compounds were correlated with their chromatographic behaviors, in which less difference of the chromatographic behaviors might have more similar bioactivities. This indicates that matrine is a potential candidate drug to prevent or cure influenza for human or animal. In conclusion, the present study showed that molecularly imprinted polymers can be used as a non-biological method for screening active components against influenza virus from TCM. PMID:24386385

Micromechanics and constitutive models for soft active materials with phase evolution

NASA Astrophysics Data System (ADS)

Wang, Binglian

Soft active materials, such as shape memory polymers, liquid crystal elastomers, soft tissues, gels etc., are materials that can deform largely in response to external stimuli. Micromechanics analysis of heterogeneous materials based on finite element method is a typically numerical way to study the thermal-mechanical behaviors of soft active materials with phase evolution. While the constitutive models that can precisely describe the stress and strain fields of materials in the process of phase evolution can not be found in the databases of some commercial finite element analysis (FEA) tools such as ANSYS or Abaqus, even the specific constitutive behavior for each individual phase either the new formed one or the original one has already been well-known. So developing a computationally efficient and general three dimensional (3D) thermal-mechanical constitutive model for soft active materials with phase evolution which can be implemented into FEA is eagerly demanded. This paper first solved this problem theoretically by recording the deformation history of each individual phase in the phase evolution process, and adopted the idea of effectiveness by regarding all the new formed phase as an effective phase with an effective deformation to make this theory computationally efficient. A user material subroutine (UMAT) code based on this theoretical constitutive model has been finished in this work which can be added into the material database in Abaqus or ANSYS and can be easily used for most soft active materials with phase evolution. Model validation also has been done through comparison between micromechanical FEA and experiments on a particular composite material, shape memory elastomeric composite (SMEC) which consisted of an elastomeric matrix and the crystallizable fibre. Results show that the micromechanics and the constitutive models developed in this paper for soft active materials with phase evolution are completely relied on.

Linear fully dry polymer actuators

NASA Astrophysics Data System (ADS)

De Rossi, Danilo; Mazzoldi, Alberto

1999-05-01

In the last period, the interest in the development of devices that emulate the properties of the 'par excellence' biological actuator, the human muscle, is considerably grown. The recent advances in the field of conducting polymers open new interesting prospects in this direction: from this point of view polyaniline (PANi), since it is easily produced in fiber form, represents an interesting material. In this conference we report the development of a linear actuator prototype that makes use of PANi fiber. All fabrication steps (fiber extrusion, solid polymer electrolyte preparation, compound realization) and experimental set-up for the electromechanical characterization are described. Quantitative measurements of isotonic length changes and isometric stress generation during electrochemical stimulation are reported. An overall assessment of PANi fibers actuative properties in wet and dry conditions is reported and possible future developments are proposed. Finally, continuum and lumped parameter models formulated to describe passive and active contractile properties of conducting polymer actuators are briefly outlined.

Application of activated barrier hopping theory to viscoplastic modeling of glassy polymers

NASA Astrophysics Data System (ADS)

Sweeney, J.; Spencer, P. E.; Vgenopoulos, D.; Babenko, M.; Boutenel, F.; Caton-Rose, P.; Coates, P. D.

2018-05-01

An established statistical mechanical theory of amorphous polymer deformation has been incorporated as a plastic mechanism into a constitutive model and applied to a range of polymer mechanical deformations. The temperature and rate dependence of the tensile yield of PVC, as reported in early studies, has been modeled to high levels of accuracy. Tensile experiments on PET reported here are analyzed similarly and good accuracy is also achieved. The frequently observed increase in the gradient of the plot of yield stress against logarithm of strain rate is an inherent feature of the constitutive model. The form of temperature dependence of the yield that is predicted by the model is found to give an accurate representation. The constitutive model is developed in two-dimensional form and implemented as a user-defined subroutine in the finite element package ABAQUS. This analysis is applied to the tensile experiments on PET, in some of which strain is localized in the form of shear bands and necks. These deformations are modeled with partial success, though adiabatic heating of the instability causes inaccuracies for this isothermal implementation of the model. The plastic mechanism has advantages over the Eyring process, is equally tractable, and presents no particular difficulties in implementation with finite elements.

Application of activated barrier hopping theory to viscoplastic modeling of glassy polymers

NASA Astrophysics Data System (ADS)

Sweeney, J.; Spencer, P. E.; Vgenopoulos, D.; Babenko, M.; Boutenel, F.; Caton-Rose, P.; Coates, P. D.

2017-10-01

An established statistical mechanical theory of amorphous polymer deformation has been incorporated as a plastic mechanism into a constitutive model and applied to a range of polymer mechanical deformations. The temperature and rate dependence of the tensile yield of PVC, as reported in early studies, has been modeled to high levels of accuracy. Tensile experiments on PET reported here are analyzed similarly and good accuracy is also achieved. The frequently observed increase in the gradient of the plot of yield stress against logarithm of strain rate is an inherent feature of the constitutive model. The form of temperature dependence of the yield that is predicted by the model is found to give an accurate representation. The constitutive model is developed in two-dimensional form and implemented as a user-defined subroutine in the finite element package ABAQUS. This analysis is applied to the tensile experiments on PET, in some of which strain is localized in the form of shear bands and necks. These deformations are modeled with partial success, though adiabatic heating of the instability causes inaccuracies for this isothermal implementation of the model. The plastic mechanism has advantages over the Eyring process, is equally tractable, and presents no particular difficulties in implementation with finite elements.

Assessing Students' Performances in Decision-Making: Coping Strategies of Biology Teachers

ERIC Educational Resources Information Center

Steffen, Benjamin; Hößle, Corinna

2017-01-01

Decision-making in socioscientific issues (SSI) constitutes a real challenge for both biology teachers and learners. The assessment of students' performances in SSIs constitutes a problem, especially for biology teachers. The study at hand was conducted in Germany and uses a qualitative approach following the research procedures of grounded theory…

Creep-induced anisotropy in covalent adaptable network polymers.

PubMed

Hanzon, Drew W; He, Xu; Yang, Hua; Shi, Qian; Yu, Kai

2017-10-11

Anisotropic polymers with aligned macromolecule chains exhibit directional strengthening of mechanical and physical properties. However, manipulating the orientation of polymer chains in a fully cured thermoset is almost impossible due to its permanently crosslinked nature. In this paper, we demonstrate that rearrangeable networks with bond exchange reactions (BERs) can be utilized to tailor the anisotropic mechanical properties of thermosetting polymers. When a constant force is maintained at BER activated temperatures, the malleable thermoset creeps in the direction of stress, and macromolecule chains align themselves in the same direction. The aligned polymer chains result in an anisotropic network with a stiffer mechanical behavior in the direction of creep, while with a more compliant behavior in the transverse direction. The degree of network anisotropy is proportional to the amount of creep strain. A multi-length scale constitutive model is developed to study the creep-induced anisotropy of thermosetting polymers. The model connects the micro-scale BER kinetics, orientation of polymer chains, and directional mechanical properties of network polymers. Without any fitting parameters, it is able to predict the evolution of creep strain at different temperatures and anisotropic stress-strain behaviors of CANs after creep. Predictions on the chain orientation are verified by molecular dynamics (MD) simulation. Based on parametric studies, it is shown that the influences of creep time and temperature on the network anisotropy can be generalized into a single parameter, and the evolution of directional modulus follows an Arrhenius type time-temperature superposition principle (TTSP). The presented work provides a facile approach to transform isotropic thermosets into anisotropic ones using simple heating, and their directional properties can be readily tailored by the processing conditions.

Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples

NASA Astrophysics Data System (ADS)

Liu, Xiaolan; He, Man; Chen, Beibei; Hu, Bin

2014-11-01

A novel method based on on-line polymer monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Au and Pd in biological samples. For this purpose, poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was prepared and functionalized with mercapto groups. The prepared monolith exhibited good selectivity to Au and Pd, and good resistance to strong acid with a long life span. Factors affecting the extraction efficiency of CME, such as sample acidity, sample flow rate, eluent conditions and coexisting ion interference were investigated in detail. Under the optimal conditions, the limits of detection (LODs, 3σ) were 5.9 ng L- 1 for Au and 8.3 ng L- 1 for Pd, and the relative standard deviations (RSDs, c = 50 ng L-1, n = 7) were 6.5% for Au and 1.1% for Pd, respectively. The developed method was successfully applied to the determination of Au and Pd in human urine and serum samples with the recovery in the range of 84-118% for spiked samples. The developed on-line polymer monolithic CME-ICP-MS method has the advantages of rapidity, simplicity, low sample/reagent consumption, high sensitivity and is suitable for the determination of trace Au and Pd in biological samples with limited amount available and complex matrix.

Optical Control of Living Cells Electrical Activity by Conjugated Polymers.

PubMed

Martino, Nicola; Bossio, Caterina; Vaquero Morata, Susana; Lanzani, Guglielmo; Antognazza, Maria Rosa

2016-01-28

Hybrid interfaces between organic semiconductors and living tissues represent a new tool for in-vitro and in-vivo applications. In particular, conjugated polymers display several optimal properties as substrates for biological systems, such as good biocompatibility, excellent mechanical properties, cheap and easy processing technology, and possibility of deposition on light, thin and flexible substrates. These materials have been employed for cellular interfaces like neural probes, transistors for excitation and recording of neural activity, biosensors and actuators for drug release. Recent experiments have also demonstrated the possibility to use conjugated polymers for all-optical modulation of the electrical activity of cells. Several in-vitro study cases have been reported, including primary neuronal networks, astrocytes and secondary line cells. Moreover, signal photo-transduction mediated by organic polymers has been shown to restore light sensitivity in degenerated retinas, suggesting that these devices may be used for artificial retinal prosthesis in the future. All in all, light sensitive conjugated polymers represent a new approach for optical modulation of cellular activity. In this work, all the steps required to fabricate a bio-polymer interface for optical excitation of living cells are described. The function of the active interface is to transduce the light stimulus into a modulation of the cell membrane potential. As a study case, useful for in-vitro studies, a polythiophene thin film is used as the functional, light absorbing layer, and Human Embryonic Kidney (HEK-293) cells are employed as the biological component of the interface. Practical examples of successful control of the cell membrane potential upon stimulation with light pulses of different duration are provided. In particular, it is shown that both depolarizing and hyperpolarizing effects on the cell membrane can be achieved depending on the duration of the light stimulus. The reported

New Materials for Biological Fuel Cells

DTIC Science & Technology

2012-04-01

polymer electrolyte membrane ( PEM ), to the membrane-less biological fuel cell (center figure) where the two electrodes are submerged in the same... PEM . MT15_4p166_173.indd 171 4/10/2012 3:46:31 PM REVIEW New materials for biological fuel cells APRIL 2012 | VOLUME 15 | NUMBER 4172 These...ISSN:1369 7021 © Elsevier Ltd 2012APRIL 2012 | VOLUME 15 | NUMBER 4166 New materials for biological fuel cells Over the last decade, there has

The structural diversity of artificial genetic polymers

PubMed Central

Anosova, Irina; Kowal, Ewa A.; Dunn, Matthew R.; Chaput, John C.; Van Horn, Wade D.; Egli, Martin

2016-01-01

Synthetic genetics is a subdiscipline of synthetic biology that aims to develop artificial genetic polymers (also referred to as xeno-nucleic acids or XNAs) that can replicate in vitro and eventually in model cellular organisms. This field of science combines organic chemistry with polymerase engineering to create alternative forms of DNA that can store genetic information and evolve in response to external stimuli. Practitioners of synthetic genetics postulate that XNA could be used to safeguard synthetic biology organisms by storing genetic information in orthogonal chromosomes. XNA polymers are also under active investigation as a source of nuclease resistant affinity reagents (aptamers) and catalysts (xenozymes) with practical applications in disease diagnosis and treatment. In this review, we provide a structural perspective on known antiparallel duplex structures in which at least one strand of the Watson–Crick duplex is composed entirely of XNA. Currently, only a handful of XNA structures have been archived in the Protein Data Bank as compared to the more than 100 000 structures that are now available. Given the growing interest in xenobiology projects, we chose to compare the structural features of XNA polymers and discuss their potential to access new regions of nucleic acid fold space. PMID:26673703

Network approach towards understanding the crazing in glassy amorphous polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Sudarkodi; Vivek-Ananth, R. P.; Sreejith, R. P.; Mangalapandi, Pattulingam; Hassanali, Ali A.; Samal, Areejit

2018-04-01

We have used molecular dynamics to simulate an amorphous glassy polymer with long chains to study the deformation mechanism of crazing and associated void statistics. The Van der Waals interactions and the entanglements between chains constituting the polymer play a crucial role in crazing. Thus, we have reconstructed two underlying weighted networks, namely, the Van der Waals network and the entanglement network from polymer configurations extracted from the molecular dynamics simulation. Subsequently, we have performed graph-theoretic analysis of the two reconstructed networks to reveal the role played by them in the crazing of polymers. Our analysis captured various stages of crazing through specific trends in the network measures for Van der Waals networks and entanglement networks. To further corroborate the effectiveness of network analysis in unraveling the underlying physics of crazing in polymers, we have contrasted the trends in network measures for Van der Waals networks and entanglement networks in the light of stress-strain behaviour and voids statistics during deformation. We find that the Van der Waals network plays a crucial role in craze initiation and growth. Although, the entanglement network was found to maintain its structure during craze initiation stage, it was found to progressively weaken and undergo dynamic changes during the hardening and failure stages of crazing phenomena. Our work demonstrates the utility of network theory in quantifying the underlying physics of polymer crazing and widens the scope of applications of network science to characterization of deformation mechanisms in diverse polymers.

α-Amino acid containing degradable polymers as functional biomaterials: rational design, synthetic pathway, and biomedical applications.

PubMed

Sun, Huanli; Meng, Fenghua; Dias, Aylvin A; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

2011-06-13

Currently, biomedical engineering is rapidly expanding, especially in the areas of drug delivery, gene transfer, tissue engineering, and regenerative medicine. A prerequisite for further development is the design and synthesis of novel multifunctional biomaterials that are biocompatible and biologically active, are biodegradable with a controlled degradation rate, and have tunable mechanical properties. In the past decades, different types of α-amino acid-containing degradable polymers have been actively developed with the aim to obtain biomimicking functional biomaterials. The use of α-amino acids as building units for degradable polymers may offer several advantages: (i) imparting chemical functionality, such as hydroxyl, amine, carboxyl, and thiol groups, which not only results in improved hydrophilicity and possible interactions with proteins and genes, but also facilitates further modification with bioactive molecules (e.g., drugs or biological cues); (ii) possibly improving materials biological properties, including cell-materials interactions (e.g., cell adhesion, migration) and degradability; (iii) enhancing thermal and mechanical properties; and (iv) providing metabolizable building units/blocks. In this paper, recent developments in the field of α-amino acid-containing degradable polymers are reviewed. First, synthetic approaches to prepare α-amino acid-containing degradable polymers will be discussed. Subsequently, the biomedical applications of these polymers in areas such as drug delivery, gene delivery and tissue engineering will be reviewed. Finally, the future perspectives of α-amino acid-containing degradable polymers will be evaluated.

Constitutive modelling of composite biopolymer networks.

PubMed

Fallqvist, B; Kroon, M

2016-04-21

The mechanical behaviour of biopolymer networks is to a large extent determined at a microstructural level where the characteristics of individual filaments and the interactions between them determine the response at a macroscopic level. Phenomena such as viscoelasticity and strain-hardening followed by strain-softening are observed experimentally in these networks, often due to microstructural changes (such as filament sliding, rupture and cross-link debonding). Further, composite structures can also be formed with vastly different mechanical properties as compared to the individual networks. In this present paper, we present a constitutive model presented in a continuum framework aimed at capturing these effects. Special care is taken to formulate thermodynamically consistent evolution laws for dissipative effects. This model, incorporating possible anisotropic network properties, is based on a strain energy function, split into an isochoric and a volumetric part. Generalisation to three dimensions is performed by numerical integration over the unit sphere. Model predictions indicate that the constitutive model is well able to predict the elastic and viscoelastic response of biological networks, and to an extent also composite structures. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computational Simulation of the High Strain Rate Tensile Response of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

2002-01-01

A research program is underway to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to high strain rate impact loads. Under these types of loading conditions, the material response can be highly strain rate dependent and nonlinear. State variable constitutive equations based on a viscoplasticity approach have been developed to model the deformation of the polymer matrix. The constitutive equations are then combined with a mechanics of materials based micromechanics model which utilizes fiber substructuring to predict the effective mechanical and thermal response of the composite. To verify the analytical model, tensile stress-strain curves are predicted for a representative composite over strain rates ranging from around 1 x 10(exp -5)/sec to approximately 400/sec. The analytical predictions compare favorably to experimentally obtained values both qualitatively and quantitatively. Effective elastic and thermal constants are predicted for another composite, and compared to finite element results.

Modeling the effect of nano-sized polymer particles on the properties of lipid membranes

NASA Astrophysics Data System (ADS)

Rossi, Giulia; Monticelli, Luca

2014-12-01

The interaction between polymers and biological membranes has recently gained significant interest in several research areas. On the biomedical side, dendrimers, linear polyelectrolytes, and neutral copolymers find application as drug and gene delivery agents, as biocidal agents, and as platforms for biological sensors. On the environmental side, plastic debris is often disposed of in the oceans and gets degraded into small particles; therefore concern is raising about the interaction of small plastic particles with living organisms. From both perspectives, it is crucial to understand the processes driving the interaction between polymers and cell membranes. In recent times progress in computer technology and simulation methods has allowed computational predictions on the molecular mechanism of interaction between polymeric materials and lipid membranes. Here we review the computational studies on the interaction between lipid membranes and different classes of polymers: dendrimers, linear charged polymers, polyethylene glycol (PEG) and its derivatives, polystyrene, and some generic models of polymer chains. We conclude by discussing some of the technical challenges in this area and future developments.

BioArtificial polymers

NASA Astrophysics Data System (ADS)

Szałata, Kamila; Gumi, Tania

2017-07-01

Nowadays, the polymer science has impact in practically all life areas. Countless benefits coming from the usage of materials with high mechanical and chemical resistance, variety of functionalities and potentiality of modification drive to the development of new application fields. Novel approaches of combining these synthetic substances with biomolecules lead to obtain multifunctional hybrid conjugates which merge the bioactivity of natural component with outstanding properties of artificial polymer. Over the decades, an immense progress in bioartificial composites domain allowed to reach a high level of knowledge in terms of natural-like systems engineering, leading to diverse strategies of biomolecule immobilization. Together with different available options, including covalent and noncovalent attachment, come various challenges, related mainly with maintaining the biological activity of fixed molecules. Even though the amount of applications that achieve commercial status is still not substantial, and is expanding continuously in the disciplines like "smart materials," biosensors, delivery systems, nanoreactors and many others. A huge number of remarkable developments reported in the literature present a potential of bioartificial conjugates as a fabrics with highly controllable structure and multiple functionalities, serving as a powerful nanotechnological tool. This novel approach brings closer biologists, chemists and engineers, who sharing their effort and complementing the knowledge can revolutionize the field of bioartificial polymer science.

Polymeric drugs: Advances in the development of pharmacologically active polymers

PubMed Central

Li, Jing; Yu, Fei; Chen, Yi; Oupický, David

2015-01-01

Synthetic polymers play a critical role in pharmaceutical discovery and development. Current research and applications of pharmaceutical polymers are mainly focused on their functions as excipients and inert carriers of other pharmacologically active agents. This review article surveys recent advances in alternative pharmaceutical use of polymers as pharmacologically active agents known as polymeric drugs. Emphasis is placed on the benefits of polymeric drugs that are associated with their macromolecular character and their ability to explore biologically relevant multivalency processes. We discuss the main therapeutic uses of polymeric drugs as sequestrants, antimicrobials, antivirals, and anticancer and anti-inflammatory agents. PMID:26410809

Orientation of contravariant and covariant polymers and associated energy transfer in elasto-inertial turbulence

NASA Astrophysics Data System (ADS)

Horiuti, Kiyosi; Suzuki, Aoi

2016-11-01

It is generally assumed that the polymers in viscoelastic turbulence are advected affinely with the macroscopically-imposed deformation, while de Gennes (1986) hypothesized that stretched polymers may exhibit rigidity. We conduct assessment on this hypothesis in homogeneous isotropic turbulence by connecting mesoscopic Brownian description of elastic dumbbells to macroscopic DNS. The dumbbells are advected either affinely (contravariant) or non-affinely (covariant). We consider the elasto-inertial regime (Valente et al. 2014). Using the approximate solution of the constitutive equation for the polymer stress, we show that when the dumbbells are highly stretched, -SikSklSli term (Sij is strain-rate tensor) governs the transfer of solvent energy either to dissipation or to the elastic energy stored in the polymers. In the contravariant polymer, the elastic energy production term Pe < 0 and the dissipation production term Pɛ > 0 . The elastic energy is transferred backwardly into the solvent and dissipation is enhanced. In the covariant polymer, Pe > 0 and Pɛ > 0 . When the dumbbells are aligned with one of eigenvectors of Sij, Pe predominates Pɛ, and marked reduction of drag is achieved.

[Polymer and oligomer based doxorubicin carriers].

PubMed

Kik, Krzysztof; Lwow, Felicja; Szmigiero, Leszek

2007-01-01

Doxorubicin and other anthracycline derivatives play an important role in the treatment of many malignant diseases. Unfortunately, clinical effectiveness of this class of drugs is limited by cumulative cardiotoxicity which occurs in significant percentage of patients at cumulative dose in the range 450-600 mg/m2. Therefore, several strategies have been developed to reduce cardiotoxicity of doxorubicin and its analogues. One of the possible ways leading to the improvement of anticancer selectivity of doxorubicin is the design of polymer and olygomer carriers which may transport drug molecules more efficiently and more specifically. Synthetic polymers are of increasing interest as therapeutic agents owing to their enhanced pharmacokinetic profiles relative to small molecule drugs. Currently a new class of multifunctional polymers is being prepared that can "mask" biologically active compounds, such as cytotoxic agents, until they reach target sites, but which can then release the agent in situ to effect the therapy. The legitimacy of the development of polymer based doxorubicine carriers is supported by the growing number of clinical reports indicating that the use of hydrophilic polymers or polymer coated liposomes as a platform for delivery of the drug results in better therapeutic effects than the free drug. In this article we present the most promising strategies directed at the development of improved anthracycline drugs formulations based of polymer and olygomer carriers. We review: 1) polyethylenoglycol-coated ("pegylated") liposomal doxorubicin; 2) extracellulary tumor-activated prodrugs which are conjugates of doxorubicin with peptides; 3) doxorubicin coated by higly polymerised glycosoaminoglycans; 4) conjugates of doxorubicin with copolymer of N-(2-hydroxypropyl)methacrylamide.

Study on the Antimicrobial Properties of Citrate-Based Biodegradable Polymers

PubMed Central

Su, Lee-Chun; Xie, Zhiwei; Zhang, Yi; Nguyen, Kytai Truong; Yang, Jian

2014-01-01

Citrate-based polymers possess unique advantages for various biomedical applications since citric acid is a natural metabolism product, which is biocompatible and antimicrobial. In polymer synthesis, citric acid also provides multiple functional groups to control the crosslinking of polymers and active binding sites for further conjugation of biomolecules. Our group recently developed a number of citrate-based polymers for various biomedical applications by taking advantage of their controllable chemical, mechanical, and biological characteristics. In this study, various citric acid derived biodegradable polymers were synthesized and investigated for their physicochemical and antimicrobial properties. Results indicate that citric acid derived polymers reduced bacterial proliferation to different degrees based on their chemical composition. Among the studied polymers, poly(octamethylene citrate) showed ~70–80% suppression to microbe proliferation, owing to its relatively higher ratio of citric acid contents. Crosslinked urethane-doped polyester elastomers and biodegradable photoluminescent polymers also exhibited significant bacteria reduction of ~20 and ~50% for Staphylococcus aureus and Escherichia coli, respectively. Thus, the intrinsic antibacterial properties in citrate-based polymers enable them to inhibit bacteria growth without incorporation of antibiotics, silver nanoparticles, and other traditional bacteria-killing agents suggesting that the citrate-based polymers are unique beneficial materials for wound dressing, tissue engineering, and other potential medical applications where antimicrobial property is desired. PMID:25023605

DNA binding and biological studies of some novel water-soluble polymer-copper(II)-phenanthroline complexes.

PubMed

Kumar, Rajendran Senthil; Arunachalam, Sankaralingam; Periasamy, Vaiyapuri Subbarayan; Preethy, Christo Paul; Riyasdeen, Anvarbatcha; Akbarsha, Mohammad Abdulkader

2008-10-01

Some novel water-soluble polymer-copper(II)-phenanthroline complex samples, [Cu(phen)2(BPEI)]Cl(2).4H2O (phen=1,10-phenanthroline, BPEI=branched polyethyleneimine), with different degrees of copper complex content in the polymer chain have been prepared by ligand substitution method in water-ethanol medium and characterized by infrared, UV-visible, EPR spectral and elemental analysis methods. The binding of these complex samples with DNA has been investigated by electronic absorption spectroscopy, emission spectroscopy and gel retardation assay. Electrostatic interactions between DNA molecule and polymer-copper(II) complex molecule containing many high positive charges have been observed. Besides these ionic interactions, van der Waals interactions, hydrogen bonding and other partial intercalation binding modes may also exist in this system. The polymer-copper(II) complex with higher degree of copper complex content was screened for its antimicrobial activity and antitumor activity.

Local-feature analysis for automated coarse-graining of bulk-polymer molecular dynamics simulations.

PubMed

Xue, Y; Ludovice, P J; Grover, M A

2012-12-01

A method for automated coarse-graining of bulk polymers is presented, using the data-mining tool of local feature analysis. Most existing methods for polymer coarse-graining define superatoms based on their covalent bonding topology along the polymer backbone, but here superatoms are defined based only on their correlated motions, as observed in molecular dynamics simulations. Correlated atomic motions are identified in the simulation data using local feature analysis, between atoms in the same or in different polymer chains. Groups of highly correlated atoms constitute the superatoms in the coarse-graining scheme, and the positions of their seed coordinates are then projected forward in time. Based on only the seed positions, local feature analysis enables the full reconstruction of all atomic positions. This reconstruction suggests an iterative scheme to reduce the computation of the simulations to initialize another short molecular dynamic simulation, identify new superatoms, and again project forward in time.

[Opportunistic pathogenic and toxic micro-fungi among synthetic polymer destructors].

PubMed

Kurakov, A V; Novikova, N D; Ozerskaia, S M; Deshevaia, E A; Gevorkian, S A; Gogiian, V B

2007-01-01

Analysis of species diversity of the micro-fungi typically detected at the sites of biodamage of synthetic polymers on space vehicles exhibited the presence of a broad variety of opportunistic pathogens and toxic species. Thus, 78 species of micromycetes of 300 polymer destructing fungi are associated with biological risk levels BSL-1 and BSL-2 (low and moderate levels, respectively). As many as 56 species are able to produce toxic compounds.

The diversification of developmental biology.

PubMed

Crowe, Nathan; Dietrich, Michael R; Alomepe, Beverly S; Antrim, Amelia F; ByrneSim, Bay Lauris; He, Yi

2015-10-01

In the 1960s, "developmental biology" became the dominant term to describe some of the research that had previously been included under the rubrics of embryology, growth, morphology, and physiology. As scientific societies formed under this new label, a new discipline took shape. Historians, however, have a number of different perspectives on what changes led to this new field of developmental biology and how the field itself was constituted during this period. Using the General Embryological Information Service, a global index of post-World War II development-related research, we have documented and visualized significant changes in the kinds of research that occurred as this new field formed. In particular, our analysis supports the claim that the transition toward developmental biology was marked by a growth in new topics and forms of research. Although many historians privilege the role of molecular biology and/or the molecularization of biology in general during this formative period, we have found that the influence of molecular biology is not sufficient to account for the wide range of new research that constituted developmental biology at the time. Overall, our work creates a robust characterization of the changes that occurred with regard to research on growth and development in the decades following World War II and provides a context for future work on the specific drivers of those changes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Design of water-soluble, thiol-reactive polymers of controlled molecular weight: a novel multivalent scaffold

NASA Astrophysics Data System (ADS)

Carrillo, Alvaro; Gujraty, Kunal V.; Rai, Prakash R.; Kane, Ravi S.

2005-07-01

Multivalent molecules, i.e. scaffolds presenting multiple copies of a suitable ligand, constitute an emerging class of nanoscale therapeutics. We present a novel approach for the design of multivalent ligands, which allows the biofunctionalization of polymers with proteins or peptides in a controlled orientation. It consists of the synthesis of water-soluble, activated polymer scaffolds of controlled molecular weight, which can be biofunctionalized with various thiolated ligands in aqueous media under mild conditions. These polymers were synthesized by ring-opening metathesis polymerization (ROMP) and further modified to make them water-soluble. The incorporation of chloride groups activated the polymers to react with thiol-containing peptides or proteins, and the formation of multivalent ligands in aqueous media was demonstrated. This strategy represents a convenient route for synthesizing multivalent ligands of controlled dimensions and valency.

Biologically inspired toys using artificial muscles

NASA Technical Reports Server (NTRS)

Bar-Cohen, Y.

2001-01-01

Recent developments in electroactive polymers, so-called artificial muscles, could one day be used to make bionics possible. Meanwhile, as this technology evolves novel mechanisms are expected to emerge that are biologically inspired.

The Constitutional Amendment Process

ERIC Educational Resources Information Center

Chism, Kahlil

2005-01-01

This article discusses the constitutional amendment process. Although the process is not described in great detail, Article V of the United States Constitution allows for and provides instruction on amending the Constitution. While the amendment process currently consists of six steps, the Constitution is nevertheless quite difficult to change.…

The biological and electrical trade-offs related to the thickness of conducting polymers for neural applications.

PubMed

Baek, Sungchul; Green, Rylie A; Poole-Warren, Laura A

2014-07-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have attracted substantial interest as coatings for platinum neuroprosthetic electrodes due to their excellent chemical stability and electrical properties. This study systematically examined PEDOT coatings formed with different amounts of charge and dopant ions, and investigated the combination of surface characteristics that were optimal for neural cell interactions. PEDOT samples were fabricated by varying the electrodeposition charge from 0.05 to 1 C cm(-2). Samples were doped with either poly(styrenesulfonate), tosylate (pTS) or perchlorate. Scanning electron micrographs revealed that both thickness and nodularity increased as the charge used to produce the sample was increased, and larger dopants produced smoother films across all thicknesses. X-ray photoelectron spectroscopy confirmed that the amount of charge directly corresponded to the thickness and amount of dopant in the samples. Additionally, with increased thickness and nodularity, the electrochemical properties of all PEDOT coatings improved. However, neural cell adhesion and outgrowth assays revealed that there is a direct biological tradeoff related to the thickness and nodularity. Cell attachment, growth and differentiation was poorer on the thicker, rougher samples, but thin, less nodular PEDOT films exhibited significant improvements over bare platinum. PEDOT/pTS fabricated with a charge density of <0.1Ccm(-2) provided superior electrochemical and biological properties over conventional platinum electrodes and would be the most suitable conducting polymer for neural interface applications. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photoresponsive polymer design for solar concentrator self-steering heliostats

NASA Astrophysics Data System (ADS)

Barker, Jessica; Basnet, Amod; Bhaduri, Moinak; Burch, Caroline; Chow, Amenda; Li, Xue; Oates, William S.; Massad, Jordan E.; Smith, Ralph

2014-03-01

Concentrating solar energy and transforming it into electricity is clean, economical and renewable. One design of solar power plants consists of an array of heliostats which redirects sunlight to a fixed receiver tower and the generated heat is converted into electricity. Currently, the angles of elevation of heliostats are controlled by motors and drives that are costly and require diverting power that can otherwise be used for producing electricity. We consider replacing the motor and drive system of the heliostat with a photosensitive polymer design that can tilt the mirror using the ability of the polymer to deform when subjected to light. The light causes the underlying molecular structure to change and subsequently, the polymer deforms. The deformation of the polymer is quantified in terms of photostrictive constitutive relations. A mathematical model is derived governing the behaviour of the angle of elevation as the photostrain varies. Photostrain depends on the composition of the polymer, intensity and temperature of light and angle of light polarization. Preliminary findings show a photomechanical rod structural design can provide 60° elevation for temperatures of about 40°C. A photomechanical beam structural design can generate more tilt at lower temperatures. The mathematical analysis illustrates that photostrains on the order of 1% to 10% are desired for both rod and beam designs to produce sufficient tilt under most heliostat field conditions.

Critical evaluation of biodegradable polymers used in nanodrugs

PubMed Central

Marin, Edgar; Briceño, Maria Isabel; Caballero-George, Catherina

2013-01-01

Use of biodegradable polymers for biomedical applications has increased in recent decades due to their biocompatibility, biodegradability, flexibility, and minimal side effects. Applications of these materials include creation of skin, blood vessels, cartilage scaffolds, and nanosystems for drug delivery. These biodegradable polymeric nanoparticles enhance properties such as bioavailability and stability, and provide controlled release of bioactive compounds. This review evaluates the classification, synthesis, degradation mechanisms, and biological applications of the biodegradable polymers currently being studied as drug delivery carriers. In addition, the use of nanosystems to solve current drug delivery problems are reviewed. PMID:23990720

Positioning Genomics in Biology Education: Content Mapping of Undergraduate Biology Textbooks†

PubMed Central

Wernick, Naomi L. B.; Ndung’u, Eric; Haughton, Dominique; Ledley, Fred D.

2014-01-01

Biological thought increasingly recognizes the centrality of the genome in constituting and regulating processes ranging from cellular systems to ecology and evolution. In this paper, we ask whether genomics is similarly positioned as a core concept in the instructional sequence for undergraduate biology. Using quantitative methods, we analyzed the order in which core biological concepts were introduced in textbooks for first-year general and human biology. Statistical analysis was performed using self-organizing map algorithms and conventional methods to identify clusters of terms and their relative position in the books. General biology textbooks for both majors and nonmajors introduced genome-related content after text related to cell biology and biological chemistry, but before content describing higher-order biological processes. However, human biology textbooks most often introduced genomic content near the end of the books. These results suggest that genomics is not yet positioned as a core concept in commonly used textbooks for first-year biology and raises questions about whether such textbooks, or courses based on the outline of these textbooks, provide an appropriate foundation for understanding contemporary biological science. PMID:25574293

Positioning genomics in biology education: content mapping of undergraduate biology textbooks.

PubMed

Wernick, Naomi L B; Ndung'u, Eric; Haughton, Dominique; Ledley, Fred D

2014-12-01

Biological thought increasingly recognizes the centrality of the genome in constituting and regulating processes ranging from cellular systems to ecology and evolution. In this paper, we ask whether genomics is similarly positioned as a core concept in the instructional sequence for undergraduate biology. Using quantitative methods, we analyzed the order in which core biological concepts were introduced in textbooks for first-year general and human biology. Statistical analysis was performed using self-organizing map algorithms and conventional methods to identify clusters of terms and their relative position in the books. General biology textbooks for both majors and nonmajors introduced genome-related content after text related to cell biology and biological chemistry, but before content describing higher-order biological processes. However, human biology textbooks most often introduced genomic content near the end of the books. These results suggest that genomics is not yet positioned as a core concept in commonly used textbooks for first-year biology and raises questions about whether such textbooks, or courses based on the outline of these textbooks, provide an appropriate foundation for understanding contemporary biological science.

Drug delivery's quest for polymers: Where are the frontiers?

PubMed

Merkle, Hans P

2015-11-01

Since the legendary 1964 article of Folkman and Long entitled "The use of silicone rubber as a carrier for prolonged drug therapy" the role of polymers in controlled drug delivery has come a long way. Today it is evident that polymers play a crucial if not the prime role in this field. The latest boost owes to the interest in drug delivery for the purpose of tissue engineering in regenerative medicine. The focus of this commentary is on a selection of general and personal observations that are characteristic for the current state of polymer therapeutics and carriers. It briefly highlights selected examples for the long march of synthetic polymer-drug conjugates from bench to bedside, comments on the ambivalence of selected polymers as inert excipients versus biological response modifiers, and on the yet unsolved dilemma of cationic polymers for the delivery of nucleic acid therapeutics. Further subjects are the complex design of multifunctional polymeric carriers including recent concepts towards functional supramolecular polymers, as well as observations on stimuli-sensitive polymers and the currently ongoing trend towards natural and naturally-derived biopolymers. The final topic is the discovery and early development of a novel type of biodegradable polyesters for parenteral use. Altogether, it is not the basic and applied research in polymer therapeutics and carriers, but the translational process that is the key hurdle to proceed towards an authoritative approval of new polymer therapeutics and carriers. Copyright © 2015 Elsevier B.V. All rights reserved.

Biomimetic Gradient Polymers with Enhanced Damping Capacities.

PubMed

Wang, Dong; Zhang, Huan; Guo, Jing; Cheng, Beichen; Cao, Yuan; Lu, Shengjun; Zhao, Ning; Xu, Jian

2016-04-01

Designing gradient structures, mimicking biological materials, such as pummelo peels and tendon, is a promising strategy for developing advanced materials with superior energy damping capacities. Here a facile and effective approach for fabricating polymers with composition gradients at millimeter length scale is presented. The gradient thiol-ene polymers (TEPs) are created by the use of density difference of ternary thiol-ene-ene precursors and the subsequent photo-crosslinking via thiol-ene reaction. The compositional gradients are analyzed via differential scanning calorimeter (DSC), compressive modulus testing, atomic force microscopy (AFM) indentation, and swelling measurements. In contrast to homogeneous TEPs networks, the resultant gradient polymer shows a broader effective damping temperature range combining with good mechanical properties. The present result provides an effective route toward high damping materials by the fabrication of gradient structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical characterization and modelling of the temperature-dependent impact behaviour of a biocompatible poly(L-lactide)/poly(ε-caprolactone) polymer blend.

PubMed

Gustafsson, Gustaf; Nishida, Masahiro; Ito, Yoshitaka; Häggblad, Hans-Åke; Jonsén, Pär; Takayama, Tetsuo; Todo, Mitsugu

2015-11-01

Poly(ε-caprolactone) (PCL) is a ductile, bioabsorbable polymer that has been employed as a blend partner for poly(L-lactic acid) (PLLA). An improvement of the material strength and impact resistance of PLLA/PCL polymer blends compared to pure PLLA has been shown previously. To use numerical simulations in the design process of new components composed of the PLLA/PCL blend, a constitutive model for the material has to be established. In this work, a constitutive model for a PLLA/PCL polymer blend is established from the results of compressive tests at high and low strain rates at three different temperatures, including the body temperature. Finite element simulations of the split Hopkinson pressure bar test using the established constitutive model are carried out under the same condition as the experiments. During the experiments, the changes in the diameter and thickness of the specimens are captured by a high-speed video camera. The accuracy of the numerical model is tested by comparing the simulation results, such as the stress, strain, thickness and diameter histories of the specimens, with those measured in the experiments. The numerical model is also validated against an impact test of non-homogenous strains and strain rates. The results of this study provide a validated numerical model for a PLLA/PCL polymer blend at strain rates of up to 1800 s(-1) in the temperature range between 22°C and 50°C. Copyright © 2015 Elsevier Ltd. All rights reserved.

Crosslinkable coatings from phosphorylcholine-based polymers.

PubMed

Lewis, A L; Cumming, Z L; Goreish, H H; Kirkwood, L C; Tolhurst, L A; Stratford, P W

2001-01-01

2-Methacryloyloxyethyl phosphorylcholine (MPC) was synthesised and then used in the preparation of crosslinked polymer membranes with lauryl methacrylate, hydroxypropyl methacrylate and trimethoxysilylpropyl methacrylate (crosslinker) comonomers. Some physical aspects of the membrane properties were evaluated in order to establish the basis for the synthesis of a series of post-crosslinkable polymers. These materials were made by copolymerisation of the constituent monomers via a free radical method, and characterised using NMR, FT-IR, viscometry and elemental analysis. The optimum crosslink density and conditions required for curing coatings of these polymers were investigated using atomic force microscopy (AFM) and showed the inclusion of 5 mol% silyl crosslinking agent to be ideal. A nanoindentation technique was employed to determine if the coating developed elasticity upon crosslinking. The biological properties of the coatings were evaluated using a variety of protein adsorption assays and blood contacting experiments, and an enzyme immunoassay was developed to detect E. coli in order to assess the level of bacterial adhesion to these biomaterials. Polymers of this type were shown to be very useful as coating materials for improving the biocompatibility of, or reducing the levels of adherent bacteria to medical devices.

Thiomers: a new generation of mucoadhesive polymers.

PubMed

Bernkop-Schnürch, Andreas

2005-11-03

Thiolated polymers or designated thiomers are mucoadhesive basis polymers, which display thiol bearing side chains. Based on thiol/disulfide exchange reactions and/or a simple oxidation process disulfide bonds are formed between such polymers and cysteine-rich subdomains of mucus glycoproteins building up the mucus gel layer. Thiomers mimic therefore the natural mechanism of secreted mucus glycoproteins, which are also covalently anchored in the mucus layer by the formation of disulfide bonds-the bridging structure most commonly encountered in biological systems. So far the cationic thiomers chitosan-cysteine, chitosan-thiobutylamidine as well as chitosan-thioglycolic acid and the anionic thiomers poly(acylic acid)-cysteine, poly(acrylic acid)-cysteamine, carboxy-methylcellulose-cysteine and alginate-cysteine have been generated. Due to the immobilization of thiol groups on mucoadhesive basis polymers, their mucoadhesive properties are 2- up to 140-fold improved. The higher efficacy of this new generation of mucoadhesive polymers in comparison to the corresponding unmodified mucoadhesive basis polymers could be verified via various in vivo studies on various mucosal membranes in different animal species and in humans. The development of first commercial available products comprising thiomers is in progress. Within this review an overview of the mechanism of adhesion and the design of thiomers as well as delivery systems comprising thiomers and their in vivo performance is provided.

Whole genome expression and biochemical correlates of extreme constitutional types defined in Ayurveda.

PubMed

Prasher, Bhavana; Negi, Sapna; Aggarwal, Shilpi; Mandal, Amit K; Sethi, Tav P; Deshmukh, Shailaja R; Purohit, Sudha G; Sengupta, Shantanu; Khanna, Sangeeta; Mohammad, Farhan; Garg, Gaurav; Brahmachari, Samir K; Mukerji, Mitali

2008-09-09

Ayurveda is an ancient system of personalized medicine documented and practiced in India since 1500 B.C. According to this system an individual's basic constitution to a large extent determines predisposition and prognosis to diseases as well as therapy and life-style regime. Ayurveda describes seven broad constitution types (Prakritis) each with a varying degree of predisposition to different diseases. Amongst these, three most contrasting types, Vata, Pitta, Kapha, are the most vulnerable to diseases. In the realm of modern predictive medicine, efforts are being directed towards capturing disease phenotypes with greater precision for successful identification of markers for prospective disease conditions. In this study, we explore whether the different constitution types as described in Ayurveda has molecular correlates. Normal individuals of the three most contrasting constitutional types were identified following phenotyping criteria described in Ayurveda in Indian population of Indo-European origin. The peripheral blood samples of these individuals were analysed for genome wide expression levels, biochemical and hematological parameters. Gene Ontology (GO) and pathway based analysis was carried out on differentially expressed genes to explore if there were significant enrichments of functional categories among Prakriti types. Individuals from the three most contrasting constitutional types exhibit striking differences with respect to biochemical and hematological parameters and at genome wide expression levels. Biochemical profiles like liver function tests, lipid profiles, and hematological parameters like haemoglobin exhibited differences between Prakriti types. Functional categories of genes showing differential expression among Prakriti types were significantly enriched in core biological processes like transport, regulation of cyclin dependent protein kinase activity, immune response and regulation of blood coagulation. A significant enrichment of

Whole genome expression and biochemical correlates of extreme constitutional types defined in Ayurveda

PubMed Central

Prasher, Bhavana; Negi, Sapna; Aggarwal, Shilpi; Mandal, Amit K; Sethi, Tav P; Deshmukh, Shailaja R; Purohit, Sudha G; Sengupta, Shantanu; Khanna, Sangeeta; Mohammad, Farhan; Garg, Gaurav; Brahmachari, Samir K; Mukerji, Mitali

2008-01-01

Background Ayurveda is an ancient system of personalized medicine documented and practiced in India since 1500 B.C. According to this system an individual's basic constitution to a large extent determines predisposition and prognosis to diseases as well as therapy and life-style regime. Ayurveda describes seven broad constitution types (Prakritis) each with a varying degree of predisposition to different diseases. Amongst these, three most contrasting types, Vata, Pitta, Kapha, are the most vulnerable to diseases. In the realm of modern predictive medicine, efforts are being directed towards capturing disease phenotypes with greater precision for successful identification of markers for prospective disease conditions. In this study, we explore whether the different constitution types as described in Ayurveda has molecular correlates. Methods Normal individuals of the three most contrasting constitutional types were identified following phenotyping criteria described in Ayurveda in Indian population of Indo-European origin. The peripheral blood samples of these individuals were analysed for genome wide expression levels, biochemical and hematological parameters. Gene Ontology (GO) and pathway based analysis was carried out on differentially expressed genes to explore if there were significant enrichments of functional categories among Prakriti types. Results Individuals from the three most contrasting constitutional types exhibit striking differences with respect to biochemical and hematological parameters and at genome wide expression levels. Biochemical profiles like liver function tests, lipid profiles, and hematological parameters like haemoglobin exhibited differences between Prakriti types. Functional categories of genes showing differential expression among Prakriti types were significantly enriched in core biological processes like transport, regulation of cyclin dependent protein kinase activity, immune response and regulation of blood coagulation. A

Design of Polymer-Grafted Particles for Biocompatability

NASA Astrophysics Data System (ADS)

Trombly, David; Ganesan, Venkat

2009-03-01

Drug designers often coat drug particles with grafted polymers in order to introduce a net repulsion between the particles and blood proteins. This net repulsion results from the energy cost of compressing grafted chains on approach of proteins. It thus overcomes the Van Der Waals attraction between drug and protein which would otherwise cause particle-protein agglomeration and ultimately thrombosis. This study proposes to develop a fundamental understanding of the role of different features in controlling the efficacy of the grafted layers. We address this issue by developing a framework to predict the interactions between a polymer-coated spherical particle and a bare spherical particle. In order to fully capture the two-sphere system, a numerical solution of polymer mean field theory is used in a bispherical coordinate system. Results for protein-particle interaction energies for different design parameters will be presented. For biological applications, polyethylene glycol is often used as the grafted polymer. The unique properties of this molecule will be accounted for using the n-cluster model.

Implementation of Fiber Substructuring Into Strain Rate Dependent Micromechanics Analysis of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

2001-01-01

A research program is in progress to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to impact loads. Previously, strain rate dependent inelastic constitutive equations developed to model the polymer matrix were incorporated into a mechanics of materials based micromechanics method. In the current work, the micromechanics method is revised such that the composite unit cell is divided into a number of slices. Micromechanics equations are then developed for each slice, with laminate theory applied to determine the elastic properties, effective stresses and effective inelastic strains for the unit cell. Verification studies are conducted using two representative polymer matrix composites with a nonlinear, strain rate dependent deformation response. The computed results compare well to experimentally obtained values.

Chemotaxis of active, self-oscillating polymer gels in solution

NASA Astrophysics Data System (ADS)

Dayal, Pratyush; Bhattacharya, Amitabh; Kuksenok, Olga; Balazs, Anna C.

2012-02-01

Fighting, fleeing and feeding are hallmarks of all living things; all these activities require some degree of mobility. Herein, we undertake the first computational study of self-oscillating polymer gels and show that this system can ``communicate'' to undergo a biomimetic, collective response to small-scale chemical changes. In this study we harness unique properties of polymer gels that undergo oscillatory Belousov-Zhabotinsky (BZ) reaction. The activator for the reaction is generated within these BZ cilia and diffuses between the neighboring gels. In order to simulate the dynamics of the BZ gels in surrounding fluid we have developed a nonlinear hybrid 3D model which captures the elasto-dynamics of polymer gel and diffusive exchange of BZ reagents between the gel and the fluid. We illustrate that multiple BZ gels in solution exhibit a distinct form of chemotaxis, moving towards the highest activator concentration in the solution. Similar ability to sense and move in response to chemical gradients constitutes a vital function in simple organisms, enabling them to find food and flee from poisons.

Constitutional Issues--Watergate and the Constitution. Teaching with Documents.

ERIC Educational Resources Information Center

National Archives and Records Administration, Washington, DC.

When U.S. President Richard Nixon resigned in 1974 in the wake of the Watergate scandal, it was only the second time that impeachment of a president had been considered. Although the U.S. Constitution has provisions for a person removed from office to be indicted, there are no guidelines in the Constitution about a President who has resigned. The…

Environmental and toxicological planning in polymer production and disposal.

PubMed Central

Levinskas, G J

1975-01-01

There is neither a prescribed format nor a rigid sequence of testing to follow for the assessment of health and environmental effects of chemicals. Conventional animal toxicity tests plus medical surveillance and monitoring of exposed human populations will provide knowledge of the biological effects of chemicals and assurance that they can be handled safely. Useful information also can be derived from other test procedures. These include extraction studies to measure the amounts of additives which can leach from polymers, toxicity tests using aquatic organisms and birds, and determination of the biodegradability of materials and their potential for accumulation and magnification in biological systems. Current concern over pyrolysis products of polymers points up the need for defining the variables involved and development of test procedures by which meaningful evaluations of potential health hazards can be made. PMID:1175554

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.

A Nano-indentation Identification Technique for Viscoelastic Constitutive Characteristics of Periodontal Ligaments

PubMed Central

Ashrafi, H.; Shariyat, M.

2016-01-01

Introduction Nano-indentation has recently been employed as a powerful tool for determining the mechanical properties of biological tissues on nano and micro scales. A majority of soft biological tissues such as ligaments and tendons exhibit viscoelastic or time-dependent behaviors. The constitutive characterization of soft tissues is among very important subjects in clinical medicine and especially, biomechanics fields. Periodontal ligament plays an important role in initiating tooth movement when loads are applied to teeth with orthodontic appliances. It is also the most accessible ligament in human body as it can be directly manipulated without any surgical intervention. From a mechanical point of view, this ligament can be considered as a thin interface made by a solid phase, consisting mainly of collagen fibers, which is immersed into a so-called ground substance. However, the viscoelastic constitutive effects of biological tissues are seldom considered rigorous during Nano-indentation tests. Methods In the present paper, a mathematical contact approach is developed to enable determining creep compliance and relaxation modulus of distinct periodontal ligaments, using constant–rate indentation and loading time histories, respectively. An adequate curve-fitting method is presented to determine these characteristics based on the Nano-indentation of rigid Berkovich tips. Generalized Voigt-Kelvin and Wiechert models are used to model constitutive equations of periodontal ligaments, in which the relaxation and creep functions are represented by series of decaying exponential functions of time. Results Time-dependent creep compliance and relaxation function have been obtained for tissue specimens of periodontal ligaments. Conclusion To improve accuracy, relaxation and creep moduli are measured from two tests separately. Stress relaxation effects appear more rapidly than creep in the periodontal ligaments. PMID:27672630

A Nano-indentation Identification Technique for Viscoelastic Constitutive Characteristics of Periodontal Ligaments.

PubMed

Ashrafi, H; Shariyat, M

2016-06-01

Nano-indentation has recently been employed as a powerful tool for determining the mechanical properties of biological tissues on nano and micro scales. A majority of soft biological tissues such as ligaments and tendons exhibit viscoelastic or time-dependent behaviors. The constitutive characterization of soft tissues is among very important subjects in clinical medicine and especially, biomechanics fields. Periodontal ligament plays an important role in initiating tooth movement when loads are applied to teeth with orthodontic appliances. It is also the most accessible ligament in human body as it can be directly manipulated without any surgical intervention. From a mechanical point of view, this ligament can be considered as a thin interface made by a solid phase, consisting mainly of collagen fibers, which is immersed into a so-called ground substance. However, the viscoelastic constitutive effects of biological tissues are seldom considered rigorous during Nano-indentation tests. In the present paper, a mathematical contact approach is developed to enable determining creep compliance and relaxation modulus of distinct periodontal ligaments, using constant-rate indentation and loading time histories, respectively. An adequate curve-fitting method is presented to determine these characteristics based on the Nano-indentation of rigid Berkovich tips. Generalized Voigt-Kelvin and Wiechert models are used to model constitutive equations of periodontal ligaments, in which the relaxation and creep functions are represented by series of decaying exponential functions of time. Time-dependent creep compliance and relaxation function have been obtained for tissue specimens of periodontal ligaments. To improve accuracy, relaxation and creep moduli are measured from two tests separately. Stress relaxation effects appear more rapidly than creep in the periodontal ligaments.

Solid-phase synthesis of protein-polymers on reversible immobilization supports.

PubMed

Murata, Hironobu; Carmali, Sheiliza; Baker, Stefanie L; Matyjaszewski, Krzysztof; Russell, Alan J

2018-02-27

Facile automated biomacromolecule synthesis is at the heart of blending synthetic and biologic worlds. Full access to abiotic/biotic synthetic diversity first occurred when chemistry was developed to grow nucleic acids and peptides from reversibly immobilized precursors. Protein-polymer conjugates, however, have always been synthesized in solution in multi-step, multi-day processes that couple innovative chemistry with challenging purification. Here we report the generation of protein-polymer hybrids synthesized by protein-ATRP on reversible immobilization supports (PARIS). We utilized modified agarose beads to covalently and reversibly couple to proteins in amino-specific reactions. We then modified reversibly immobilized proteins with protein-reactive ATRP initiators and, after ATRP, we released and analyzed the protein polymers. The activity and stability of PARIS-synthesized and solution-synthesized conjugates demonstrated that PARIS was an effective, rapid, and simple method to generate protein-polymer conjugates. Automation of PARIS significantly reduced synthesis/purification timelines, thereby opening a path to changing how to generate protein-polymer conjugates.

Functional Hybrid Biomaterials based on Peptide-Polymer Conjugates for Nanomedicine

NASA Astrophysics Data System (ADS)

Shu, Jessica Yo

The focus of this dissertation is the design, synthesis and characterization of hybrid functional biomaterials based on peptide-polymer conjugates for nanomedicine. Generating synthetic materials with properties comparable to or superior than those found in nature has been a "holy grail" for the materials community. Man-made materials are still rather simplistic when compared to the chemical and structural complexity of a cell. Peptide-polymer conjugates have the potential to combine the advantages of the biological and synthetic worlds---that is they can combine the precise chemical structure and diverse functionality of biomolecules with the stability and processibility of synthetic polymers. As a new family of soft matter, they may lead to materials with novel properties that have yet to be realized with either of the components alone. In order for peptide-polymer conjugates to reach their full potential as useful materials, the structure and function of the peptide should be maintained upon polymer conjugation. The success in achieving desirable, functional assemblies relies on fundamentally understanding the interactions between each building block and delicately balancing and manipulating these interactions to achieve targeted assemblies without interfering with designed structures and functionalities. Such fundamental studies of peptide-polymer interactions were investigated as the nature of the polymer (hydrophilic vs. hydrophobic) and the site of its conjugation (end-conjugation vs. side-conjugation) were varied. The fundamental knowledge gained was then applied to the design of amphiphiles that self-assemble to form stable functional micelles. The micelles exhibited exceptional monodispersity and long-term stability, which is atypical of self-assembled systems. Thus such micelles based on amphiphilic peptide-polymer conjugates may meet many current demands in nanomedicine, in particular for drug delivery of hydrophobic anti-cancer therapeutics. Lastly

Tandem catalysis: a new approach to polymers.

PubMed

Robert, Carine; Thomas, Christophe M

2013-12-21

The creation of polymers by tandem catalysis represents an exciting frontier in materials science. Tandem catalysis is one of the strategies used by Nature for building macromolecules. Living organisms generally synthesize macromolecules by in vivo enzyme-catalyzed chain growth polymerization reactions using activated monomers that have been formed within cells during complex metabolic processes. However, these biological processes rely on highly complex biocatalysts, thus limiting their industrial applications. In order to obtain polymers by tandem catalysis, homogeneous and enzyme catalysts have played a leading role in the last two decades. In the following feature article, we will describe selected published efforts to achieve these research goals.

Designing polymers with sugar-based advantages for bioactive delivery applications.

PubMed

Zhang, Yingyue; Chan, Jennifer W; Moretti, Alysha; Uhrich, Kathryn E

2015-12-10

Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of sugar-based polymers for drug delivery applications, with a particular focus on the utility of the sugar component(s) to provide benefits for drug targeting and stimuli responsive systems. Specifically, numerous synthetic methods have been developed to reliably modify naturally-occurring polysaccharides, conjugate sugar moieties to synthetic polymer scaffolds to generate glycopolymers, and utilize sugars as a multifunctional building block to develop sugar-linked polymers. The design of sugar-based polymer systems has tremendous implications on both the physiological and biological properties imparted by the saccharide units and are unique from synthetic polymers. These features include the ability of glycopolymers to preferentially target various cell types and tissues through receptor interactions, exhibit bioadhesion for prolonged residence time, and be rapidly recognized and internalized by cancer cells. Also discussed are the distinct stimuli-sensitive properties of saccharide-modified polymers to mediate drug release under desired conditions. Saccharide-based systems with inherent pH- and temperature-sensitive properties, as well as enzyme-cleavable polysaccharides for targeted bioactive delivery, are covered. Overall, this work emphasizes inherent benefits of sugar-containing polymer systems for bioactive delivery.

Quaternized poly(vinyl alcohol)/alumina composite polymer membranes for alkaline direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen; Chiu, Shwu-Jer; Chien, Wen-Chen; Chiu, Sheng-Shin

The quaternized poly(vinyl alcohol)/alumina (designated as QPVA/Al 2O 3) nanocomposite polymer membrane was prepared by a solution casting method. The characteristic properties of the QPVA/Al 2O 3 nanocomposite polymer membranes were investigated using thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cell (ADMFC) comprised of the QPVA/Al 2O 3 nanocomposite polymer membrane were assembled and examined. Experimental results indicate that the DMFC employing a cheap non-perfluorinated (QPVA/Al 2O 3) nanocomposite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC with 4 M KOH + 1 M CH 3OH, 2 M CH 3OH, and 4 M CH 3OH solutions are 28.33, 32.40, and 36.15 mW cm -2, respectively, at room temperature and in ambient air. The QPVA/Al 2O 3 nanocomposite polymer membranes constitute a viable candidate for applications on alkaline DMFC.

Creep-Fatigue Relationsihps in Electroactive Polymer Systems and Predicted Effects in an Actuator Design

NASA Technical Reports Server (NTRS)

Vinogradov, Aleksandra M.; Ihlefeld, Curtis M.; Henslee, Issac

2009-01-01

The paper concerns the time-dependent behavior of electroactive polymers (EAP) and their use in advanced intelligent structures for space exploration. Innovative actuator design for low weight and low power valves required in small plants planned for use on the moon for chemical analysis is discussed. It is shown that in-depth understanding of cyclic loading effects observed through accelerated creep rates due to creep-fatigue interaction in polymers is critical in terms of proper functioning of EAP based actuator devices. In the paper, an overview of experimental results concerning the creep properties and cyclic creep response of a thin film piezoelectric polymer polyvinylidene fluoride (PVDF) is presented. The development of a constitutive creep-fatigue interaction model to predict the durability and service life of electroactive polymers is discussed. A novel method is proposed to predict damage accumulation and fatigue life of polymers under oyclic loading conditions in the presence of creep. The study provides a basis for ongoing research initiatives at the NASA Kennedy Space Center in the pursuit of new technologies using EAP as active elements for lunar exploration systems.

Essential Medicines in National Constitutions

PubMed Central

Toebes, Brigit; Hogerzeil, Hans

2016-01-01

Abstract A constitutional guarantee of access to essential medicines has been identified as an important indicator of government commitment to the progressive realization of the right to the highest attainable standard of health. The objective of this study was to evaluate provisions on access to essential medicines in national constitutions, to identify comprehensive examples of constitutional text on medicines that can be used as a model for other countries, and to evaluate the evolution of constitutional medicines-related rights since 2008. Relevant articles were selected from an inventory of constitutional texts from WHO member states. References to states’ legal obligations under international human rights law were evaluated. Twenty-two constitutions worldwide now oblige governments to protect and/or to fulfill accessibility of, availability of, and/or quality of medicines. Since 2008, state responsibilities to fulfill access to essential medicines have expanded in five constitutions, been maintained in four constitutions, and have regressed in one constitution. Government commitments to essential medicines are an important foundation of health system equity and are included increasingly in state constitutions. PMID:27781006

Modular analysis of biological networks.

PubMed

Kaltenbach, Hans-Michael; Stelling, Jörg

2012-01-01

The analysis of complex biological networks has traditionally relied on decomposition into smaller, semi-autonomous units such as individual signaling pathways. With the increased scope of systems biology (models), rational approaches to modularization have become an important topic. With increasing acceptance of de facto modularity in biology, widely different definitions of what constitutes a module have sparked controversies. Here, we therefore review prominent classes of modular approaches based on formal network representations. Despite some promising research directions, several important theoretical challenges remain open on the way to formal, function-centered modular decompositions for dynamic biological networks.

The Porosity of Autonomy: Social and Biological Constitution of the Patient in Biomedicine.

PubMed

Beever, Jonathan; Morar, Nicolae

2016-01-01

The nature and role of the patient in biomedicine comprise issues central to bioethical inquiry. Given its developmental history grounded firmly in a backlash against 20th-century cases of egregious human subjects abuse, contemporary medical bioethics has come to rely on a fundamental assumption: the unit of care (and the unit of value) is the autonomous self-directing patient. In this article we examine first the structure of the feminist social critique of autonomy. Then we show that a parallel argument can be made against relational autonomy as well, demonstrating how this second concept of autonomy fails to take sufficiently into account an array of biological determinants, particularly those from microbial biology. Finally, in light of this biological critique, we question whether or to what extent any relevant and meaningful view of autonomy can be recovered in the contemporary landscape of bioethics.

Alkyl Passivation and Amphiphilic Polymer Coating of Silicon Nanocrystals for Diagnostic Imaging

PubMed Central

Hessel, Colin M.; Rasch, Michael R.; Hueso, Jose L.; Goodfellow, Brian W.; Akhavan, Vahid A.; Puvanakrishnan, Priyaveena; Tunnell, James W.

2011-01-01

We show a method to produce biocompatible polymer-coated silicon (Si) nanocrystals for medical imaging. Silica-embedded Si nanocrystals are formed by HSQ thermolysis. The nanocrystals are then liberated from the oxide and terminated with Si-H bonds by HF etching, followed by alkyl monolayer passivation by thermal hydrosilylation. The Si nanocrystals have an average diameter of 2.1 ± 0.6 nm and photoluminesce (PL) with a peak emission wavelength of 650 nm, which lies within the transmission window of 650–900 nm that is useful for biological imaging. The hydrophobic Si nanocrystals are then coated with an amphiphilic polymer for dispersion in aqueous media with pH ranging between 7 and 10 and ionic strength between 30 mM and 2 M, while maintaining a bright and stable PL and a hydrodynamic radius of only 20 nm. Fluorescence imaging of polymer-coated Si nanocrystals in a biological tissue host is demonstrated, showing the potential for in vivo imaging. PMID:20818646

Making the Constitution Meaningful.

ERIC Educational Resources Information Center

Pelow, Randall A.

1989-01-01

Describes learning activities based on the U.S. Constitution that enhance higher level thinking skills in elementary students. One activity proposes a hypothetical constitutional amendment banning Saturday cartoons; a second taxes children's earnings; and other activities focus on dramatizing events surrounding the Constitutional Convention. (LS)

Nanoscale porosity in polymer films: fabrication and therapeutic applications

PubMed Central

Bernards, Daniel A.; Desai, Tejal A.

2011-01-01

This review focuses on current developments in the field of nanostructured bulk polymers and their application in bioengineering and therapeutic sciences. In contrast to well-established nanoscale materials, such as nanoparticles and nanofibers, bulk nanostructured polymers combine nanoscale structure in a macroscopic construct, which enables unique application of these materials. Contemporary fabrication and processing techniques capable of producing nanoporous polymer films are reviewed. Focus is placed on techniques capable of sub-100 nm features since this range approaches the size scale of biological components, such as proteins and viruses. The attributes of these techniques are compared, with an emphasis on the characteristic advantages and limitations of each method. Finally, application of these materials to biofiltration, immunoisolation, and drug delivery are reviewed. PMID:22140398

Impact of co-incorporating laminin peptide dopants and neurotrophic growth factors on conducting polymer properties.

PubMed

Green, Rylie A; Lovell, Nigel H; Poole-Warren, Laura A

2010-01-01

Conductive neural interfaces tailored for cell interaction by incorporation of bioactive factors are hypothesized to produce superior neuroprostheses with improved charge transfer capabilities. This study examined the effect of entrapping nerve growth factor (NGF) within the conducting polymer poly(ethylene dioxythiophene) (PEDOT) during electrodeposition to create a polymer capable of stimulating neurite outgrowth from proximal neural tissue. NGF entrapment was performed on polymers doped with laminin peptides DEDEDYFQRYLI and DCDPGYIGSR and, additionally, a conventional dopant, paratoluene sulphonate (pTS). All polymer coatings were analysed for a range of physical, electrical and mechanical properties, with the biological activity of ligands examined using a PC12 neurite outgrowth assay. NGF was successfully entrapped in PEDOT during electrodeposition and was shown to produce a softer interface than conventional conducting polymers and films without the NGF modification. However, it was found that the use of a peptide dopant combined with NGF entrapment resulted in polymers with diminished electrical and mechanical stability. Entrapped NGF was determined to be biologically active, with PEDOT/pTS/NGF producing neurite outgrowth comparable with control films where NGF was supplied via the medium. Future studies will determine the effect of typical neural prosthetic stimulation regimes on the release of neurotrophins and subsequent cell response.

Numerical-graphical method for describing the creep of damaged highly filled polymer materials

NASA Astrophysics Data System (ADS)

Bykov, D. L.; Martynova, E. D.; Mel'nikov, V. P.

2015-09-01

A method for describing the creep behavior until fracture of a highly filled polymer material previously damaged in preliminary tests is proposed. The constitutive relations are the relations of nonlinear endochronic theory of aging viscoelastic materials (NETAVEM) [1]. The numerical-graphical method for identifying the functions occurring in NETAVEM, which was proposed in [2] for describing loading processes at a constant strain rate, is used here for the first time in creep theory. We use the results of experiments with undamaged and preliminary damaged specimens under the action of the same constant tensile loads. The creep kernel is determined in experiments with an undamaged specimen. The reduced time function contained in NETAVEM is determined from the position of points corresponding to the same values of strain on the creep curves of the damaged and undamaged specimens. An integral equation is solved to obtain the aging function, and then the viscosity function is determined. The knowledge of all functions contained in the constitutive relations permits solving the creep problem for products manufactured from a highly filled polymer material.

Nanometrization of Lanthanide-Based Coordination Polymers.

PubMed

Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

2015-11-23

Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterizing viscoelastic mechanical properties of highly compliant polymers and biological tissues using impact indentation.

PubMed

Mijailovic, Aleksandar S; Qing, Bo; Fortunato, Daniel; Van Vliet, Krystyn J

2018-04-15

Precise and accurate measurement of viscoelastic mechanical properties becomes increasingly challenging as sample stiffness decreases to elastic moduli <1 kPa, largely due to difficulties detecting initial contact with the compliant sample surface. This limitation is particularly relevant to characterization of biological soft tissues and compliant gels. Here, we employ impact indentation which, in contrast to shear rheology and conventional indentation, does not require contact detection a priori, and present a novel method to extract viscoelastic moduli and relaxation time constants directly from the impact response. We first validate our approach by using both impact indentation and shear rheology to characterize polydimethylsiloxane (PDMS) elastomers of stiffness ranging from 100 s of Pa to nearly 10 kPa. Assuming a linear viscoelastic constitutive model for the material, we find that the moduli and relaxation times obtained from fitting the impact response agree well with those obtained from fitting the rheological response. Next, we demonstrate our validated method on hydrated, biological soft tissues obtained from porcine brain, murine liver, and murine heart, and report the equilibrium shear moduli, instantaneous shear moduli, and relaxation time constants for each tissue. Together, our findings provide a new and straightforward approach capable of probing local mechanical properties of highly compliant viscoelastic materials with millimeter scale spatial resolution, mitigating complications involving contact detection or sample geometric constraints. Characterization and optimization of mechanical properties can be essential for the proper function of biomaterials in diverse applications. However, precise and accurate measurement of viscoelastic mechanical properties becomes increasingly difficult with increased compliance (particularly for elastic moduli <1 kPa), largely due to challenges detecting initial contact with the compliant sample surface

Multi-stimuli-responsive biohybrid nanoparticles with cross-linked albumin coronae self-assembled by a polymer-protein biodynamer.

PubMed

Wang, Lin; Liu, Li; Dong, Bingyang; Zhao, Hanying; Zhang, Mingming; Chen, Wenjuan; Hong, Yanhang

2017-05-01

. The prepared biodynamer can offer a potential platform for intracellular protein delivery. The multi-stimuli-responsive biohybrid nanoparticles containing disulfide functionalities are constructed by cross-linking albumin coronae of the biodynamer micelles. With the combination of a thermoresponsive polymer, protein and reversible covalent bonds, the biohybrid nanoparticles are endowed with highly biocompatible, environmentally responsive and adaptive features. These nanoparticles present the ability to undergo changes in their constitution, hydrodynamic size and nanostructure in response to physical, chemical and biological stimuli, which make them interesting candidates as vehicles for drug delivery application and a biomimetic platform to investigate the biological process in nature. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

[The Constitutional Court and new scenarios of biomedicine. (Constitutional reflections on the decision of the Constitutional Tribunal 116/1999, June 17)].

PubMed

Arruego Rodríguez, G; Chueca Rodríguez, R

2000-01-01

The recent ruling by the Constitutional Court (116/1999, 17 June) ended the process which had been initiated by the challenge filed by 63 conservative MPs against Law 35/1988, 22 November, on the Law on Human Assisted Reproduction Techniques. In our opinion, this ruling helps define the scope of the constitutional provisions used by the appellants in their challenge, provisions which had already been interpreted in lower rulings. The considerations given in this article are designed to establish the terms and framework which lawmakers and law experts should bear in mind when they prepare future, as will necessarily be the case. In view of some of the arguments used in the ruling, we believe it is appropriate to draw attention to some of the most salient constitutional aspects, such as the scope of the Constitutional Court's role as the ultimate judge of constitutionality, and the exact nature of the constitutional notion of fundamental right which, although complicated at times, is nonetheless a precise and accurate legal concept.

A critical review of the application of polymer of low concern and regulatory criteria to fluoropolymers.

PubMed

Henry, Barbara J; Carlin, Joseph P; Hammerschmidt, Jon A; Buck, Robert C; Buxton, L William; Fiedler, Heidelore; Seed, Jennifer; Hernandez, Oscar

2018-05-01

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated substances that are in the focus of researchers and regulators due to widespread presence in the environment and biota, including humans, of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Fluoropolymers, high molecular weight polymers, have unique properties that constitute a distinct class within the PFAS group. Fluoropolymers have thermal, chemical, photochemical, hydrolytic, oxidative, and biological stability. They have negligible residual monomer and oligomer content and low to no leachables. Fluoropolymers are practically insoluble in water and not subject to long-range transport. With a molecular weight well over 100 000 Da, fluoropolymers cannot cross the cell membrane. Fluoropolymers are not bioavailable or bioaccumulative, as evidenced by toxicology studies on polytetrafluoroethylene (PTFE): acute and subchronic systemic toxicity, irritation, sensitization, local toxicity on implantation, cytotoxicity, in vitro and in vivo genotoxicity, hemolysis, complement activation, and thrombogenicity. Clinical studies of patients receiving permanently implanted PTFE cardiovascular medical devices demonstrate no chronic toxicity or carcinogenicity and no reproductive, developmental, or endocrine toxicity. This paper brings together fluoropolymer toxicity data, human clinical data, and physical, chemical, thermal, and biological data for review and assessment to show that fluoropolymers satisfy widely accepted assessment criteria to be considered as "polymers of low concern" (PLC). This review concludes that fluoropolymers are distinctly different from other polymeric and nonpolymeric PFAS and should be separated from them for hazard assessment or regulatory purposes. Grouping fluoropolymers with all classes of PFAS for "read across" or structure-activity relationship assessment is not scientifically appropriate. Integr Environ Assess Manag 2018;14:316-334. © 2018 The Authors

Framework for analyzing hyper-viscoelastic polymers

NASA Astrophysics Data System (ADS)

Trivedi, Akash; Siviour, Clive

2017-06-01

Hyper-viscoelastic polymers have multiple areas of application including aerospace, biomedicine, and automotive. Their mechanical responses are therefore extremely important to understand, particularly because they exhibit strong rate and temperature dependence, including a low temperature brittle transition. Relationships between the response at various strain rates and temperatures are investigated and a framework developed to predict response at rates where experiments are unfeasible. A master curve of the storage modulus's rate dependence at a reference temperature is constructed using a DMA test of the polymer. A frequency sweep spanning two decades and a temperature range from pre-glass transition to pre-melt is used. A fractional derivative model is fitted to the experimental data, and this model's parameters are used to derive stress-strain relationships at a desired strain rate. Finite element simulations with this constitutive model are used for verification with experimental data. This material is based upon work supported by the Air Force Office of Scientific Research, Air Force Materiel Command, USAF under Award No. FA9550-15-1-0448.

Molecularly imprinted polymer sensors for detection in the gas, liquid, and vapor phase.

PubMed

Jenkins, Amanda L; Ellzy, Michael W; Buettner, Leonard C

2012-06-01

Fast, reliable, and inexpensive analytical techniques for detection of airborne chemical warfare agents are desperately needed. Recent advances in the field of molecularly imprinted polymers have created synthetic nanomaterials that can sensitively and selectively detect these materials in aqueous environments, but thus far, they have not been demonstrated to work for detection of vapors. The imprinted polymers function by mimicking the function of biological receptors. They can provide high sensitivity and selectivity but, unlike their biological counterparts, maintain excellent thermal and mechanical stability. The traditional imprinted polymer approach is further enhanced in this work by the addition of a luminescent europium that has been introduced into the polymers to provide enhanced chemical affinity as well as a method for signal transduction to indicate the binding event. The europium in these polymers is so sensitive to the bound target; it can distinguish between species differing by a single methyl group. The imprinted polymer technology is fiber optic-based making it inexpensive and easily integratable with commercially available miniature fiber optic spectrometer technologies to provide a shoebox size device. In this work, we will describe efforts to apply these sensors for detection of airborne materials and vapors. Successful application of this technology will provide accurate low level vapor detection of chemical agents or pesticides with little to no false positives. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.

Macro and micro analysis of small molecule diffusion in amorphous polymers

NASA Astrophysics Data System (ADS)

Putta, Santosh Krishna

In this study, both macroscopic and microscopic numerical techniques have been explored, to model and understand the diffusion behavior of small molecules in amorphous polymers, which very often do not follow the classical Fickian law. It was attempted to understand the influence of various aspects of the molecular structure of a polymer on its macroscopic diffusion behavior. At the macroscopic level, a hybrid finite-element/finite-difference model is developed to implement the coupled diffusion and deformation constitutive equations. A viscoelasticity theory, combined with time-freevolume superposition is used to model the deformation processes. A freevolume-based model is used to model the diffusion processes. The freevolume in the polymer is used as a coupling factor between the deformation and the diffusion processes. The model is shown to qualitatively describe some of the typical non-Fickian diffusion behavior in polymers. However, it does not directly involve the microstructure of a polymer. Further, some of the input parameters to the model are difficult to obtain experimentally. A numerical microscopic approach is therefore adopted to study the molecular structure of polymers. A molecular mechanics and dynamics technique combined with a modified Rotational Isomeric State (RIS) approach, is followed to generate the molecular structure for two types of polycarbonates, and, two types of polyacrylates, starting only with their chemical structures. A new efficient 3-D algorithm for Delaunay Tessellation is developed, and, then applied to discretize the molecular structure into Delaunay Tetrahedra. By using the dicretized molecular structure, size, shape, and, connectivity of free-spaces for small molecule diffusion in the above mentioned polymers, are then studied in relation to their diffusion properties. The influence of polymer and side chain flexibility, and diffusant-diffusant and diffusant-polymer molecular interactions, is also discussed with respect to

Understanding selective molecular recognition in integrated carbon nanotube-polymer sensors by simulating physical analyte binding on carbon nanotube-polymer scaffolds.

PubMed

Lin, Shangchao; Zhang, Jingqing; Strano, Michael S; Blankschtein, Daniel

2014-08-28

Macromolecular scaffolds made of polymer-wrapped single-walled carbon nanotubes (SWCNTs) have been explored recently (Zhang et al., Nature Nanotechnology, 2013) as a new class of molecular-recognition motifs. However, selective analyte recognition is still challenging and lacks the underlying fundamental understanding needed for its practical implementation in biological sensors. In this report, we combine coarse-grained molecular dynamics (CGMD) simulations, physical adsorption/binding theories, and photoluminescence (PL) experiments to provide molecular insight into the selectivity of such sensors towards a large set of biologically important analytes. We find that the physical binding affinities of the analytes on a bare SWCNT partially correlate with their distribution coefficients in a bulk water/octanol system, suggesting that the analyte hydrophobicity plays a key role in determining the binding affinities of the analytes considered, along with the various specific interactions between the analytes and the polymer anchor groups. Two distinct categories of analytes are identified to demonstrate a complex picture for the correlation between optical sensor signals and the simulated binding affinities. Specifically, a good correlation was found between the sensor signals and the physical binding affinities of the three hormones (estradiol, melatonin, and thyroxine), the neurotransmitter (dopamine), and the vitamin (riboflavin) to the SWCNT-polymer scaffold. The four amino acids (aspartate, glycine, histidine, and tryptophan) and the two monosaccharides (fructose and glucose) considered were identified as blank analytes which are unable to induce sensor signals. The results indicate great success of our physical adsorption-based model in explaining the ranking in sensor selectivities. The combined framework presented here can be used to screen and select polymers that can potentially be used for creating synthetic molecular recognition motifs.

Design of polymer motifs for nucleic acid recognition and assembly stabilization

NASA Astrophysics Data System (ADS)

Zhou, Zhun

This dissertation describes the synthesis and assembly of bio-functional polymers and the applications of these polymers to drug encapsulation, delivery, and multivalent biomimetic macromolecular recognition between synthetic polymer and nucleic acids. The main content is divided into three parts: (1) polyacidic domains as strongly stabilizing design elements for aqueous phase polyacrylate diblock assembly; (2) small molecule/polymer recognition triggered macromolecular assembly and drug encapsulation; (3) trizaine derivatized polymer as a novel class of "bifacial polymer nucleic acid" (bPoNA) and applications of bPoNA to nanoparticle loading of DNA/RNA, silencing delivery as well as control of aptamer function. Through the studies in part (1) and part (2), it was demonstrated that well-designed polymer motifs are not only able to enhance assemblies driven by non-specific hydrophobic effect, but are also able to direct assemblies based on specific recognitions. In part (3) of this dissertation, this concept was further extended by the design of polyacrylate polymers that are capable of discrete and robust hybridization with nucleic acids. This surprising finding demonstrated both fundamental and practical applications. Overall, these studies provided insights into the rational design elements for improving the bio-functions of synthetic polymers, and significantly expanded the scope of biological applications in which polymers synthesized via controlled radical polymerization may play a role.

Pyro-electrification of polymer membranes for cell patterning

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

Rega, R.; Gennari, O.; Mecozzia, L.

2016-05-18

In the recent years, much attention has been devoted to the possibility of charging polymer-based materials, due to their potential in developing large-scale and inexpensive flexible thin-film technology. The availability of localized electrostatic fields is in of great interest for a huge amount of applications such as distribution of biomolecules and cells from the liquid phase. Here we report a voltage-free pyro-electrification (PE) process able to induce permanent dipoles into polymer layers; the lithium niobate (LN) crystal is the key component that plays the multi-purpose role of sustaining, heating and poling the polymer layer that is then peeled-off easily inmore » order to have a free-standing charged membrane. The results show the fascinating application for the living cell patterning. It well known that cell behaviour is affected by chemical and topographical cues of substrate. In fact, polymers, such as polystyrene (PS) and poly(methyl methacrylate) (PMMA), are naturally cytophobic and require specific functionalization treatments in order to promote cell adhesion. Through our proposal technique, it’s possible to obtain spontaneous organization and a driven growth of SH-SY5Y cells that is solely dictated by the nature of the charge polymer surface, opening, in this way, the innovative chance to manipulate and transfer biological samples on a free-standing polymer layer [1].« less

Modelling electro-active polymers with a dispersion-type anisotropy

NASA Astrophysics Data System (ADS)

Hossain, Mokarram; Steinmann, Paul

2018-02-01

We propose a novel constitutive framework for electro-active polymers (EAPs) that can take into account anisotropy with a chain dispersion. To enhance actuation behaviour, particle-filled EAPs become promising candidates nowadays. Recent studies suggest that particle-filled EAPs, which can be cured under an electric field during the manufacturing time, do not necessarily form perfect anisotropic composites, rather they create composites with dispersed chains. Hence in this contribution, an electro-mechanically coupled constitutive model is devised that considers the chain dispersion with a probability distribution function in an integral form. To obtain relevant quantities in discrete form, numerical integration over the unit sphere is utilized. Necessary constitutive equations are derived exploiting the basic laws of thermodynamics that result in a thermodynamically consistent formulation. To demonstrate the performance of the proposed electro-mechanically coupled framework, we analytically solve a non-homogeneous boundary value problem, the extension and inflation of an axisymmetric cylindrical tube under electro-mechanically coupled load. The results capture various electro-mechanical couplings with the formulation proposed for EAP composites.

Constitutional Thinness and Anorexia Nervosa: A Possible Misdiagnosis?

PubMed Central

Estour, Bruno; Galusca, Bogdan; Germain, Natacha

2014-01-01

Clinical and biological aspects of restrictive anorexia nervosa (R-AN) are well documented. More than 10,000 articles since 1911 and more than 600 in 2013 have addressed R-AN psychiatric, somatic, and biological aspects. Genetic background, ineffectiveness of appetite regulating hormones on refeeding process, bone loss, and place of amenorrhea in the definition are widely discussed and reviewed. Oppositely, constitutional thinness (CT) is an almost unknown entity. Only 32 articles have been published on this topic since 1953. Similar symptoms associating low body mass index, low fat, and bone mass are reported in both CT and R-AN subjects. Conversely, menses are preserved in CT women and almost the entire hormonal profile is normal, except for leptin and PYY. The aim of the present review is to alert the clinician on the confusing clinical presentation of these two situations, a potential source of misdiagnosis, especially since R-AN definition has changed in DSM5. PMID:25368605

Constitutional thinness and anorexia nervosa: a possible misdiagnosis?

PubMed

Estour, Bruno; Galusca, Bogdan; Germain, Natacha

2014-01-01

Clinical and biological aspects of restrictive anorexia nervosa (R-AN) are well documented. More than 10,000 articles since 1911 and more than 600 in 2013 have addressed R-AN psychiatric, somatic, and biological aspects. Genetic background, ineffectiveness of appetite regulating hormones on refeeding process, bone loss, and place of amenorrhea in the definition are widely discussed and reviewed. Oppositely, constitutional thinness (CT) is an almost unknown entity. Only 32 articles have been published on this topic since 1953. Similar symptoms associating low body mass index, low fat, and bone mass are reported in both CT and R-AN subjects. Conversely, menses are preserved in CT women and almost the entire hormonal profile is normal, except for leptin and PYY. The aim of the present review is to alert the clinician on the confusing clinical presentation of these two situations, a potential source of misdiagnosis, especially since R-AN definition has changed in DSM5.

Modelling Polymer Deformation and Welding Behaviour during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

2016-11-01

3D printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The most common method, fused deposition modelling, involves melting a thermoplastic, followed by layer-by-layer extrusion of the material to fabricate a three-dimensional object. The key to the ensuring strength at the weld between these layers is successful inter-diffusion. However, as the printed layer cools towards the glass transition temperature, the time available for diffusion is limited. In addition, the extrusion process significantly deforms the polymer micro-structure prior to welding and consequently affects how the polymers "re-entangle" across the weld. We have developed a simple model of the non-isothermal printing process to explore the effects that typical printing conditions and amorphous polymer rheology have on the ultimate weld structure. In particular, we incorporate both the stretch and orientation of the polymer using the Rolie-Poly constitutive equation to examine how the melt flows through the nozzle and is deposited onto the build plate. We then address how this deformation relaxes and contributes to the thickness and structure of the weld. National Institute for Standards and Technology (NIST) and Georgetown University.

Polymer-ceramic nanocomposites for applications in the bone surgery

NASA Astrophysics Data System (ADS)

Stodolak, E.; Gadomska, K.; Lacz, A.; Bogun, M.

2009-01-01

The subject of this work was preparation and investigation of properties of a nanocomposite material based on polymer matrix modified with nanometric silica particles (SiO2). The composite matrix consisted of resorbable P(L/DL)LA polymer with certified biocompatibility. Nanometric silica was introduced into the matrix by means of ultrasonic homogenisation and/or mechanical stirring. The silica was introduced directly e.g. as nanoparticles or inside calcium alginate fibres which contained 3 wt.% of amorphous SiO2. Proper dispersion of nano-filliers was confirmed by means of thermal analysis (TG/DTA, DSC). It was observed, that the presence of inorganic nanoparticles influenced several surface parameters of the nanocomposites i.e. hydrophility (a decrease of surface energy) and topography (both in micro- and nano-scale). Additionally, the nanocomposites exhibited enhanced mechanical properties (Young's modulus, tensile strength) compared to the pure polymer. The nanocomposites were bioactive materials (SBF/3 days/37oC). Biological tests (MTT test) showed a good viability of human osteoblasts (hFOB 1.19) in contact with the nanocomposites surface. Results of preliminary biological tests carried out with the use of mother cells extracted from human bone marrow showed that the nanocomposites may provide differenation of bone cells.

Constitutive Endocytosis of VEGFR2 Protects the Receptor against Shedding.

PubMed

Basagiannis, Dimitris; Christoforidis, Savvas

2016-08-05

VEGFR2 plays a fundamental role in blood vessel formation and in life threatening diseases, such as cancer angiogenesis and cardiovascular disorders. Although inactive growth factor receptors are mainly localized at the plasma membrane, VEGFR2 undergoes constitutive endocytosis (in the absence of ligand) and recycling. Intriguingly, the significance of these futile transport cycles of VEGFR2 remains unclear. Here we found that, unexpectedly, the function of constitutive endocytosis of VEGFR2 is to protect the receptor against plasma membrane cleavage (shedding), thereby preserving the functional state of the receptor until the time of activation by VEGF. Inhibition of constitutive endocytosis of VEGFR2, by interference with the function of clathrin, dynamin, or Rab5, increases dramatically the cleavage/shedding of VEGFR2. Shedding of VEGFR2 produces an N-terminal soluble fragment (100 kDa, s100), which is released in the extracellular space, and a residual C-terminal part (130 kDa, p130) that remains integrated at the plasma membrane. The released soluble fragment (s100) co-immunoprecipitates with VEGF, in line with the topology of the VEGF-binding domain at the N terminus of VEGFR2. Increased shedding of VEGFR2 (via inhibition of constitutive endocytosis) results in reduced response to VEGF, consistently with the loss of the VEGF-binding domain from the membrane remnant of VEGFR2. These data suggest that constitutive internalization of VEGFR2 protects the receptor against shedding and provides evidence for an unprecedented mechanism via which endocytosis can regulate the fate and activity of growth factor receptors. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

What Would Constitute Evidence for Life on Icy Moons?

NASA Technical Reports Server (NTRS)

Pohorille, A.; Hoehler, T. M.

2017-01-01

For the first time since Viking, NASA is considering missions that would include life detection as a primary objective, making it critical to develop and evaluate a diverse set of strategies for seeking evidence of life. The central question is: what should be the target of our search that, if found, would constitute a near-certain evidence for life? Since life on icy moons might be quite different from terrestrial life, we should concentrate on features of biological systems that are considered universal and are unlikely to emerge through abiotic means.

Identification of Novel Activators of Constitutive Androstane Receptor from FDA-approved Drugs by Integrated Computational and Biological Approaches

PubMed Central

Lynch, Caitlin; Pan, Yongmei; Li, Linhao; Ferguson, Stephen S.; Xia, Menghang; Swaan, Peter W.; Wang, Hongbing

2012-01-01

Purpose The constitutive androstane receptor (CAR, NR1I3) is a xenobiotic sensor governing the transcription of numerous hepatic genes associated with drug metabolism and clearance. Recent evidence suggests that CAR also modulates energy homeostasis and cancer development. Thus, identification of novel human (h) CAR activators is of both clinical importance and scientific interest. Methods Docking and ligand-based structure-activity models were used for virtual screening of a database containing over 2000 FDA-approved drugs. Identified lead compounds were evaluated in cell-based reporter assays to determine hCAR activation. Potential activators were further tested in human primary hepatocytes (HPHs) for the expression of the prototypical hCAR target gene CYP2B6. Results Nineteen lead compounds with optimal modeling parameters were selected for biological evaluation. Seven of the 19 leads exhibited moderate to potent activation of hCAR. Five out of the seven compounds translocated hCAR from the cytoplasm to the nucleus of HPHs in a concentration-dependent manner. These compounds also induce the expression of CYP2B6 in HPHs with rank-order of efficacies closely resembling that of hCAR activation. Conclusion These results indicate that our strategically integrated approaches are effective in the identification of novel hCAR modulators, which may function as valuable research tools or potential therapeutic molecules. PMID:23090669

Engineering the bio-nano interface using a multi-functional polymer coating

NASA Astrophysics Data System (ADS)

Wang, Wentao

Interfacing inorganic nanoparticles with biological systems to develop a variety of novel imaging, sensing and diagnostic tools has generated great interest and much activity over the past two decades. However, the effectiveness of this approach hinges on the ability to prepare water dispersible nanoparticles, with compact size and long term colloidal stability in biological environments, and the development of controlled conjugation to various biomolecules. The primary focus of this dissertation is the design and synthesis, characterization and use of a series of new multidentate and multifunctional coordinating polymers as ligands that render various inorganic nanocrystals water soluble, In Chapter 1 we introduce the basic physical properties of quantum dots (QDs), gold nanocrystals and magnetic nanocrystals along with brief description of their syntheses. We then provide an overview of surface functionalization strategies and recent progress in the ligand chemistry, followed by highlights of a few conjugation approaches applied to nanoparticles in biology. We then discuss modulation of the optical and spectroscopic properties of QDs via energy and charge transfer interactions. We conclude by presenting a few related examples on the incorporation of QD-conjugates into sensor design and intracellular imaging. In Chapter 2, we report the design of a series of multifunctional polymers as ligands for surface engineering of QDs and facilitating their use in bioconjugation. First, we introduce a novel PEGylated polymer that combines the synergies of metal-chelation promoted by lipoic acid and imidazole groups, as effective coating for the surface functionalization of QDs; one of the goals was to address the problems associated with thiol oxidation and weak imidazole affinity. Second, to minimize the hydrodynamic radius of the QDs without sacrificing aqueous solubility, a set of polymer ligands appended with zwitterion and imidazole motifs have been synthesized applied

Microstereolithography for polymer-based based MEMS

NASA Astrophysics Data System (ADS)

Varadan, Vijay K.; Xie, Jining

2003-07-01

Microfabrication techniques such as bulk micromachining and surface micromachining currently employed to conceive MEMS are largely derived from the standard IC and microelectronics technology. Even though many MEMS devices with integrated electronics have been achieved by using the traditional micromachining techniques, some limitations have nevertheless to be underlined: 1) these techniques are very expensive and need specific installations as well as a cleanroom environment, 2) the materials that can be used up to now are restricted to silicon and metals, 3) the manufacture of 3D parts having curved surfaces or an important number of layers is not possible. Moreover, for some biological applications, the materials used for sensors must be compatible with human body and the actuators need to have high strain and displacement which the current silicon based MEMS do not provide. It is thus natural for the researchers to 'look' for alternative methods such as Microstereolithography (MSL) to make 3D sensors and actuators using polymeric based materials. For MSL techniques to be successful as their silicon counterparts, one has to come up with multifunctional polymers with electrical properties comparable to silicon. These multifunctional polymers should not only have a high sensing capability but also a high strain and actuation performance. A novel UV-curable polymer uniformly bonded with functionalized nanotubes was synthesized via a modified three-step in-situ polymerization. Purified multi-walled nanotubes, gained from the microwave chemical vapor deposition method, were functionalized by oxidation. The UV curable polymer was prepared from toluene diisocyanate (TDI), functionalized nanotubes, and 2-hydroxyethyl methacrylate (HEMA). The chemical bonds between -NCO groups of TDI and -OH, -COOH groups of functionalized nanotubes help for conceiving polymeric based MEMS devices. A cost effective fabrication techniques was presented using Micro Stereo Lithography and

Thermodynamics and mechanics of photochemcially reacting polymers

NASA Astrophysics Data System (ADS)

Long, Rong; Qi, H. Jerry; Dunn, Martin L.

2013-11-01

We develop a thermodynamics and mechanics theory for polymers that when irradiated with light, undergo photochemical reactions that alter their macromolecular structure, e.g., by bond breaking and/or reformation, and in turn affect their mechanical and physical behavior. This emerging class of highly-engineered active materials shows great promise for myriad applications and is a subset of a broader class of polymers with covalent bonds that can be dynamically tuned with various environmental stimuli. We formulate a general thermodynamic and kinetic framework to model the complex photochemical-thermal-mechanical coupling in these materials. Our theory considers the behavior of a polymer that is subjected to the combination of mechanical and thermal loading while simultaneously irradiated by light with multiple frequency components and directions. We introduce an approach to model the photochemical reactions that can change the network topology, resulting chemical species transport, heat conduction and finite deformation. We describe the interaction of the material with light via a radiometric description and show how it can be linked to a full electromagnetic treatment when appropriate and if desired. Our approach is sufficiently general to permit the modeling of various materials that operate via different photochemical reaction mechanisms. After formulating the general theory, we specialize it to a polymer that when irradiated with light undergoes a series of photochemical reactions that cause chain scission and reformation which continuously rearrange the polymer network into a stress-free configuration. Based on the operant physical mechanisms we develop a constitutive model using a polymer chain decomposition and evolution approach to track the molecular structure changes during simultaneous irradiation and mechanical loading. In the special case of isothermal conditions with monochromatic and unidirectional irradiation, we recover a previous model based on

This Constitution: A Bicentennial Chronicle.

ERIC Educational Resources Information Center

This Constitution, 1984

1984-01-01

A series of articles focus on enduring Constitutional issues and methods for teaching about these in the classroom. Article 1 explores the nature of the judiciary as it has developed under the Constitution. Article 2, by discussing the uses of the Constitution in plays of the Federal Theater Project of the 1930's, examines the Constitution as a…

Exploring the role of peptides in polymer-based gene delivery.

PubMed

Sun, Yanping; Yang, Zhen; Wang, Chunxi; Yang, Tianzhi; Cai, Cuifang; Zhao, Xiaoyun; Yang, Li; Ding, Pingtian

2017-09-15

Polymers are widely studied as non-viral gene vectors because of their strong DNA binding ability, capacity to carry large payload, flexibility of chemical modifications, low immunogenicity, and facile processes for manufacturing. However, high cytotoxicity and low transfection efficiency substantially restrict their application in clinical trials. Incorporating functional peptides is a promising approach to address these issues. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we systematically summarize the role of peptides in polymer-based gene delivery, and elaborate how to rationally design polymer-peptide based gene delivery vectors. Polymers are widely studied as non-viral gene vectors, but suffer from high cytotoxicity and low transfection efficiency. Incorporating short, bioactive peptides into polymer-based gene delivery systems can address this issue. Peptides demonstrate various functions in polymer-based gene delivery systems, such as targeting to specific cells, breaching membrane barriers, facilitating DNA condensation and release, and lowering cytotoxicity. In this review, we highlight the peptides' roles in polymer-based gene delivery, and elaborate how to utilize various functional peptides to enhance the transfection efficiency of polymers. The optimized peptide-polymer vectors should be able to alter their structures and functions according to biological microenvironments and utilize inherent intracellular pathways of cells, and consequently overcome the barriers during gene delivery to enhance transfection efficiency. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

High Strain Rate Deformation Modeling of a Polymer Matrix Composite. Part 2; Composite Micromechanical Model

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Stouffer, Donald C.

1998-01-01

Recently applications have exposed polymer matrix composite materials to very high strain rate loading conditions, requiring an ability to understand and predict the material behavior under these extreme conditions. In this second paper of a two part report, a three-dimensional composite micromechanical model is described which allows for the analysis of the rate dependent, nonlinear deformation response of a polymer matrix composite. Strain rate dependent inelastic constitutive equations utilized to model the deformation response of a polymer are implemented within the micromechanics method. The deformation response of two representative laminated carbon fiber reinforced composite materials with varying fiber orientation has been predicted using the described technique. The predicted results compare favorably to both experimental values and the response predicted by the Generalized Method of Cells, a well-established micromechanics analysis method.

Tellurium-containing polymer micelles: competitive-ligand-regulated coordination responsive systems.

PubMed

Cao, Wei; Gu, Yuwei; Meineck, Myriam; Li, Tianyu; Xu, Huaping

2014-04-02

Nanomaterials capable of achieving tunable cargo release kinetics are of significance in a fundamental sense and various biological or medical applications. We report a competitive coordination system based on a novel tellurium-containing polymer and its ligand-regulated release manners. Tellurium was introduced to water-soluble polymers for the first time as drug delivery vehicles. The coordination chemistry between platinum and tellurium was designed to enable the load of platinum-based drugs. Through the competitive coordination of biomolecules, the drugs could be released in a controlled manner. Furthermore, the release kinetics could be modulated by the competitive ligands involved due to their different coordination ability. This tellurium-containing polymer may enrich the family of delivery systems and provide a new platform for future biomedical nanotechnologies.

The analytical change in plasma creatinine that constitutes a biologic/physiologic change.

PubMed

Toffaletti, John G; Hammett-Stabler, Catherine A; Gearhart, Margaret; Roy Choudhury, Kingshuk; Handel, Elizabeth A

2016-08-01

Accurate and precise measurements of creatinine are necessary to evaluate changes in kidney function related to a decreased glomerular filtration rate (GFR). When serial measurements of creatinine are monitored in an individual, it is useful to know what magnitude of an analytical change in creatinine indicates a true physiologic/biologic change in plasma creatinine that might warrant clinical intervention. We compared results between three different methods for creatinine using large chemistry analyzers, two based on alkaline picrate (AP1 and AP2), and one based on dry-slide enzymatic conversion (ENZ). On each of three different segments or days of the study spaced 1-2months apart, we selected 10 different plasma samples having creatinine concentrations ranging from about 0.5mg/dL to 4.5mg/dL (44 to 400μmol/L). Each sample was analyzed in triplicate on each of two same-model analyzers at each institution, then from this data we determined the precision of each model of analyzer. The within-instrument precision of each analyzer was evaluated from the differences between the triplicate results on each sample by each analyzer (mean and SD of the differences). The between-instrument precision was evaluated as the differences between results on the same sample (1, 2, 3, etc.) analyzed on different analyzers of the same model (A and B). This between-analyzer precision data was used to determine both the range and mean±2SD of the differences that could be used to indicate that greater changes in creatinine concentrations would represent a biologic change. The within-instrument precision was best for the ENZ method in comparison to the two alkaline picrate rate methods. The between-instrument precision of the 90 consecutive measurements (30 samples×triplicate analyses) between the same-model analyzers were (mean and SD of differences in mg/dL): -0.018 and 0.029 (ENZ); 0.016 and 0.11 (AP1), and -0.058 and 0.071 (AP2). While all three of the creatinine methods studied

Healable thermoset polymer composite embedded with stimuli-responsive fibres

PubMed Central

Li, Guoqiang; Meng, Harper; Hu, Jinlian

2012-01-01

Severe wounds in biological systems such as human skin cannot heal themselves, unless they are first stitched together. Healing of macroscopic damage in thermoset polymer composites faces a similar challenge. Stimuli-responsive shape-changing polymeric fibres with outstanding mechanical properties embedded in polymers may be able to close macro-cracks automatically upon stimulation such as heating. Here, a stimuli-responsive fibre (SRF) with outstanding mechanical properties and supercontraction capability was fabricated for the purpose of healing macroscopic damage. The SRFs and thermoplastic particles (TPs) were incorporated into regular thermosetting epoxy for repeatedly healing macroscopic damages. The system works by mimicking self-healing of biological systems such as human skin, close (stitch) then heal, i.e. close the macroscopic crack through the thermal-induced supercontraction of the SRFs, and bond the closed crack through melting and diffusing of TPs at the crack interface. The healing efficiency determined using tapered double-cantilever beam specimens was 94 per cent. The self-healing process was reasonably repeatable. PMID:22896563

Dual-emissive Polymer Dots for Rapid Detection of Fluoride in Pure Water and Biological Systems with Improved Reliability and Accuracy

PubMed Central

Zhao, Qiang; Zhang, Chuanqi; Liu, Shujuan; Liu, Yahong; Zhang, Kenneth Yin; Zhou, Xiaobo; Jiang, Jiayang; Xu, Wenjuan; Yang, Tianshe; Huang, Wei

2015-01-01

It is of paramount importance to develop new probes that can selectively, sensitively, accurately and rapidly detect fluoride in aqueous media and biological systems, because F- is found to be closely related to many health and environmental concerns. Herein, a dual-emissive conjugated polyelectrolyte P1 containing phosphorescent iridium(III) complex was designed and synthesized, which can form ultrasmall polymer dots (Pdots) in aqueous media. The F--responsive tert-butyldiphenylsilyl moiety was introduced into iridium(III) complex as the signaling unit for sensing F− with the quenched phosphorescence. Thus, the dual-emissive Pdots can rapidly and accurately detect F− in aqueous media and live cells as a ratiometric probe by measuring the change in the ratio of the F−-sensitive red phosphorescence from iridium(III) complex to the F−-insensitive blue fluorescence from polyfluorene. Moreover, the interaction of Pdots with F− also changes its emission lifetime, and the lifetime-based detection of F− in live cells has been realized through photoluminescence lifetime imaging microscopy for the first time. Both the ratiometric luminescence and lifetime imaging have been demonstrated to be resistant to external influences, such as the probe’s concentration and excitation power. This study provides a new perspective for the design of promising Pdots-based probes for biological applications. PMID:26552859

Energy transfer and drag reduction in elasto-inertial turbulence laden with elongated contravariant and covariant polymers

NASA Astrophysics Data System (ADS)

Horiuti, Kiyosi

2015-11-01

We study elongation and energy-transfer process of polymers released in the homogeneous isotropic turbulence by connecting mesoscopic Brownian description of elastic dumbbells to macroscopic description for the solvent (DNS). The dumbbells are allowed to be advected either affinely with the macroscopically-imposed deformation (contravariant) or completely non-affinely (covariant). We consider the elasto-inertial regime in which the relaxation time of polymer is in the order of the eddy turnover time. Highly-elongated contravariant polymers remove more energy from the large scales than they can dissipate and transfer the excess energy back into the solvent as in P.C. Valente et al. (2014). By deriving the approximate solution of the constitutive equation for the polymer stress (Horiuti et al. 2013), we identified the term responsible for causing this transfer. The skewness of the strain-rate tensor (SikSklSli) in the elastic energy production term transfer the elastic energy back into the smallest scale of the solvent and increase the dissipation. In the covariant polymers, this trend is reversed and leads to enhancement of drag reduction, in accordance with the hypothesis that stretched polymers may behave like rods and exhibit rigidity (de Gennes 1986).

Contesting the Constitution: The Constitutional Dialogues.

ERIC Educational Resources Information Center

Hilenski, Ferdinand Alexi

This historical dramatization, prepared for presentation at the 1985 Wyoming Chatauqua, contains three dialogues, set during the administration of President Thomas Jefferson and presenting the issues surrounding the drafting and ratification of the U.S. Constitution. The dialogues are designed to be presented in three segments to permit discussion…

Biomaterials-based electronics: polymers and interfaces for biology and medicine.

PubMed

Muskovich, Meredith; Bettinger, Christopher J

2012-05-01

Advanced polymeric biomaterials continue to serve as a cornerstone for new medical technologies and therapies. The vast majority of these materials, both natural and synthetic, interact with biological matter in the absence of direct electronic communication. However, biological systems have evolved to synthesize and utilize naturally-derived materials for the generation and modulation of electrical potentials, voltage gradients, and ion flows. Bioelectric phenomena can be translated into potent signaling cues for intra- and inter-cellular communication. These cues can serve as a gateway to link synthetic devices with biological systems. This progress report will provide an update on advances in the application of electronically active biomaterials for use in organic electronics and bio-interfaces. Specific focus will be granted to covering technologies where natural and synthetic biological materials serve as integral components such as thin film electronics, in vitro cell culture models, and implantable medical devices. Future perspectives and emerging challenges will also be highlighted. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biomaterials-Based Electronics: Polymers and Interfaces for Biology and Medicine

PubMed Central

Muskovich, Meredith; Bettinger, Christopher J.

2012-01-01

Advanced polymeric biomaterials continue to serve as a cornerstone of new medical technologies and therapies. The vast majority of these materials, both natural and synthetic, interact with biological matter without direct electronic communication. However, biological systems have evolved to synthesize and employ naturally-derived materials for the generation and modulation of electrical potentials, voltage gradients, and ion flows. Bioelectric phenomena can be interpreted as potent signaling cues for intra- and inter-cellular communication. These cues can serve as a gateway to link synthetic devices with biological systems. This progress report will provide an update on advances in the application of electronically active biomaterials for use in organic electronics and bio-interfaces. Specific focus will be granted to the use of natural and synthetic biological materials as integral components in technologies such as thin film electronics, in vitro cell culture models, and implantable medical devices. Future perspectives and emerging challenges will also be highlighted. PMID:23184740

Towards highly stable polymer electronics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Nikolka, Mark; Nasrallah, Iyad; Broch, Katharina; Sadhanala, Aditya; Hurhangee, Michael; McCulloch, Iain; Sirringhaus, Henning

2016-11-01

Due to their ease of processing, organic semiconductors are promising candidates for applications in high performance flexible displays and fast organic electronic circuitry. Recently, a lot of advances have been made on organic semiconductors exhibiting surprisingly high performance and carrier mobilities exceeding those of amorphous silicon. However, there remain significant concerns about their operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode (OLED) displays. Here, we report a novel technique for dramatically improving the operational stress stability, performance and uniformity of high mobility polymer field-effect transistors by the addition of specific small molecule additives to the polymer semiconductor film. We demonstrate for the first time polymer FETs that exhibit stable threshold voltages with threshold voltage shifts of less than 1V when subjected to a constant current operational stress for 1 day under conditions that are representative for applications in OLED active matrix displays. The approach constitutes in our view a technological breakthrough; it also makes the device characteristics independent of the atmosphere in which it is operated, causes a significant reduction in contact resistance and significantly improves device uniformity. We will discuss in detail the microscopic mechanism by which the molecular additives lead to this significant improvement in device performance and stability.

"Polymeromics": Mass spectrometry based strategies in polymer science toward complete sequencing approaches: a review.

PubMed

Altuntaş, Esra; Schubert, Ulrich S

2014-01-15

Mass spectrometry (MS) is the most versatile and comprehensive method in "OMICS" sciences (i.e. in proteomics, genomics, metabolomics and lipidomics). The applications of MS and tandem MS (MS/MS or MS(n)) provide sequence information of the full complement of biological samples in order to understand the importance of the sequences on their precise and specific functions. Nowadays, the control of polymer sequences and their accurate characterization is one of the significant challenges of current polymer science. Therefore, a similar approach can be very beneficial for characterizing and understanding the complex structures of synthetic macromolecules. MS-based strategies allow a relatively precise examination of polymeric structures (e.g. their molar mass distributions, monomer units, side chain substituents, end-group functionalities, and copolymer compositions). Moreover, tandem MS offer accurate structural information from intricate macromolecular structures; however, it produces vast amount of data to interpret. In "OMICS" sciences, the software application to interpret the obtained data has developed satisfyingly (e.g. in proteomics), because it is not possible to handle the amount of data acquired via (tandem) MS studies on the biological samples manually. It can be expected that special software tools will improve the interpretation of (tandem) MS output from the investigations of synthetic polymers as well. Eventually, the MS/MS field will also open up for polymer scientists who are not MS-specialists. In this review, we dissect the overall framework of the MS and MS/MS analysis of synthetic polymers into its key components. We discuss the fundamentals of polymer analyses as well as recent advances in the areas of tandem mass spectrometry, software developments, and the overall future perspectives on the way to polymer sequencing, one of the last Holy Grail in polymer science. Copyright © 2013 Elsevier B.V. All rights reserved.

Simulation of magnetic active polymers for versatile microfluidic devices

NASA Astrophysics Data System (ADS)

Gusenbauer, Markus; Özelt, Harald; Fischbacher, Johann; Reichel, Franz; Exl, Lukas; Bance, Simon; Kataeva, Nadezhda; Binder, Claudia; Brückl, Hubert; Schrefl, Thomas

2013-01-01

We propose to use a compound of magnetic nanoparticles (20-100 nm) embedded in a flexible polymer (Polydimethylsiloxane PDMS) to filter circulating tumor cells (CTCs). The analysis of CTCs is an emerging tool for cancer biology research and clinical cancer management including the detection, diagnosis and monitoring of cancer. The combination of experiments and simulations lead to a versatile microfluidic lab-on-chip device. Simulations are essential to understand the influence of the embedded nanoparticles in the elastic PDMS when applying a magnetic gradient field. It combines finite element calculations of the polymer, magnetic simulations of the embedded nanoparticles and the fluid dynamic calculations of blood plasma and blood cells. With the use of magnetic active polymers a wide range of tunable microfluidic structures can be created. The method can help to increase the yield of needed isolated CTCs.

Functional and Multifunctional Polymers: Materials for Smart Structures

NASA Technical Reports Server (NTRS)

Arnold, S.; Pratt, L. M.; Li, J.; Wuagaman, M.; Khan, I. M.

1996-01-01

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three

Systems Biology: Impressions from a Newcomer Graduate Student in 2016

ERIC Educational Resources Information Center

Simpson, Melanie Rae

2016-01-01

As a newcomer, the philosophical basis of systems biology seems intuitive and appealing, the underlying philosophy being that the whole of a living system cannot be completely understood by the study of its individual parts. Yet answers to the questions "What is systems biology?" and "What constitutes a systems biology approach in…

The Ultrasensitivity of Living Polymers

NASA Astrophysics Data System (ADS)

O'Shaughnessy, Ben; Vavylonis, Dimitrios

2003-03-01

Synthetic and biological living polymers are self-assembling chains whose chain length distributions (CLDs) are dynamic. We show these dynamics are ultrasensitive: Even a small perturbation (e.g., temperature jump) nonlinearly distorts the CLD, eliminating or massively augmenting short chains. The origin is fast relaxation of mass variables (mean chain length, monomer concentration) which perturbs CLD shape variables before these can relax via slow chain growth rate fluctuations. Viscosity relaxation predictions agree with experiments on the best-studied synthetic system, α-methylstyrene.

Fate of Eight Different Polymers under Uncontrolled Composting Conditions: Relationships Between Deterioration, Biofilm Formation, and the Material Surface Properties.

PubMed

Mercier, Anne; Gravouil, Kevin; Aucher, Willy; Brosset-Vincent, Sandra; Kadri, Linette; Colas, Jenny; Bouchon, Didier; Ferreira, Thierry

2017-02-21

With the ever-increasing volume of polymer wastes and their associated detrimental impacts on the environment, the plastic life cycle has drawn increasing attention. Here, eight commercial polymers selected from biodegradable to environmentally persistent materials, all formulated under a credit card format, were incubated in an outdoor compost to evaluate their fate over time and to profile the microbial communities colonizing their surfaces. After 450 days in compost, the samples were all colonized by multispecies biofilms, these latest displaying different amounts of adhered microbial biomass and significantly distinct bacterial and fungal community compositions depending on the substrate. Interestingly, colonization experiments on the eight polymers revealed a large core of shared microbial taxa, predominantly composed of microorganisms previously reported from environments contaminated with petroleum hydrocarbons or plastics debris. These observations suggest that biofilms may contribute to the alteration process of all the polymers studied. Actually, four substrates, independently of their assignment to a polymer group, displayed a significant deterioration, which might be attributed to biologically mediated mechanisms. Relevantly, the deterioration appears strongly associated with the formation of a high-cell density biofilm onto the polymer surfaces. The analysis of various surface properties revealed that roughness and hydrophilicity are likely prominent parameters for driving the biological interactions with the polymers.

Tuning Adsorption Duration To Control the Diffusion of a Nanoparticle in Adsorbing Polymers.

PubMed

Cao, Xue-Zheng; Merlitz, Holger; Wu, Chen-Xu

2017-06-15

Controlling the nanoparticle (NP) diffusion in polymers is a prerequisite to obtain polymer nanocomposites (PNCs) with desired dynamical and rheological properties and to achieve targeted delivery of nanomedicine in biological systems. Here we determine the suppression mechanism of direct NP-polymer attraction to hamper the NP mobility in adsorbing polymers and then quantify the dependence of the effective viscosity η eff felt by the NP on the adsorption duration τ ads of polymers on the NP using scaling theory analysis and molecular dynamics simulations. We propose and confirm that participation of adsorbed chains in the NP motion break up at time intervals beyond τ ads due to the rearrangement of polymer segments at the NP surface, which accounts for the onset of Fickian NP diffusion on a time scale of t ≈ τ ads . We develop a power law, η eff ∼ (τ ads ) ν , where ν is the scaling exponent of the dependence of polymer coil size on the chain length, which leads to a theoretical basis for the design of PNCs and nanomedicine with desired applications through tuning the polymer adsorption duration.

Modeling and Simulation of Ballistic Penetration of Ceramic-Polymer-Metal Layered Systems

DTIC Science & Technology

2016-01-01

ARL-RP-0562 ● JAN 2016 US Army Research Laboratory Modeling and Simulation of Ballistic Penetration of Ceramic-Polymer-Metal...manufacturer’s or trade names does not constitute an official endorsement or approval of the use thereof. Destroy this report when it is no longer needed...Do not return it to the originator. ARL-RP-0562 ● JAN 2016 US Army Research Laboratory Modeling and Simulation of Ballistic

Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

DOE PAGES

Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; ...

2015-04-24

In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks).more » The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.« less

Stretching of Single Polymer Chains Using the Atomic Force Microscope

NASA Astrophysics Data System (ADS)

Ortiz, C.; van der Vegte, E. W.; van Swieten, E.; Robillard, G. T.; Hadziioannou, G.

1998-03-01

A variety of macroscopic phenomenon involve "nanoscale" polymer deformation including rubber elasticity, shear yielding, strain hardening, stress relaxation, fracture, and flow. With the advent of new and improved experimental techniques, such as the atomic force microscope (AFM), the probing of physical properties of polymers has reached finer and finer scales. The development of mixed self-assembling monolayer techniques and the chemical functionalization of AFM probe tips has allowed for mechanical experiments on single polymer chains of molecular dimensions. In our experiments, mixed monolayers are prepared in which end-functionalized, flexible polymer chains of thiol-terminated poly(methacrylic acid) are covalently bonded, isolated, and randomly distributed on gold substrates. The coils are then imaged, tethered to a gold-coated AFM tip, and stretched between the tip and the substrate in a conventional force / distance experiment. An increase in the attractive force due to entropic, elastic resistance to stretching, as well as fracture of the polymer chain is observed. The effect of chain stiffness, topological constraints, strain rate, mechanical hysteresis, and stress relaxation were investigated. Force modulation techniques were also employed in order to image the viscoelastic character of the polymer chains. Parallel work includes similar studies of biological systems such as wheat gluten proteins and polypeptides.

Simulation of Biomimetic Recognition between Polymers and Surfaces

NASA Astrophysics Data System (ADS)

Golumbfskie, Aaron J.; Pande, Vijay S.; Chakraborty, Arup K.

1999-10-01

Many biological processes, such as transmembrane signaling and pathogen-host interactions, are initiated by a protein recognizing a specific pattern of binding sites on part of a membrane or cell surface. By recognition, we imply that the polymer quickly finds and then adsorbs strongly on the pattern-matched region and not on others. The development of synthetic systems that can mimic such recognition between polymers and surfaces could have significant impact on advanced applications such as the development of sensors, molecular-scale separation processes, and synthetic viral inhibition agents. Attempting to affect recognition in synthetic systems by copying the detailed chemistries to which nature has been led over millenia of evolution does not seem practical for most applications. This leads us to the following question: Are there any universal strategies that can affect recognition between polymers and surfaces? Such generic strategies may be easier to implement in abiotic applications. We describe results that suggest that biomimetic recognition between synthetic polymers and surfaces is possible by exploiting certain generic strategies, and we elucidate the kinetic mechanisms by which this occurs. Our results suggest convenient model systems for experimental studies of dynamics in free energy landscapes characteristic of frustrated systems.

Organic Chemistry and Biology: Chemical Biology Through the Eyes of Collaboration

PubMed Central

Hruby, Victor J.

2011-01-01

From a scientific perspective, efforts to understand biology including what constitutes health and disease has become a chemical problem. However, chemists and biologists “see” the problems of understanding biology from different perspectives, and this has retarded progress in solving the problems especially as they relate to health and disease. This suggests that close collaboration between chemists and biologists is not only necessary but essential for progress in both the biology and chemistry that will provide solutions to the global questions of biology. This perspective has directed my scientific efforts for the past 45 years, and in this overview I provide my perspective of how the applications of synthetic chemistry, structural design, and numerous other chemical principles have intersected in my collaborations with biologists to provide new tools, new science, and new insights that were only made possible and fruitful by these collaborations. PMID:20000552

Fungistatic activity of composts with the addition of polymers obtained from thermoplastic corn starch and polyethylene - An innovative cleaner production alternative.

PubMed

Mierzwa-Hersztek, Monika; Gleń-Karolczyk, Katarzyna; Gondek, Krzysztof

2018-04-22

Compost extracts with the addition of polymers obtained from thermoplastic corn starch and polyethylene are novel organic amendments, which can be typically applied to suppress soil-borne diseases. Considering the diversity of biologically active substances, including those growth-promoting and stabilizing various pathogens contained in extracts, composts have a large potential to successfully replace the massively used pesticides. The effect of various concentrations of water compost extracts with the addition of polymers obtained from thermoplastic corn starch and polyethylene on the linear growth, biomass, and sporulation of the following polyphagous fungi was assessed under in situ and in vitro conditions: Fusarium culmorum (W.G. Smith), Fusarium graminearum Schwabe, Sclerotinia sclerotiorum (Lib.) de Bary, Rhizoctonia solani Kühn, Alternaria alternata (Fr.) Keissler. The studies revealed that the fungistatic activity was determined by the kind and concentration of compost extract added to the medium, as well as by the fungus kind. The analyzed compost extracts blocked the linear growth of the tested fungi on average by 22%, biomass increment by 51%, and sporulation by 57%. F. culmorum and S. sclerotiorum proved to be the most sensitive to the tested compost extracts. It was found that the extract from compost with the addition of polymer with the highest share of polyethylene blocked the sporulation of F. culmorum by 87% and F. graminearum by 92%. In turn, composts with the addition of polymers with the highest share of a biocomponent weakened the fungistatic activity of composts. The authors demonstrated that the addition of microbiological inoculum to one of the composts enhanced the fungistatic activity with respect to S. sclerotiorum, F. graminearum, and F. culmorum. The obtained results can be used to better understand the growth-promoting and suppression effects of compost extracts with polymer addition, help to enhance crop production, and constitute a

The biological response to nanometre-sized polymer particles.

PubMed

Liu, Aiqin; Richards, Laura; Bladen, Catherine L; Ingham, Eileen; Fisher, John; Tipper, Joanne L

2015-09-01

Recently, nanometre-sized UHMWPE particles generated from hip and knee replacements have been identified in vitro and in vivo. UHMWPE particles in the 0.1-1.0μm size range have been shown to be more biologically active than larger particles, provoking an inflammatory response implicated in late aseptic loosening of total joint replacements. The biological activity of nanometre-sized particles has not previously been studied. The biological response to clinically-relevant UHMWPE wear particles including nanometre-sized and micrometre-sized, along with polystyrene particles (FluoSpheres 20nm, 60nm, 200nm and 1.0μm), and nanometre-sized model polyethylene particles (Ceridust 3615®), was determined in terms of osteolytic cytokine release from primary human peripheral blood mononuclear cells (PBMNCs). Nanometre-sized UHMWPE wear particles, nanometre-sized Ceridust 3615® and 20nm FluoSpheres had no significant effect on TNF-α, IL-1β, IL-6 and IL-8 release from PBMNCs at a concentration of 100μm(3) particles per cell after 12 and 24h. The micrometre-size UHMWPE wear particles (0.1-1.0μm) and 60nm, 200nm and 1.0μm FluoSpheres caused significantly elevated osteolytic cytokine release from PBMNCs. These results indicated that particles below circa 50nm fail to activate PBMNCs and that particle size, composition and morphology played a crucial role in cytokine release by particle stimulated macrophages. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The biological response to nanometre-sized polymer particles

PubMed Central

Liu, Aiqin; Richards, Laura; Bladen, Catherine L.; Ingham, Eileen; Fisher, John; Tipper, Joanne L.

2015-01-01

Recently, nanometre-sized UHMWPE particles generated from hip and knee replacements have been identified in vitro and in vivo. UHMWPE particles in the 0.1–1.0 μm size range have been shown to be more biologically active than larger particles, provoking an inflammatory response implicated in late aseptic loosening of total joint replacements. The biological activity of nanometre-sized particles has not previously been studied. The biological response to clinically-relevant UHMWPE wear particles including nanometre-sized and micrometre-sized, along with polystyrene particles (FluoSpheres 20 nm, 60 nm, 200 nm and 1.0 μm), and nanometre-sized model polyethylene particles (Ceridust 3615®), was determined in terms of osteolytic cytokine release from primary human peripheral blood mononuclear cells (PBMNCs). Nanometre-sized UHMWPE wear particles, nanometre-sized Ceridust 3615® and 20 nm FluoSpheres had no significant effect on TNF-α, IL-1β, IL-6 and IL-8 release from PBMNCs at a concentration of 100 μm3 particles per cell after 12 and 24 h. The micrometre-size UHMWPE wear particles (0.1–1.0 μm) and 60 nm, 200 nm and 1.0 μm FluoSpheres caused significantly elevated osteolytic cytokine release from PBMNCs. These results indicated that particles below circa 50 nm fail to activate PBMNCs and that particle size, composition and morphology played a crucial role in cytokine release by particle stimulated macrophages. PMID:26004221

Correlating antimicrobial activity and model membrane leakage induced by nylon-3 polymers and detergents.

PubMed

Hovakeemian, Sara G; Liu, Runhui; Gellman, Samuel H; Heerklotz, Heiko

2015-09-14

Most antimicrobial peptides act upon target microorganisms by permeabilizing their membranes. The mode of action is often assessed by vesicle leakage experiments that use model membranes, with the assumption that biological activity correlates with the permeabilization of the lipid bilayer. The current work aims to extend the interpretation of vesicle leakage results and examine the correlation between vesicle leakage and antimicrobial activity. To this end, we used a lifetime-based leakage assay with calcein-loaded vesicles to study the membrane permeabilizing properties of a novel antifungal polymer poly-NM, two of its analogs, and a series of detergents. In conjunction, the biological activities of these compounds against Candida albicans were assessed and correlated with data from vesicle leakage. Poly-NM induces all-or-none leakage in polar yeast lipid vesicles at the polymer's MIC, 3 μg mL(-1). At this and higher concentrations, complete leakage after an initial lag time was observed. Concerted activity tests imply that this polymer acts independently of the detergent octyl glucoside (OG) for both vesicle leakage and activity against C. albicans spheroplasts. In addition, poly-NM was found to have negligible activity against zwitterionic vesicles and red blood cells. Our results provide a consistent, detailed picture of the mode of action of poly-NM: this polymer induces membrane leakage by electrostatic lipid clustering. In contrast, poly-MM:CO, a nylon-3 polymer comprised of both cationic and hydrophobic segments, seems to act by a different mechanism that involves membrane asymmetry stress. Vesicle leakage for this polymer is transient (limited to <100%) and graded, non-specific among zwitterionic and polar yeast lipid vesicles, additive with detergent action, and correlates poorly with biological activity. Based on these results, we conclude that comprehensive leakage experiments can provide a detailed description of the mode of action of membrane

Characterization of Polymer Blends: Optical Microscopy (*Polarized, Interference and Phase Contrast Microscopy*) and Confocal Microscopy

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

Ramanathan, Nathan Muruganathan; Darling, Seth B.

2015-01-01

Chapter 15 surveys the characterization of macro, micro and meso morphologies of polymer blends by optical microscopy. Confocal Microscopy offers the ability to view the three dimensional morphology of polymer blends, popular in characterization of biological systems. Confocal microscopy uses point illumination and a spatial pinhole to eliminate out-of focus light in samples that are thicker than the focal plane.

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers.

PubMed

Wang, Jun; Bonnesen, Peter V; Rangel, E; Vallejo, E; Sanchez-Castillo, Ariadna; James Cleaves Ii, H; Baddorf, Arthur P; Sumpter, Bobby G; Pan, Minghu; Maksymovych, Petro; Fuentes-Cabrera, Miguel

2016-01-04

Self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N(9)-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two or more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. These characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Further, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.

Chemical degradation and morphological instabilities during focused ion beam prototyping of polymers.

PubMed

Orthacker, A; Schmied, R; Chernev, B; Fröch, J E; Winkler, R; Hobisch, J; Trimmel, G; Plank, H

2014-01-28

Focused ion beam processing of low melting materials, such as polymers or biological samples, often leads to chemical and morphological instabilities which prevent the straight-forward application of this versatile direct-write structuring method. In this study the behaviour of different polymer classes under ion beam exposure is investigated using different patterning parameters and strategies with the aim of (i) correlating local temperatures with the polymers' chemistry and its morphological consequences; and (ii) finding a way of processing sensitive polymers with lowest chemical degradation while maintaining structuring times. It is found that during processing of polymers three temperature regimes can be observed: (1) at low temperatures all polymers investigated show stable chemical and morphological behaviour; (2) very high temperatures lead to strong chemical degradation which entails unpredictable morphologies; and (3) in the intermediate temperature regime the behaviour is found to be strongly material dependent. A detailed look reveals that polymers which rather cross-link in the proximity of the beam show stable morphologies in this intermediate regime, while polymers that rather undergo chain scission show tendencies to develop a creeping phase, where material follows the ion beam movement leading to instable and unpredictable morphologies. Finally a simple, alternative patterning strategy is suggested, which allows stable processing conditions with lowest chemical damage even for challenging polymers undergoing chain scission.

Mechanical transduction via a single soft polymer

NASA Astrophysics Data System (ADS)

Hou, Ruizheng; Wang, Nan; Bao, Weizhu; Wang, Zhisong

2018-04-01

Molecular machines from biology and nanotechnology often depend on soft structures to perform mechanical functions, but the underlying mechanisms and advantages or disadvantages over rigid structures are not fully understood. We report here a rigorous study of mechanical transduction along a single soft polymer based on exact solutions to the realistic three-dimensional wormlike-chain model and augmented with analytical relations derived from simpler polymer models. The results reveal surprisingly that a soft polymer with vanishingly small persistence length below a single chemical bond still transduces biased displacement and mechanical work up to practically significant amounts. This "soft" approach possesses unique advantages over the conventional wisdom of rigidity-based transduction, and potentially leads to a unified mechanism for effective allosterylike transduction and relay of mechanical actions, information, control, and molecules from one position to another in molecular devices and motors. This study also identifies an entropy limit unique to the soft transduction, and thereby suggests a possibility of detecting higher efficiency for kinesin motor and mutants in future experiments.

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

Polymer Crowding in Confined Polymer-Nanoparticle Mixtures

NASA Astrophysics Data System (ADS)

Davis, Wyatt J.; Denton, Alan R.

Crowding can influence the conformations and thus functionality of macromolecules in quasi-two-dimensional environments, such as DNA or proteins confined to a cell membrane. We explore such crowding within a model of polymers as penetrable ellipses, whose shapes are governed by the statistics of a 2D random walk. The principal radii of the polymers fluctuate according to probability distributions of the eigenvalues of the gyration tensor. Within this coarse-grained model, we perform Monte Carlo simulations of mixtures of polymers and hard nanodisks, including trial changes in polymer conformation (shape and orientation). Penetration of polymers by nanodisks is incorporated with a free energy cost predicted by polymer field theory. Over ranges of size ratio and nanodisk density, we analyze the influence of crowding on polymer shape by computing eigenvalue distributions, mean radius of gyration, and mean asphericity of the polymer. We compare results with predictions of free-volume theory and with corresponding results in three dimensions. Our approach may help to interpret recent (and motivate future) experimental studies of biopolymers interacting with cell membranes, with relevance for drug delivery and gene therapy. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Silicone-containing aqueous polymer dispersions with hybrid particle structure.

PubMed

Kozakiewicz, Janusz; Ofat, Izabela; Trzaskowska, Joanna

2015-09-01

In this paper the synthesis, characterization and application of silicone-containing aqueous polymer dispersions (APD) with hybrid particle structure are reviewed based on available literature data. Advantages of synthesis of dispersions with hybrid particle structure over blending of individual dispersions are pointed out. Three main processes leading to silicone-containing hybrid APD are identified and described in detail: (1) emulsion polymerization of organic unsaturated monomers in aqueous dispersions of silicone polymers or copolymers, (2) emulsion copolymerization of unsaturated organic monomers with alkoxysilanes or polysiloxanes with unsaturated functionality and (3) emulsion polymerization of alkoxysilanes (in particular with unsaturated functionality) and/or cyclic siloxanes in organic polymer dispersions. The effect of various factors on the properties of such hybrid APD and films as well as on hybrid particles composition and morphology is presented. It is shown that core-shell morphology where silicones constitute either the core or the shell is predominant in hybrid particles. Main applications of silicone-containing hybrid APD and related hybrid particles are reviewed including (1) coatings which show specific surface properties such as enhanced water repellency or antisoiling or antigraffiti properties due to migration of silicone to the surface, and (2) impact modifiers for thermoplastics and thermosets. Other processes in which silicone-containing particles with hybrid structure can be obtained (miniemulsion polymerization, polymerization in non-aqueous media, hybridization of organic polymer and polysiloxane, emulsion polymerization of silicone monomers in silicone polymer dispersions and physical methods) are also discussed. Prospects for further developments in the area of silicone-containing hybrid APD and related hybrid particles are presented. Copyright © 2015. Published by Elsevier B.V.

Lessons learnt from early failure of a patient trial with a polymer-on-polymer resurfacing hip arthroplasty

PubMed Central

Van Susante, Job L C; Verdonschot, Nico; Bom, L Paul A; Tomaszewski, Pawel; Campbell, Pat; Ebramzadeh, Edward; Schreurs, B Wim

2018-01-01

Background and purpose Hip resurfacing (HR) is a treatment option promoted for hip arthritis in young and active patients. However, adverse reactions to metal are a concern and the search for non-metallic bearing options proceeds. We present the first clinical study performed in patients using a newly developed hydrophilic polymer-on-polymer hip resurfacing device. Patients and methods After performing extensive hip simulator tests, biocompatibility testing and animal tests (ISO 14242-1,3; 10993-3,4,5,10,11), approval was obtained from the IRB committee to enroll 15 patients in the first clinical study in humans using this experimental polymer-on-polymer hip resurfacing device. All surgeries were done by 2 experienced hip resurfacing surgeons. Clinical scores and standard radiographs as well as routine MRIs were obtained at regular intervals. Results The surgical technique proved feasible with successful implantation of the new device using PMMA cement fixation on both sides without complications. Postoperative imaging revealed a well-positioned and well-fixed polymer resurfacing hip arthroplasty in all 4 initial cases. All 4 patients were free of pain and had good function for the first 2 months. However, in all 4 cases early cup loosening occurred between 8 and 11 weeks after surgery, necessitating immediate closure of the study. All 4 patients had a reoperation and were revised to a conventional THA. Retrieval analyses confirmed early cup loosening at the implant–cement interface in all 4 cases. The femoral components remained well attached to the cement. The periprosthetic tissues showed only small amounts of polymeric wear debris and there was only a very mild inflammatory reaction to this. Interpretation Early cup loosening mandated a premature arrest of this study. After additional laboratory testing this failure mode was found to be the result of a small, yet measurable contraction in the cup size after exposing these implants to biological fluid divalent

Lessons learnt from early failure of a patient trial with a polymer-on-polymer resurfacing hip arthroplasty.

PubMed

Van Susante, Job L C; Verdonschot, Nico; Bom, L Paul A; Tomaszewski, Pawel; Campbell, Pat; Ebramzadeh, Edward; Schreurs, B Wim

2018-02-01

Background and purpose - Hip resurfacing (HR) is a treatment option promoted for hip arthritis in young and active patients. However, adverse reactions to metal are a concern and the search for non-metallic bearing options proceeds. We present the first clinical study performed in patients using a newly developed hydrophilic polymer-on-polymer hip resurfacing device. Patients and methods - After performing extensive hip simulator tests, biocompatibility testing and animal tests (ISO 14242-1,3; 10993-3,4,5,10,11), approval was obtained from the IRB committee to enroll 15 patients in the first clinical study in humans using this experimental polymer-on-polymer hip resurfacing device. All surgeries were done by 2 experienced hip resurfacing surgeons. Clinical scores and standard radiographs as well as routine MRIs were obtained at regular intervals. Results - The surgical technique proved feasible with successful implantation of the new device using PMMA cement fixation on both sides without complications. Postoperative imaging revealed a well-positioned and well-fixed polymer resurfacing hip arthroplasty in all 4 initial cases. All 4 patients were free of pain and had good function for the first 2 months. However, in all 4 cases early cup loosening occurred between 8 and 11 weeks after surgery, necessitating immediate closure of the study. All 4 patients had a reoperation and were revised to a conventional THA. Retrieval analyses confirmed early cup loosening at the implant-cement interface in all 4 cases. The femoral components remained well attached to the cement. The periprosthetic tissues showed only small amounts of polymeric wear debris and there was only a very mild inflammatory reaction to this. Interpretation - Early cup loosening mandated a premature arrest of this study. After additional laboratory testing this failure mode was found to be the result of a small, yet measurable contraction in the cup size after exposing these implants to biological fluid

New polymers for low-gravity purification of cells by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1983-01-01

A potentially powerful technique for separating different biological cell types is based on the partitioning of these cells between the immiscible aqueous phases formed by solution of certain polymers in water. This process is gravity-limited because cells sediment rather than associate with the phase most favored on the basis of cell-phase interactions. In the present contract we have been involved in the synthesis of new polymers both to aid in understanding the partitioning process and to improve the quality of separations. The prime driving force behind the design of these polymers is to produce materials which will aid in space experiments to separate important cell types and to study the partitioning process in the absence of gravity (i.e., in an equilibrium state).

Volume effect of non-polar solvent towards the synthesis of hydrophilic polymer nanoparticles prepares via inverse miniemulsion polymerization

NASA Astrophysics Data System (ADS)

Kamaruddin, Nur Nasyita; Kassim, Syara; Harun, Noor Aniza

2017-09-01

Polymeric nanoparticles have drawn tremendous attention to researchers and have utilized in diverse fields especially in biomedical applications. Nevertheless, question has raised about the safety and hydrophilicity of the nanoparticles to be utilized in medical and biological applications. One promising solution to this problem is to develop biodegradable polymeric nanoparticles with improve hydrophilicity. This study is focusing to develop safer and "greener" polymeric nanoparticles via inverse miniemulsion polymerization techniques, a robust and convenient method to produce water-soluble polymer nanoparticles. Acrylamide (Am), acrylic acid (AA) and methacrylic acid (MAA) monomers have chosen, as they are biocompatible, non-toxic and ecological. The effect of different volumes of cyclohexane towards the formation of polymer nanoparticles, particle size, particle size distribution and morphology of polymer nanoparticles are investigated. The formation and morphology of polymer nanoparticles are determined using FTIR and SEM respectively. The mean diameters of the polymer nanoparticles were in a range of 80 - 250 nm and with broad particle size distributions as determined by dynamic light scattering (DLS). Hydrophilic polyacrylamide (pAm), poly(acrylic acid) (pAA) and poly(methacrylic acid) (pMAA) nanoparticles were successfully achieved by inverse miniemulsion polymerization and have potentiality to be further utilized in the fabrication of hybrid polymer composite nanoparticles especially in biological and medical applications.

Biopolymers and supramolecular polymers as biomaterials for biomedical applications

PubMed Central

Freeman, Ronit; Boekhoven, Job; Dickerson, Matthew B.; Naik, Rajesh R.

2015-01-01

Protein- and peptide-based structural biopolymers are abundant building blocks of biological systems. Either in their natural forms, such as collagen, silk or fibronectin, or as related synthetic materials they can be used in various technologies. An emerging area is that of biomimetic materials inspired by protein-based biopolymers, which are made up of small molecules rather than macromolecules and can therefore be described as supramolecular polymers. These materials are very useful in biomedical applications because of their ability to imitate the extracellular matrix both in architecture and their capacity to signal cells. This article describes important features of the natural extracellular matrix and highlight how these features are being incorporated into biomaterials composed of biopolymers and supramolecular polymers. We particularly focus on the structures, properties, and functions of collagen, fibronectin, silk, and the supramolecular polymers inspired by them as biomaterials for regenerative medicine. PMID:26989295

Teleology and its constitutive role for biology as the science of organized systems in nature.

PubMed

Toepfer, Georg

2012-03-01

'Nothing in biology makes sense, except in the light of teleology'. This could be the first sentence in a textbook about the methodology of biology. The fundamental concepts in biology, e.g. 'organism' and 'ecosystem', are only intelligible given a teleological framework. Since early modern times, teleology has often been considered methodologically unscientific. With the acceptance of evolutionary theory, one popular strategy for accommodating teleological reasoning was to explain it by reference to selection in the past: functions were reconstructed as 'selected effects'. But the theory of evolution obviously presupposes the existence of organisms as organized and regulated, i.e. functional systems. Therefore, evolutionary theory cannot provide the foundation for teleology. The underlying reason for the central methodological role of teleology in biology is not its potential to offer particular forms of (evolutionary) explanations for the presence of parts, but rather an ontological one: organisms and other basic biological entities do not exist as physical bodies do, as amounts of matter with a definite form. Rather, they are dynamic systems in stable equilibrium; despite changes of their matter and form (in metabolism and metamorphosis) they maintain their identity. What remains constant in these kinds of systems is their 'organization', i.e. the causal pattern of interdependence of parts with certain effects of each part being relevant for the working of the system. Teleological analysis consists in the identification of these system-relevant effects and at the same time of the system as a whole. Therefore, the identity of biological systems cannot be specified without teleological reasoning. Copyright © 2011 Elsevier Ltd. All rights reserved.

Three-dimensional bioprinting of cell-laden constructs with polycaprolactone protective layers for using various thermoplastic polymers.

PubMed

Kim, Byoung Soo; Jang, Jinah; Chae, Suhun; Gao, Ge; Kong, Jeong-Sik; Ahn, Minjun; Cho, Dong-Woo

2016-08-22

Three-dimensional (3D) cell-printed constructs have been recognized as promising biological substitutes for tissue/organ regeneration. They provide tailored physical properties and biological cues via multi-material printing process. In particular, hybrid bioprinting, enabling to use biodegradable synthetic polymers as framework, has been an attractive method to support weak hydrogels. The constructs with controlled architecture and high shape fidelity were fabricated through this method, depositing spatial arrangement of multi-cell types into microscale constructs. Among biodegradable synthetic polymers, polycaprolactone (PCL) has been commonly chosen in fabrication of cell-printed constructs because of its low melting temperature of 60 °C to be dispensed with extrusion-based bioprinting system. However, in addition to PCL, various synthetic polymers have been widely applied for tissue regeneration. These polymers have distinctive characteristics essential for tissue/organ regeneration. Nevertheless, it is difficult to use some polymers, such as poly (lactic-co-glycolic acid) (PLGA) and polylactic acid (PLA) with 3D bioprinting technology because of their high melting temperature to be dispensed, which can result in thermal damage to the cells in the printed constructs during the fabrication process. We present a novel bioprinting method to use various synthetic polymers in fabrication of cell-printed constructs. PCL was introduced as a protective layer to prevent thermal damage caused by high temperature of polymers during fabrication. Remarkable improvement in cellular activities in the printed constructs with PCL layers was observed compared with the construct without PCL. This bioprinting method can be applied to fabricate more tissue-like constructs through the use of various biomaterials.

Chemical & Biological Point Detection Decontamination

DTIC Science & Technology

2002-04-01

high priority in biological defense. Research on multivalent assays is also ongoing. Biased libraries, generated from immunized animals, or unbiased ...2003 TBD decontamination and modeling and simulation I I The Chem-Bio Point Detection Roadmap The summary level updated and expanded Bio Point... Molecular Imprinted Polymer Sensor, Dendrimer-based Antibody Assays, Pyrolysis-GC-ion mobility spectrometry, and surface enhanced Raman spectroscopy. Data

Flow-induced adhesion of shear-activated polymers to a substrate

NASA Astrophysics Data System (ADS)

Hoore, Masoud; Rack, Kathrin; Fedosov, Dmitry A.; Gompper, Gerhard

2018-02-01

Adhesion of polymers and proteins to substrates plays a crucial role in many technological applications and biological processes. A prominent example is the von Willebrand factor (VWF) protein, which is essential in blood clotting as it mediates adhesion of blood platelets to the site of injury at high shear rates. VWF is activated by flow and is able to bind efficiently to damaged vessel walls even under extreme flow-stress conditions; however, its adhesion is reversible when the flow strength is significantly reduced or the flow is ceased. Motivated by the properties and behavior of VWF in flow, we investigate adhesion of shear-activated polymers to a planar wall in flow and whether the adhesion is reversible under flow stasis. The main ingredients of the polymer model are cohesive inter-monomer interactions, a catch bond with the adhesive surface, and the shear activation/deactivation of polymer adhesion correlated with its stretching in flow. The cohesive interactions within the polymer maintain a globular conformation under low shear stresses and allow polymer stretching if a critical shear rate is exceeded, which is directly associated with its activation for adhesion. Our results show that polymer adhesion at high shear rates is significantly stabilized by catch bonds, while at the same time they also permit polymer dissociation from a surface at low or no flow stresses. In addition, the activation/deactivation mechanism for adhesion plays a crucial role in the reversibility of its adhesion. These observations help us better understand the adhesive behavior of VWF in flow and interpret its adhesion malfunctioning in VWF-related diseases.

This Constitution: A Bicentennial Chronicle.

ERIC Educational Resources Information Center

This Constitution, 1986

1986-01-01

Providing a link between constitutional scholars and the planners of school and public programs observing the Bicentennial of the United States Constitution, this series of the Bicentennial Chronicles features articles that provide a link between scholars of the Constitution and the people who will be planning programs for the public and for the…

Biocompatibility of polymer-infiltrated-ceramic-network (PICN) materials with Human Gingival Fibroblasts (HGFs).

PubMed

Grenade, Charlotte; De Pauw-Gillet, Marie-Claire; Gailly, Patrick; Vanheusden, Alain; Mainjot, Amélie

2016-09-01

Polymer-infiltrated-ceramic-network (PICN) materials constitute an innovative class of CAD-CAM materials offering promising perspectives in prosthodontics, but no data are available in the literature regarding their biological properties. The objective of the present study was to evaluate the in vitro biocompatibility of PICNs with human gingival fibroblasts (HGFs) in comparison with materials typically used for implant prostheses and abutments. HGF attachment, proliferation and spreading on discs made of PICN, grade V titanium (Ti), yttrium zirconia (Zi), lithium disilicate glass-ceramic (eM) and polytetrafluoroethylene (negative control), were evaluated using a specific insert-based culture system (IBS-R). Sample surface properties were characterized by XPS, contact angle measurement, profilometry and SEM. Ti and Zi gave the best results regarding HGF viability, morphology, number and coverage increase with time in comparison with the negative control, while PICN and eM gave intermediate results, cell spreading being comparable for PICN, Ti, Zi and eM. Despite the presence of polymers and their related hydrophobicity, PICN exhibited comparable results to glass-ceramic materials, which could be explained by the mode of polymerization of the monomers. The results of the present study confirm that the currently employed materials, i.e. Ti and Zi, can be considered to be the gold standard of materials in terms of HGF behavior, while PICN gave intermediate results comparable to eM. The impact of the present in vitro results needs to be further investigated clinically, particularly in the view of the utilization of PICNs for prostheses on bone-level implants. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Polymer films

DOEpatents

Granick, Steve; Sukhishvili, Svetlana A.

2004-05-25

A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

Polymer films

DOEpatents

Granick, Steve [Champaign, IL; Sukhishvili, Svetlana A [Maplewood, NJ

2008-12-30

A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

Adsorption and flocculation by polymers and polymer mixtures.

PubMed

Gregory, John; Barany, Sandor

2011-11-14

Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

Revisiting structure-property relationship of pH-responsive polymers for drug delivery applications.

PubMed

Bazban-Shotorbani, Salime; Hasani-Sadrabadi, Mohammad Mahdi; Karkhaneh, Akbar; Serpooshan, Vahid; Jacob, Karl I; Moshaverinia, Alireza; Mahmoudi, Morteza

2017-05-10

pH-responsive polymers contain ionic functional groups as pendants in their structure. The total number of charged groups on polymer chains determines the overall response of the system to changes in the external pH. This article reviews various pH-responsive polymers classified as polyacids (e.g., carboxylic acid based polymers, sulfonamides, anionic polysaccharides, and anionic polypeptides) and polybases (e.g., polyamines, pyridine and imidazole containing polymers, cationic polysaccharides, and cationic polypeptides). We correlate the pH variations in the body at the organ level (e.g., gastrointestinal tract and vaginal environment), tissue level (e.g., cancerous and inflamed tissues), and cellular level (e.g., sub-cellular organelles), with the intrinsic properties of pH-responsive polymers. This knowledge could help to select more effective ('smart') polymeric systems based on the biological target. Considering the pH differences in the body, various drug delivery systems can be designed by utilizing smart biopolymeric compounds with the required pH-sensitivity. We also review the pharmaceutical application of pH-responsive polymeric carriers including hydrogels, polymer-drug conjugates, micelles, dendrimers, and polymersomes. © 2016.

Long ligands reinforce biological adhesion under shear flow

NASA Astrophysics Data System (ADS)

Belyaev, Aleksey V.

2018-04-01

In this work, computer modeling has been used to show that longer ligands allow biological cells (e.g., blood platelets) to withstand stronger flows after their adhesion to solid walls. A mechanistic model of polymer-mediated ligand-receptor adhesion between a microparticle (cell) and a flat wall has been developed. The theoretical threshold between adherent and non-adherent regimes has been derived analytically and confirmed by simulations. These results lead to a deeper understanding of numerous biophysical processes, e.g., arterial thrombosis, and to the design of new biomimetic colloid-polymer systems.

Hydrostatic Stress Effects Incorporated Into the Analysis of the High-Strain-Rate Deformation of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Roberts, Gary D.

2003-01-01

Procedures for modeling the effect of high strain rate on composite materials are needed for designing reliable composite engine cases that are lighter than the metal cases in current use. The types of polymer matrix composites that are likely to be used in such an application have a deformation response that is nonlinear and that varies with strain rate. The nonlinearity and strain rate dependence of the composite response is primarily due to the matrix constituent. Therefore, in developing material models to be used in the design of impact-resistant composite engine cases, the deformation of the polymer matrix must be correctly analyzed. However, unlike in metals, the nonlinear response of polymers depends on the hydrostatic stresses, which must be accounted for within an analytical model. An experimental program has been carried out through a university grant with the Ohio State University to obtain tensile and shear deformation data for a representative polymer for strain rates ranging from quasi-static to high rates of several hundred per second. This information has been used at the NASA Glenn Research Center to develop, characterize, and correlate a material model in which the strain rate dependence and nonlinearity (including hydrostatic stress effects) of the polymer are correctly analyzed. To obtain the material data, Glenn s researchers designed and fabricated test specimens of a representative toughened epoxy resin. Quasi-static tests at low strain rates and split Hopkinson bar tests at high strain rates were then conducted at the Ohio State University. The experimental data confirmed the strong effects of strain rate on both the tensile and shear deformation of the polymer. For the analytical model, Glenn researchers modified state variable constitutive equations previously used for the viscoplastic analysis of metals to allow for the analysis of the nonlinear, strain-rate-dependent polymer deformation. Specifically, we accounted for the effects of

Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

NASA Astrophysics Data System (ADS)

Archer, Lynden

Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

Functionalization of silicon nanowires by conductive and non-conductive polymers

NASA Astrophysics Data System (ADS)

Belhousse, S.; Tighilt, F.-Z.; Sam, S.; Lasmi, K.; Hamdani, K.; Tahanout, L.; Megherbi, F.; Gabouze, N.

2017-11-01

The work reports on the development of hybrid devices based on silicon nanowires (SiNW) with polymers and the difference obtained when using conductive and non-conductive polymers. SiNW have attracted much attention due to their importance in understanding the fundamental properties at low dimensionality as well as their potential application in nanoscale devices as in field effect transistors, chemical or biological sensors, battery electrodes and photovoltaics. SiNW arrays were formed using metal assisted chemical etching method. This process is simple, fast and allows obtaining a wide range of silicon nanostructures. Hydrogen-passivated SiNW surfaces show relatively poor stability. Surface modification with organic species confers the desired stability and enhances the surface properties. For this reason, this work proposes a covalent grafting of organic material onto SiNW surface. We have chosen a non-conductive polymer polyvinylpyrrolidone (PVP) and conductive polymers polythiophene (PTh) and polypyrrole (PPy), in order to evaluate the electric effect of the polymers on the obtained materials. The hybrid structures were elaborated by the polymerization of the corresponding conjugated monomers by electrochemical route; this electropolymerization offers several advantages such as simplicity and rapidity. SiNW functionalization by conductive polymers has shown to have a huge effect on the electrical mobility. Hybrid surface morphologies were characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR-ATR) and contact angle measurements.

Nanostructured conjugated polymers in chemical sensors: synthesis, properties and applications.

PubMed

Correa, D S; Medeiros, E S; Oliveira, J E; Paterno, L G; Mattoso, Luiz C

2014-09-01

Conjugated polymers are organic materials endowed with a π-electron conjugation along the polymer backbone that present appealing electrical and optical properties for technological applications. By using conjugated polymeric materials in the nanoscale, such properties can be further enhanced. In addition, the use of nanostructured materials makes possible miniaturize devices at the micro/nano scale. The applications of conjugated nanostructured polymers include sensors, actuators, flexible displays, discrete electronic devices, and smart fabric, to name a few. In particular, the use of conjugated polymers in chemical and biological sensors is made feasible owning to their sensitivity to the physicochemical conditions of its surrounding environment, such as chemical composition, pH, dielectric constant, humidity or even temperature. Subtle changes in these conditions bring about variations on the electrical (resistivity and capacitance), optical (absorptivity, luminescence, etc.), and mechanical properties of the conjugated polymer, which can be precisely measured by different experimental methods and ultimately associated with a specific analyte and its concentration. The present review article highlights the main features of conjugated polymers that make them suitable for chemical sensors. An especial emphasis is given to nanostructured sensors systems, which present high sensitivity and selectivity, and find application in beverage and food quality control, pharmaceutical industries, medical diagnosis, environmental monitoring, and homeland security, and other applications as discussed throughout this review.

Stimulation of immune systems by conjugated polymers and their potential as an alternative vaccine adjuvant

NASA Astrophysics Data System (ADS)

Gong, Hua; Xiang, Jian; Xu, Ligeng; Song, Xuejiao; Dong, Ziliang; Peng, Rui; Liu, Zhuang

2015-11-01

Recently, conjugated polymers have been widely explored in the field of nanomedicine. Careful evaluations of their biological effects are thus urgently needed. Hereby, we systematically evaluated the biological effects of different types of conjugated polymers on macrophages and dendritic cells (DCs), which play critical roles in the innate and adaptive immune systems, respectively. While naked poly-(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) exhibits a high level of cytotoxicity, polyethylene glycol (PEG) modified PEDOT:PSS (PEDOT:PSS-PEG) shows greatly reduced toxicity to various types of cells. To our surprise, PEGylation of PEDOT:PSS could obviously enhance the cellular uptake of these nanoparticles, leading to subsequent immune stimulations of both macrophages and DCs. In contrast, another type of conjugated polymer, polypyrrole (PPy), is found to be an inert material with neither significant cytotoxicity nor noticeable immune-stimulation activity. Interestingly, utilizing ovalbumin (OVA) as a model antigen, it is further uncovered in our ex vivo experiment that PEDOT:PSS-PEG may serve as an adjuvant to greatly enhance the immunogenicity of OVA upon simple mixing. Our study on the one hand suggests the promise of developing novel nano-adjuvants based on conjugated polymers, and on the other hand highlights the importance of careful evaluations of the impacts of any new nanomaterials developed for nanomedicine on the immune systems.Recently, conjugated polymers have been widely explored in the field of nanomedicine. Careful evaluations of their biological effects are thus urgently needed. Hereby, we systematically evaluated the biological effects of different types of conjugated polymers on macrophages and dendritic cells (DCs), which play critical roles in the innate and adaptive immune systems, respectively. While naked poly-(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) exhibits a high level of cytotoxicity

Liquid-crystalline aromatic-aliphatic copolyester bioresorbable polymers.

PubMed

de Oca, Horacio Montes; Wilson, Joanne E; Penrose, Andrew; Langton, David M; Dagger, Anthony C; Anderson, Melissa; Farrar, David F; Lovell, Christopher S; Ries, Michael E; Ward, Ian M; Wilson, Andrew D; Cowling, Stephen J; Saez, Isabel M; Goodby, John W

2010-10-01

The synthesis and characterisation of a series of liquid-crystalline aromatic-aliphatic copolyesters are presented. Differential scanning calorimetry showed these polymers have a glass transition temperature in the range 72 degrees C-116 degrees C. Polarised optical microscopy showed each polymer exhibits a nematic mesophase on heating to the molten state at temperatures below 165 degrees C. Melt processing is demonstrated by the production of injection moulded and compression moulded specimens with Young's modulus of 5.7 +/- 0.3 GPa and 2.3 +/- 0.3 GPa, respectively. Wide-angle X-ray scattering data showed molecular orientation is responsible for the increase of mechanical properties along the injection direction. Degradation studies in the temperature range 37 degrees C-80 degrees C are presented for one polymer of this series and a kinetic constant of 0.002 days(-1) is obtained at 37 degrees C assuming a first order reaction. The activation energy (83.4 kJ mol(-1)) is obtained following the Arrhenius analysis of degradation, showing degradation of this material is less temperature sensitive compared with other commercially available biodegradable polyesters. In vitro and in vivo biocompatibility data are presented and it is shown the unique combination of degradative, mechanical and biological properties of these polymers may represent in the future an alternative for medical device manufacturers. Copyright 2010 Elsevier Ltd. All rights reserved.

Feasibility and Biocompatibility of 3D-Printed Photopolymerized and Laser Sintered Polymers for Neuronal, Myogenic, and Hepatic Cell Types.

PubMed

Rimington, Rowan P; Capel, Andrew J; Player, Darren J; Bibb, Richard J; Christie, Steven D R; Lewis, Mark P

2018-06-13

The integration of additive manufacturing (AM) technology within biological systems holds significant potential, specifically when refining the methods utilized for the creation of in vitro models. Therefore, examination of cellular interaction with the physical/physicochemical properties of 3D-printed polymers is critically important. In this work, skeletal muscle (C 2 C 12 ), neuronal (SH-SY5Y) and hepatic (HepG2) cell lines are utilized to ascertain critical evidence of cellular behavior in response to 3D-printed candidate polymers: Clear-FL (stereolithography, SL), PA-12 (laser sintering, LS), and VeroClear (PolyJet). This research outlines initial critical evidence for a framework of polymer/AM process selection when 3D printing biologically receptive scaffolds, derived from industry standard, commercially available AM instrumentation. C 2 C 12 , SH-SY5Y, and HepG2 cells favor LS polymer PA-12 for applications in which cellular adherence is necessitated. However, cell type specific responses are evident when cultured in the chemical leachate of photopolymers (Clear-FL and VeroClear). With the increasing prevalence of 3D-printed biointerfaces, the development of rigorous cell type specific biocompatibility data is imperative. Supplementing the currently limited database of functional 3D-printed biomaterials affords the opportunity for experiment-specific AM process and polymer selection, dependent on biological application and intricacy of design features required. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conjugated polymers: Watching polymers dance

NASA Astrophysics Data System (ADS)

Rothberg, Lewis

2011-06-01

Single-molecule spectroscopy allows fluctuations of conjugated polymer conformation to be monitored during solvent vapour annealing. Dramatic changes in fluorescence behaviour are observed and interpreted in terms of transformations between extended and collapsed polymer geometries.

Conjugated Polymer for Voltage-Controlled Release of Molecules.

PubMed

Liu, Shenghua; Fu, Ying; Li, Guijun; Li, Li; Law, Helen Ka-Wai; Chen, Xianfeng; Yan, Feng

2017-09-01

Conjugated polymers are attractive in numerous biological applications because they are flexible, biocompatible, cost-effective, solution-processable, and electronic/ionic conductive. One interesting application is for controllable drug release, and this has been realized previously using organic electronic ion pumps. However, organic electronic ion pumps show high operating voltages and limited transportation efficiency. Here, the first report of low-voltage-controlled molecular release with a novel organic device based on a conjugated polymer poly(3-hexylthiophene) is presented. The releasing rate of molecules can be accurately controlled by the duration of the voltage applied on the device. The use of a handy mobile phone to remotely control the releasing process and its application in delivering an anticancer drug to treat cancer cells are also successfully demonstrated. The working mechanism of the device is attributed to the unique switchable permeability of poly(3-hexylthiophene) in aqueous solutions under a bias voltage that can tune the wettability of poly(3-hexylthiophene) via oxidation or reduction processes. The organic devices are expected to find many promising applications for controllable drug delivery in biological systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer structure-property requirements for stereolithographic 3D printing of soft tissue engineering scaffolds.

PubMed

Mondschein, Ryan J; Kanitkar, Akanksha; Williams, Christopher B; Verbridge, Scott S; Long, Timothy E

2017-09-01

This review highlights the synthesis, properties, and advanced applications of synthetic and natural polymers 3D printed using stereolithography for soft tissue engineering applications. Soft tissue scaffolds are of great interest due to the number of musculoskeletal, cardiovascular, and connective tissue injuries and replacements humans face each year. Accurately replacing or repairing these tissues is challenging due to the variation in size, shape, and strength of different types of soft tissue. With advancing processing techniques such as stereolithography, control of scaffold resolution down to the μm scale is achievable along with the ability to customize each fabricated scaffold to match the targeted replacement tissue. Matching the advanced manufacturing technique to polymer properties as well as maintaining the proper chemical, biological, and mechanical properties for tissue replacement is extremely challenging. This review discusses the design of polymers with tailored structure, architecture, and functionality for stereolithography, while maintaining chemical, biological, and mechanical properties to mimic a broad range of soft tissue types. Copyright © 2017 Elsevier Ltd. All rights reserved.

Flexible Polymer/Metal/Polymer and Polymer/Metal/Inorganic Trilayer Transparent Conducting Thin Film Heaters with Highly Hydrophobic Surface.

PubMed

Kang, Tae-Woon; Kim, Sung Hyun; Kim, Cheol Hwan; Lee, Sang-Mok; Kim, Han-Ki; Park, Jae Seong; Lee, Jae Heung; Yang, Yong Suk; Lee, Sang-Jin

2017-09-27

Polymer/metal/polymer and polymer/metal/inorganic trilayer-structured transparent electrodes with fluorocarbon plasma polymer thin film heaters have been proposed. The polymer/metal/polymer and polymer/metal/inorganic transparent conducting thin films fabricated on a large-area flexible polymer substrate using a continuous roll-to-roll sputtering process show excellent electrical properties and visible-light transmittance. They also exhibit water-repelling surfaces to prevent wetting and to remove contamination. In addition, the adoption of a fluorocarbon/metal/fluorocarbon film permits an outer bending radius as small as 3 mm. These films have a sheet resistance of less than 5 Ω sq -1 , sufficient to drive light-emitting diode circuits. The thin film heater with the fluorocarbon/Ag/SiN x structure exhibits excellent heating characteristics, with a temperature reaching 180 °C under the driving voltage of 13 V. Therefore, the proposed polymer/metal/polymer and polymer/metal/inorganic transparent conducting electrodes using polymer thin films can be applied in flexible and rollable displays as well as automobile window heaters and other devices.

Hydrophilization of synthetic biodegradable polymer scaffolds for improved cell/tissue compatibility.

PubMed

Oh, Se Heang; Lee, Jin Ho

2013-02-01

Porous scaffolds have been widely used in tissue engineering because they can guide cells and tissues to grow, synthesize extracellular matrix and other biological molecules, and facilitate the formation of functional tissues and organs. Although various natural and synthetic biodegradable polymers have been used to fabricate the scaffolds, synthetic polymers have been more widely used for scaffolds since they have good mechanical strength, reproducible/controllable mechanical-chemical properties, and controllable biodegradation rates. However, the 'hydrophobic character' of common synthetic polymers is considered a limitation for tissue engineering applications because it can lead to a low initial cell seeding density, heterogeneous cell distribution in the scaffold, and slow cell growth due to insufficient absorption/diffusion of cell culture medium into scaffold and lack of specific interaction sites with cells. The hydrophilization of porous synthetic polymer scaffolds has been considered as one of the simple but effective approaches to achieve desirable in vitro cell culture and in vivo tissue regeneration within the scaffolds. In this review paper, representative synthetic biodegradable polymers and techniques to fabricate porous scaffolds are briefly summarized and their hydrophilization techniques to improve cell/tissue compatibility are discussed.

Microstructure synthesis control of biological polyhydroxyalkanoates with mass spectrometry

NASA Astrophysics Data System (ADS)

Pederson, Erik Norman

Polyhydroxyalkanoates (PHA's) are a class of biologically produced polymers, or plastic, that is synthesized by various microorganisms. PHA's are made from biorenewable resources and are fully biodegradable and biocompatible, making them an environmentally friendly green polymer. A method of incorporating polymer microstructure into the PHA synthesized in Ralstonia eutropha was developed. These microstructures were synthesized with polyhydroxybutyrate (PHB) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) as the polymer domains. To synthesize the PHB V copolymer, the additional presence of valerate was required. To control valerate substrate additions to the bioreactor, an off-gas mass spectrometry (MS) feedback control system was developed. Important process information including the cell physiology, growth kinetics, and product formation kinetics in the bioreactor was obtained with MS and used to control microstructure synthesis. The two polymer microstructures synthesized were core-shell granules and block copolymers. Block copolymers control the structure of the individual polymer chains while core-shell granules control the organization of many polymer chains. Both these microstructures result in properties unattainable by blending the two polymers together. The core-shell structures were synthesized with controlled domain thickness based on a developed model. Different block copolymers compositions were synthesized by varying the switching time of the substrate pulses responsible for block copolymer synthesis. The block copolymers were tested to determine their chemical properties and cast into films to determine the materials properties. These block copolymer films possessed new properties not achieved by copolymers or blends of the two polymers.

A molecular model for cohesive slip at polymer melt/solid interfaces.

PubMed

Tchesnokov, M A; Molenaar, J; Slot, J J M; Stepanyan, R

2005-06-01

A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulk+boundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.

Nanoparticle interface to biology: applications in probing and modulating biological processes.

PubMed

Kah, James Chen Yong; Yeo, Eugenia Li Ling; Koh, Wee Ling; Poinard, Barbara Elodie Ariane; Neo, Dawn Jing Hui

2013-01-01

Nanomaterials can be considered as "pseudo" subcellular entities that are similar to endogenous biomolecules because of their size and ability to interact with other biomolecules. The interaction between nanoparticles and biomolecules gives rise to the nano-bio interface between a nanoparticle and its biological environment. This is often defined in terms of the biomolecules that are present on the surface of the nanoparticles. The nano-bio interface alters the surface characteristics and is what the biological system sees and interacts with. The nanoparticle can thus be viewed as a "scaffold" to which molecules are attached. Intelligent design of this nano-bio interface is therefore crucial to the functionality of nanoscale systems in biology. In this review, we discuss the most common nano-bio interfaces formed from molecules including DNA, polymers, proteins, and antibodies, and discuss their applications in probing and modulating biological processes. We focus our discussion on the nano-bio interface formed on gold nanoparticles as our nanoparticle "scaffold" of interest in part because of our research interest as well as their unique physicochemical properties. While not exhaustive, this review provides a good overview of the latest advances in the use of gold nanomaterial interface to probe and modulate biological processes.

Monitoring and modulating ion traffic in hybrid lipid/polymer vesicles

DOE PAGES

Paxton, Walter F.; McAninch, Patrick T.; Achyuthan, Komandoor E.; ...

2017-08-01

Controlling the traffic of molecules and ions across membranes is a critical feature in a number of biologically relevant processes and highly desirable for the development of technologies based on membrane materials. In this study, ion transport behavior of hybrid lipid/polymer membranes was studied in the absence and presence of ion transfer agents. A pH-sensitive fluorophore was used to investigate ion (H +/OH -) permeability across hybrid lipid/polymer membranes as a function of the fraction of amphiphilic block copolymer. It was observed that vesicles with intermediate lipid/polymer ratios tend to be surprisingly more permeable to ion transport than the puremore » lipid or pure polymer vesicles. Hybrid vesicle permeability could be further modulated with valinomycin, nigericin, or gramicidin A, which significantly expedite the dissipation of externally-imposed pH gradients by facilitating the transport of the rate-limiting co-ions (e.g. K +) ions across the membrane. For gramicidin A, ion permeability decreased with increasing polymer mole fraction, and the method of introduction of gramicidin A into the membrane played an important role. Finally, strategies to incorporate biofunctional molecules and facilitate their activity in synthetic systems are highly desirable for developing artificial organelles or other synthetic compartmentalized structures requiring control over molecular traffic across biomimetic membranes.« less

Modular and Orthogonal Synthesis of Hybrid Polymers and Networks

PubMed Central

Liu, Shuang; Dicker, Kevin T.; Jia, Xinqiao

2015-01-01

Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions. PMID:25572255

Global Survey of National Constitutions: Mapping Constitutional Commitments to Sexual and Reproductive Health and Rights.

PubMed

Pizzarossa, Lucía Berro; Perehudoff, Katrina

2017-12-01

General Comment No. 22, issued in 2016 by the Committee on Economic, Social and Cultural Rights (CESCR), clarifies states' legal duties to respect, protect, and fulfill the right to sexual and reproductive health (SRH). Our study analyzes domestic constitutions around the world to investigate whether and to what extent the right to sexual and reproductive health is respected, protected, and fulfilled; to what extent these provisions are inclusive and non-discriminatory; and to what degree the interlinkages between this and other human rights are acknowledged. Of the 195 constitutions accessed, 27 enshrine sexual and/or reproductive health, and seven adopt restrictive approaches to this right. In the 27 constitutions, provisions most frequently enshrine respect of one's sexual health and family planning decisions, the protection of sexual health, and the provision of reproductive health care and family planning services (fulfillment). Most of the 27 constitutions fail to adequately respect reproductive health rights; to protect reproductive health, family planning, and abortion services from third-party interference; and to fulfill all dimensions of sexual health and access to abortion. Three of the 27 constitutions enshrine a universal right to SRH, and additional constitutions protect specific vulnerable groups (such as women, children) and/or restrict the scope of rights holders to couples. Among the 27 constitutions, nine explicitly link the right to sexual and reproductive health to the rights to education, science, and/or to make autonomous decisions about sexuality and reproduction. Our results can serve as a baseline measure to track constitutional reforms in pursuit of the realization of sexual and reproductive health and rights, and as building blocks for future lawmakers committed to realizing these rights through domestic legal reform.

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers

DOE PAGES

Wang, Jun; Bonnesen, Peter V; Rangel, E.; ...

2016-01-04

The self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N9-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two ormore » more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. The resulting characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Moreover, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.« less

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers

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

Wang, Jun; Bonnesen, Peter V; Rangel, E.

The self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N9-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two ormore » more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. The resulting characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Moreover, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.« less

Distinguishing pathological from constitutional small for gestational age births in population-based studies.

PubMed

Ananth, Cande V; Vintzileos, Anthony M

2009-10-01

Small for gestational age (SGA) can occur following a pathological process or may represent constitutionally small fetuses. However, distinguishing these processes is often difficult, especially in large studies, where the term SGA is often used as a proxy for restricted fetal growth. Since biologic variation in fetal size is largely a third trimester phenomenon, we hypothesized that the definition of SGA at term may include a sizeable proportion of constitutionally small fetuses. In contrast, since biologic variation in fetal size is not fully expressed in (early) preterm gestations, it is plausible that SGA in early preterm gestations would comprise a large proportion of growth restricted fetuses. We compared mortality and morbidity rates between SGA and appropriate for gestational age (AGA) babies. A population-based study of over 19million non-malformed, singleton births (1995-04) in the United States was performed. Gestational age (24-44weeks) was based on a clinical estimate. SGA and AGA were defined as sex-specific birthweight <10th and 25-74th centiles, respectively, for gestational age. All analyses were adjusted for a variety of confounding factors. Excess mortality risk in SGA and AGA babies. On an additive scale, stillbirth and neonatal mortality rates were higher at every preterm gestation among SGA than AGA births, and similar at term gestations. An inverse relationship between gestational age and excess deaths between SGA and AGA babies delivered at <37weeks was evident. In early preterm gestations, the definition of SGA may well be justified as a proxy for IUGR. In contrast, SGA babies that are delivered at term are likely to be constitutionally small.

Polymer based drug delivery systems for mycobacterial infections.

PubMed

Pandey, Rajesh; Khuller, G K

2004-07-01

In the last decade, polymer based technologies have found wide biomedical applications. Polymers, whether synthetic (e.g. polylactide-co-glycolide or PLG) or natural (e.g. alginate, chitosan etc.), have the property of encapsulating a diverse range of molecules of biological interest and bear distinct therapeutic advantages such as controlled release of drugs, protection against the premature degradation of drugs and reduction in drug toxicity. These are important considerations in the long-duration treatment of chronic infectious diseases such as tuberculosis in which patient non-compliance is the major obstacle to successful chemotherapy. Antitubercular drugs, singly or in combination, have been encapsulated in polymers to provide controlled drug release and the system also offers the flexibility of selecting various routes of administration such as oral, subcutaneous and aerosol. The present review highlights the approaches towards the preparation of polymeric antitubercular drug delivery systems, emphasizing how the route of administration may influence drug bioavailability as well as the chemotherapeutic efficacy. In addition, the pros and cons of the various delivery systems are also discussed.

Electron transfer in biology

NASA Astrophysics Data System (ADS)

Williams, R. J. P.

Electron transfer is one of the key reactions of biology not just in catalysis of oxidation/reduction reactions but in the conversion of sources of energy such as light to usable form for chemical transformations. There are then two intriguing problems. What is the nature of the matrix in which electrons flow in a biological cell after the initial charge separation due for example to the absorption of light. Here we are examining biological structures similar to man's electronic wires and the construction must be of low resistance in what are apparently insulators - organic polymers. It has been found that the electronic conduction system is largely made from metallo-proteins associated with lipid membranes. We understand much about these biological wires today. The second problem concerns the conversion of the energy captured from the light into usable chemical form. The major synthetic step in the production of biological polymers, including proteins, DNA, RNA, polysaccharides and fats, is condensation, i.e. the removal of water in the formation of amides, esters and so on. Now these condensation reactions are driven in biology by using a drying agent in water, namely the anhydride, pyrophosphate, in a special compound ATP, adenosine triphosphate. The central problem is to discover exactly how the flow of electrons can be related to the synthesis of (bound) pyrophosphate. (In a thermodynamic sense pyrophosphate is a water soluble kinetically stable drying agent comparable with solid P2O5.) In the biological systems the connection between these different classes of reaction, electron transfer and condensation, is known to be via the production of an energized gradient of protons across the biological membrane which arises from the flow of electrons across the same membrane in the electron transport wires of biology. However we do not understand thoroughly the steps which lead from electron flow in a membrane to proton gradients in that membrane, i.e. electron

Global Survey of National Constitutions

PubMed Central

Perehudoff, Katrina

2017-01-01

Abstract General Comment No. 22, issued in 2016 by the Committee on Economic, Social and Cultural Rights (CESCR), clarifies states’ legal duties to respect, protect, and fulfill the right to sexual and reproductive health (SRH). Our study analyzes domestic constitutions around the world to investigate whether and to what extent the right to sexual and reproductive health is respected, protected, and fulfilled; to what extent these provisions are inclusive and non-discriminatory; and to what degree the interlinkages between this and other human rights are acknowledged. Of the 195 constitutions accessed, 27 enshrine sexual and/or reproductive health, and seven adopt restrictive approaches to this right. In the 27 constitutions, provisions most frequently enshrine respect of one’s sexual health and family planning decisions, the protection of sexual health, and the provision of reproductive health care and family planning services (fulfillment). Most of the 27 constitutions fail to adequately respect reproductive health rights; to protect reproductive health, family planning, and abortion services from third-party interference; and to fulfill all dimensions of sexual health and access to abortion. Three of the 27 constitutions enshrine a universal right to SRH, and additional constitutions protect specific vulnerable groups (such as women, children) and/or restrict the scope of rights holders to couples. Among the 27 constitutions, nine explicitly link the right to sexual and reproductive health to the rights to education, science, and/or to make autonomous decisions about sexuality and reproduction. Our results can serve as a baseline measure to track constitutional reforms in pursuit of the realization of sexual and reproductive health and rights, and as building blocks for future lawmakers committed to realizing these rights through domestic legal reform. PMID:29302182

Correlating antimicrobial activity and model membrane leakage induced by nylon-3 polymers and detergents

PubMed Central

Hovakeemian, Sara G.; Liu, Runhui; Gellman, Samuel H.; Heerklotz, Heiko

2015-01-01

Most antimicrobial peptides act upon target microorganisms by permeabilizing their membranes. The mode of action is often assessed by vesicle leakage experiments that use model membranes, with the assumption that biological activity arises from permeabilization of the lipid bilayer. The current work aims to extend the interpretation of vesicle leakage results and examine the correlation between vesicle leakage and antimicrobial activity. To this end, we used a lifetime-based leakage assay with calcein-loaded vesicles to study the membrane permeabilizing properties of a novel antifungal polymer poly-NM, two of its analogs, and a series of detergents. In conjunction, the biological activities of these compounds against Candida albicans were assessed and correlated with data from vesicle leakage. Poly-NM induces all-or-none leakage in polar yeast lipid vesicles at the polymer’s MIC, 3 μg/mL. At this and higher concentrations, complete leakage after an initial lag time was observed. Concerted activity tests imply that this polymer acts independently of the detergent octyl glucoside (OG) for both vesicle leakage and activity against C. albicans spheroplasts. In addition, Poly-NM was found to have negligible activity against zwitterionic vesicles and red blood cells. Our results provide a consistent, detailed picture of the mode of action of Poly-NM: this polymer induces membrane leakage by electrostatic lipid clustering. In contrast, Poly-MM:CO, a nylon-3 polymer comprised of both cationic and hydrophobic segments, seems to act by a different mechanism that involves membrane asymmetry stress. Vesicle leakage for this polymer is transient (limited to <100%) and graded, non-specific among zwitterionic and polar yeast lipid vesicles, additive with detergent action, and correlates poorly with biological activity. Based on these results, we conclude that comprehensive leakage experiments can provide a detailed description of the mode of action of membrane permeabilizing

Teaching About the Constitution.

ERIC Educational Resources Information Center

White, Charles S.

1988-01-01

Reviews "The U.S. Constitution Then and Now," a two-unit program using the integrated database and word processing capabilities of AppleWorks. For grades 7-12, the units simulate the constitutional convention and the principles of free speech and privacy. Concludes that with adequate time, the program can provide a potentially powerful…

The U.S. Constitution in Today's World.

ERIC Educational Resources Information Center

Patrick, John J.

A comparative study of constitutions and governments in world history is a key to deeper understanding of the U.S. Constitution. While many countries have constitutions, the United States is among a minority of nations in today's world that has a constitutional government. Many nations' constitutions truly guarantee few protections of individual…

Biological and physicochemical properties of carbon-graphite fibre-reinforced polymers intended for implant suprastructures.

PubMed

Segerström, Susanna; Sandborgh-Englund, Gunilla; Ruyter, Eystein I

2011-06-01

The aim of this study was to determine water sorption, water solubility, dimensional change caused by water storage, residual monomers, and possible cytotoxic effects of heat-polymerized carbon-graphite fibre-reinforced composites with different fibre loadings based on methyl methacrylate/poly(methyl methacrylate) (MMA/PMMA) and the copolymer poly (vinyl chloride-co-vinyl acetate). Two different resin systems were used. Resin A contained ethylene glycol dimethacrylate (EGDMA) and 1,4-butanediol dimethacrylate (1,4-BDMA); the cross-linker in Resin B was diethylene glycol dimethacrylate (DEGDMA). The resin mixtures were reinforced with 24, 36 and 47 wt% surface-treated carbon-graphite fibres. In addition, polymer B was reinforced with 58 wt% fibres. Water sorption was equal to or below 3.34±1.18 wt%, except for the 58 wt% fibre loading of polymer B (5.27±1.22 wt%). Water solubility was below 0.36±0.015 wt%, except for polymer B with 47 and 58 wt% fibres. For all composites, the volumetric increase was below 0.01±0.005 vol%. Residual MMA monomer was equal to or below 0.68±0.05 wt% for the fibre composites. The filter diffusion test and the (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) (MTT) assay demonstrated no cytotoxicity for the carbon-graphite fibre-reinforced composites, and residual cross-linking agents and vinyl chloride were not detectable by high-performance liquid chromatography (HPLC) analysis. © 2011 Eur J Oral Sci.

Controlled Radical Polymerization as an Enabling Approach for the Next Generation of Protein-Polymer Conjugates.

PubMed

Pelegri-O'Day, Emma M; Maynard, Heather D

2016-09-20

Protein-polymer conjugates are unique constructs that combine the chemical properties of a synthetic polymer chain with the biological properties of a biomacromolecule. This often leads to improved stabilities, solubilities, and in vivo half-lives of the resulting conjugates, and expands the range of applications for the proteins. However, early chemical methods for protein-polymer conjugation often required multiple polymer modifications, which were tedious and low yielding. To solve these issues, work in our laboratory has focused on the development of controlled radical polymerization (CRP) techniques to improve synthesis of protein-polymer conjugates. Initial efforts focused on the one-step syntheses of protein-reactive polymers through the use of functionalized initiators and chain transfer agents. A variety of functional groups such as maleimide and pyridyl disulfide could be installed with high end-group retention, which could then react with protein functional groups through mild and biocompatible chemistries. While this grafting to method represented a significant advance in conjugation technique, purification and steric hindrance between large biomacromolecules and polymer chains often led to low conjugation yields. Therefore, a grafting from approach was developed, wherein a polymer chain is grown from an initiating site on a functionalized protein. These conjugates have demonstrated improved homogeneity, characterization, and easier purification, while maintaining protein activity. Much of this early work utilizing CRP techniques focused on polymers made up of biocompatible but nonfunctional monomer units, often containing oligoethylene glycol meth(acrylate) or N-isopropylacrylamide. These branched polymers have significant advantages compared to the historically used linear poly(ethylene glycols) including decreased viscosities and thermally responsive behavior, respectively. Recently, we were motivated to use CRP techniques to develop polymers with

Stimulation of immune systems by conjugated polymers and their potential as an alternative vaccine adjuvant.

PubMed

Gong, Hua; Xiang, Jian; Xu, Ligeng; Song, Xuejiao; Dong, Ziliang; Peng, Rui; Liu, Zhuang

2015-12-07

Recently, conjugated polymers have been widely explored in the field of nanomedicine. Careful evaluations of their biological effects are thus urgently needed. Hereby, we systematically evaluated the biological effects of different types of conjugated polymers on macrophages and dendritic cells (DCs), which play critical roles in the innate and adaptive immune systems, respectively. While naked poly-(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) ( PSS) exhibits a high level of cytotoxicity, polyethylene glycol (PEG) modified PSS (PEDOT:PSS-PEG) shows greatly reduced toxicity to various types of cells. To our surprise, PEGylation of PSS could obviously enhance the cellular uptake of these nanoparticles, leading to subsequent immune stimulations of both macrophages and DCs. In contrast, another type of conjugated polymer, polypyrrole (PPy), is found to be an inert material with neither significant cytotoxicity nor noticeable immune-stimulation activity. Interestingly, utilizing ovalbumin (OVA) as a model antigen, it is further uncovered in our ex vivo experiment that PSS-PEG may serve as an adjuvant to greatly enhance the immunogenicity of OVA upon simple mixing. Our study on the one hand suggests the promise of developing novel nano-adjuvants based on conjugated polymers, and on the other hand highlights the importance of careful evaluations of the impacts of any new nanomaterials developed for nanomedicine on the immune systems.

Shape memory polymers

DOEpatents

Wilson, Thomas S.; Bearinger, Jane P.

2017-08-29

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Shape memory polymers

DOEpatents

Wilson, Thomas S.; Bearinger, Jane P.

2015-06-09

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Mechanisms of Morphology Development and Control in Polymer- Polymer Blends

NASA Astrophysics Data System (ADS)

Macosko, Christopher W.

1998-03-01

Polymer-polymer blends continue to be the most important method for achieving optimization of properties in plastics products. Over 30 percent of all plastics are blends. While miscible blends generally give average properties between the components, immiscible blends offer synergistic possibilities such as high modulus with high toughness; high flow with high impact strength or diffusion barriers with good mechanical properties and low cost. The key to performance of these immiscible blends is their morphology. There are several important types of morphology which can lead to valuable property improvement: emulsion - small polymer spheres well dispersed in a polymer matrix. double emulsion - spheres inside spheres which are dispersed in another matrix. microlayer - thin, parallel layers of one polymer in a matrix. cocontinuous - two (or more) continuous, interpenetrating polymer phases. To be economical it is desirable to create these morphologies via melt mixing of powder or pellets in conventional compounding equipment. The melting stage during compounding is very important for morphology development. This presentation will demonstrate the role of melting or softening of each phase as well as their viscosity, elasticity and interfacial tension in morphology development. Interfacial modification with premade block copolymers or reactively formed copolymers can greatly alter morphology formation and stability. Experimental results will be presented which quantify the role of these additives. References to recent work in this area by our group are listed below: DeBrule, M. B., L. Levitt and C.W. Macosko, "The Rheology and Morphology of Layered Polymer Melts in Shear," Soc. Plastics Eng. Tech Papers (ANTEC), 84-89 (1996). Guegan, P., C. W. Macosko, T. Ishizone, A. Hirao and S. Nakahama, "Kinetics of Chain Coupling at Melt Interfaces, Macromol. 27, 4993-4997 (1994). Lee, M. S., T.P. Lodge, and C. W. Macosko, "Can Random Copolymers Serve as Effective Polymeric

Spectral and time-resolved properties of photoinduced hydroxyquinolines doped thin polymer films

NASA Astrophysics Data System (ADS)

Mehata, Mohan Singh

2018-01-01

Quinoline and its derivatives have a wide range of biological and pharmacological activities. Quinoline ring is used to design functional materials (quinoline derivatives) for OLEDs and field-induce electrooptics. It possesses antibacterial, antifungal, antimalarial, cardiotonic, anthelmintic, anti-inflammatory, anticonvulsant and analgesic activity. Here, we have examined photoexcitation dynamics of 6-hydroxyquinoline (6-HQ) doped in polymer films of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) and cellulose acetate (CA) at atmospheric conditions. The absorption maximum of 6-HQ in polymer films was observed at 333 ± 1 nm, whereas fluorescence (FL) maximum fell in the range of 365-371 nm. In PVA film, in addition to the typical FL, a band maximum at 432 nm appeared as a result of an excited-state intermolecular proton transfer (ESIPT) reaction facilitated in the hydrogen-bonded complex formed in the ground state between 6-HQ:PVA. The multi-exponential decay behavior of 6-HQ in all the three polymer films indicates a nanoscale heterogeneity of the polymer environments.

The compressive behaviour and constitutive equation of polyimide foam in wide strain rate and temperature

NASA Astrophysics Data System (ADS)

Yoshimoto, Akifumi; Kobayashi, Hidetoshi; Horikawa, Keitaro; Tanigaki, Kenichi

2015-09-01

These days, polymer foams, such as polyurethane foam and polystyrene foam, are used in various situations as a thermal insulator or shock absorber. In general, however, their strength is insufficient in high temperature environments because of their low glass transition temperature. Polyimide is a polymer which has a higher glass transition temperature and high strength. Its mechanical properties do not vary greatly, even in low temperature environments. Therefore, polyimide foam is expected to be used in the aerospace industry. Thus, the constitutive equation of polyimide foam that can be applied across a wide range of strain rates and ambient temperature is very useful. In this study, a series of compression tests at various strain rates, from 10-3 to 103 s-1 were carried out in order to examine the effect of strain rate on the compressive properties of polyimide foam. The flow stress of polyimide foam increased rapidly at dynamic strain rates. The effect of ambient temperature on the properties of polyimide foam was also investigated at temperature from - 190 °C to 270°∘C. The flow stress decreased with increasing temperature.

Modelling of electrokinetic phenomena involving confined polymers: Applications to DNA separation and electroosmotic flow control

NASA Astrophysics Data System (ADS)

Tessier, Frederic

Microfluidic and nanofluidic technology is revolutionizing experimental practices in analytical chemistry, molecular biology and medicine. Indeed, the development of systems of small dimensions for the processing of fluids heralds the miniaturization of traditional, cumbersome laboratory equipment onto robust, portable and efficient microchip devices (similar to the electronic microchips found in computers). Moreover, the conjunction of scale between the smallest man-made device and the largest macromolecules evolved by Nature is fertile ground for the blooming of our knowledge about the key processes of life. In fact, the conjunction is threefold, because modern computational resources also allow us to contemplate a rather explicit modelling of physical systems between the nanoscale and the microscale. In the five articles comprising this thesis, we present the results of computer simulations that address specific questions concerning the operation of two different model systems relevant to the development of small-scale fluidic devices for the manipulation and analysis of biomolecules. First, we use a Bond-Fluctuation Monte Carlo approach to study the electrophoretic drift of macromolecules across an entropic trap array built for the length separation of long, double-stranded DNA molecules. We show that the motion of the molecules is consistent with a simple balance between electric and entropic forces, in terms of a single characteristic parameter. We also extract detailed information on polymer deformation during migration, predict the separation of topoisomers, and investigate innovative ratchet driving regimes. Secondly, we present theoretical derivations, numerical calculations and Molecular Dynamics simulation results for an electrolyte confined in a capillary of nanoscopic dimensions. In particular, we study the effectiveness of neutral grafted polymer chains in reducing the magnitude of electroosmotic flow (fluid flow induced by an external electric field

Polymer/Polymer Blend Solar Cells Using Tetraazabenzodifluoranthene Diimide Conjugated Polymers as Electron Acceptors

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

Li, Haiyan; Hwang, Ye-Jin; Earmme, Taeshik

2015-03-02

Two n-type semiconducting polymers with alternating arylene (thiophene or selenophene)–tetraazabenzodifluoranthene diimide (BFI) donor–acceptor architecture have been investigated as new electron acceptors in polymer/polymer blend solar cells. The new selenophene-linked polymer, PBFI-S, has a significantly smaller optical band gap (1.13 eV) than the thiophene-linked PBFI-T (1.38 eV); however, both polymers have similar HOMO/LUMO energy levels determined from cyclic voltammetry. Blends of PBFI-T with the thiazolothiazole–dithienylsilole donor polymer (PSEHTT) gave a 2.60% power conversion efficiency (PCE) with a 7.34 mA/cm2 short-circuit current. In contrast, PBFI-S:PSEHTT blends had a 0.75% PCE with similarly reduced photocurrent and external quantum efficiency. Reduced free energy formore » charge transfer and reduced bulk electron mobility in PBFI-S:PSEHTT blends compared to PBFI-T:PSEHTT blends as well as significant differences in bulk film morphology are among the reasons for the large loss in efficiency in PBFI-S:PSEHTT blend solar cells.« less

Integration of culture and biology in human development.

PubMed

Mistry, Jayanthi

2013-01-01

The challenge of integrating biology and culture is addressed in this chapter by emphasizing human development as involving mutually constitutive, embodied, and epigenetic processes. Heuristically rich constructs extrapolated from cultural psychology and developmental science, such as embodiment, action, and activity, are presented as promising approaches to the integration of cultural and biology in human development. These theoretical notions are applied to frame the nascent field of cultural neuroscience as representing this integration of culture and biology. Current empirical research in cultural neuroscience is then synthesized to illustrate emerging trends in this body of literature that examine the integration of biology and culture.

We the People: Indiana and the United States Constitution. Lectures in Observance of the Bicentennial of the Constitution.

ERIC Educational Resources Information Center

Furlong, Partick J.; And Others

These lectures, presented in observance of the U.S. Constitution bicentennial celebration, consider selected constitutionally significant law cases that occurred in Indiana. These cases are representative of U.S. constitutional development and of the relationship of Indiana to the U.S. Constitution. Patrick Furlong, in "The South Bend…

Review paper: progress in the field of conducting polymers for tissue engineering applications.

PubMed

Bendrea, Anca-Dana; Cianga, Luminita; Cianga, Ioan

2011-07-01

This review focuses on one of the most exciting applications area of conjugated conducting polymers, which is tissue engineering. Strategies used for the biocompatibility improvement of this class of polymers (including biomolecules' entrapment or covalent grafting) and also the integrated novel technologies for smart scaffolds generation such as micropatterning, electrospinning, self-assembling are emphasized. These processing alternatives afford the electroconducting polymers nanostructures, the most appropriate forms of the materials that closely mimic the critical features of the natural extracellular matrix. Due to their capability to electronically control a range of physical and chemical properties, conducting polymers such as polyaniline, polypyrrole, and polythiophene and/or their derivatives and composites provide compatible substrates which promote cell growth, adhesion, and proliferation at the polymer-tissue interface through electrical stimulation. The activities of different types of cells on these materials are also presented in detail. Specific cell responses depend on polymers surface characteristics like roughness, surface free energy, topography, chemistry, charge, and other properties as electrical conductivity or mechanical actuation, which depend on the employed synthesis conditions. The biological functions of cells can be dramatically enhanced by biomaterials with controlled organizations at the nanometer scale and in the case of conducting polymers, by the electrical stimulation. The advantages of using biocompatible nanostructures of conducting polymers (nanofibers, nanotubes, nanoparticles, and nanofilaments) in tissue engineering are also highlighted.

The Constitution by Cell

ERIC Educational Resources Information Center

Greenhut, Stephanie; Jones, Megan

2010-01-01

On their visit to the National Archives Experience in Washington, D.C., students in Jenni Ashley and Gay Brock's U.S. history classes at the Potomac School in McLean, Virginia, participated in a pilot program called "The Constitution by Cell." Armed with their cell phones, a basic understanding of the Constitution, and a willingness to…

Polymer therapeutics at a crossroads? Finding the path for improved translation in the twenty-first century.

PubMed

Duncan, Ruth

Despite the relatively small early investment, first generation 'polymer therapeutics' have been remarkably successful with more than 25 products licenced for human use as polymeric drugs, sequestrants, conjugates, and as an imaging agent. Many exhibit both clinical and commercial success with new concepts already in clinical trials. Nevertheless after four decades of evolution, this field is arriving at an important crossroads. Over the last decade, the landscape has changed rapidly. There are an increasing number of failed clinical trials, the number of 'copy' and 'generic' products is growing (danger of ignoring the biological rationale for design and suppression of innovation), potential drawbacks of PEG are becoming more evident, and the 'nanomedicine' boom has brought danger of loss of scientific focus/hype. Grasping opportunities provided by advances in understanding of the patho-physiology and molecular basis of diseases, new polymer/conjugate synthetic and analytical methods, as well as the large database of clinical experience will surely ensure a successful future for innovative polymer therapeutics. Progress will, however, be in jeopardy if polymer safety is overlooked in respect of the specific route of administration/clinical use, poorly characterised materials/formulations are used to define biological or early clinical properties, and if clinical trial protocols fail to select patients most likely to benefit from these macromolecular therapeutics. Opportunities to improve clinical trial design for polymer-anticancer drug conjugates are discussed. This short personal perspective summarises some of the important challenges facing polymer therapeutics in R&D today, and future opportunities to improve successful translation.

Surface functionalization of quantum dots with fine-structured pH-sensitive phospholipid polymer chains.

PubMed

Liu, Yihua; Inoue, Yuuki; Ishihara, Kazuhiko

2015-11-01

To add novel functionality to quantum dots (QDs), we synthesized water-soluble and pH-responsive block-type polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were composed of cytocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer segments, which contain a small fraction of active ester groups and can be used to conjugate biologically active compounds to the polymer, and pH-responsive poly(2-(N,N-diethylamino) ethyl methacrylate (DEAEMA)) segments. One terminal of the polymer chain had a hydrophobic alkyl group that originated from the RAFT initiator. This hydrophobic group can bind to the hydrophobic layer on the QD surface. A fluorescent dye was conjugated to the polymer chains via the active ester group. The block-type polymers have an amphiphilic nature in aqueous medium. The polymers were thus easily bound to the QD surface upon evaporation of the solvent from a solution containing the block-type polymer and QDs, yielding QD/fluorescence dye-conjugated polymer hybrid nanoparticles. Fluorescence resonance energy transfer (FRET) between the QDs (donors) and the fluorescent dye molecules (acceptors) was used to obtain information on the conformational dynamics of the immobilized polymers. Higher FRET efficiency of the QD/fluorescent dye-conjugated polymer hybrid nanoparticles was observed at pH 7.4 as compared to pH 5.0 due to a stretching-shrinking conformational motion of the poly(DEAEMA) segments in response to changes in pH. We concluded that the block-type MPC polymer-modified nanoparticles could be used to evaluate the pH of cells via FRET fluorescence based on the cytocompatibility of the MPC polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

A small great history of the sister Societies of Developmental Biology in Spain and Portugal.

PubMed

Palmeirim, Isabel; Aréchaga, Juan

2009-01-01

We revise the historical evolution of the societies devoted to Developmental Biology from the early activities of the Institut International dEmbryologie (IIE), founded in 1911, with particular emphasis on the more recent constitution of the Spanish Sociedad Española de Biología del Desarrollo (SEBD), founded in 1994, and the Portuguese Sociedade Portuguesa de Biologia do Desenvolvimento (SPBD), founded in 2006. We also describe the role played by The International Journal of Developmental Biology (IJDB) in the constitution of the SEBD and its projection and support to international Developmental Biology societies and individual researchers in the world, according to its mission to be a non-for-profit publication for scientists, by scientists.

Electro-Statically Stricted Polymers (ESSP)

NASA Technical Reports Server (NTRS)

Liu, C.; Bar-Cohen, Y.; Leary, S.

1999-01-01

Miniature, lightweight, miser actuators that operate similar to biological muscles can be used to develop robotic devices with unmatched capabilities and impact many technology areas. Electroactive polymers (EAP) offer the potential to producing such actuators and their main attractive feature is their ability to induce relatively large bending or longitudinal strain. EAP actuators can change the paradigm about the complexity of robots, where robotic components such as motors, gears, bearings, and others can be eliminated with simple drive mechanisms. Generally, these materials produce a relatively low force and the applications that can be considered at the current state of the art are relatively limited. While improved material are being developed there is a need for methods to develop longitudinal actuators that can contract similar to muscles. In this study, the authors began investigating the electromechanical behavior of polymers in reaction to a complex configuration of electric fields. A computer model was used to simulate the electromechanical response. Efforts were made to develop both the material basis as well as the electromechanical modeling of the actuator.

Microgravity Polymers

NASA Technical Reports Server (NTRS)

1986-01-01

A one-day, interactive workshop considering the effects of gravity on polymer materials science was held in Cleveland, Ohio, on May 9, 1985. Selected programmatic and technical issues were reviewed to introduce the field to workshop participants. Parallel discussions were conducted in three disciplinary working groups: polymer chemistry, polymer physics, and polymer engineering. This proceedings presents summaries of the workshop discussions and conclusions.

Physical models of biological information and adaptation.

PubMed

Stuart, C I

1985-04-07

The bio-informational equivalence asserts that biological processes reduce to processes of information transfer. In this paper, that equivalence is treated as a metaphor with deeply anthropomorphic content of a sort that resists constitutive-analytical definition, including formulation within mathematical theories of information. It is argued that continuance of the metaphor, as a quasi-theoretical perspective in biology, must entail a methodological dislocation between biological and physical science. It is proposed that a general class of functions, drawn from classical physics, can serve to eliminate the anthropomorphism. Further considerations indicate that the concept of biological adaptation is central to the general applicability of the informational idea in biology; a non-anthropomorphic treatment of adaptive phenomena is suggested in terms of variational principles.

Constitutional Reform for Conflict Management

DTIC Science & Technology

2014-04-01

conflict. Empirical studies reveal that both accommodative and integrative constitutional design can produce political stability , if properly...reform, and the ability of various constitutional designs to promote democracy and political stability .

Detection of Waterborne Viruses Using High Affinity Molecularly Imprinted Polymers.

PubMed

Altintas, Zeynep; Gittens, Micah; Guerreiro, Antonio; Thompson, Katy-Anne; Walker, Jimmy; Piletsky, Sergey; Tothill, Ibtisam E

2015-07-07

Molecularly imprinted polymers (MIPs) are artificial receptor ligands which can recognize and specifically bind to a target molecule. They are more resistant to chemical and biological damage and inactivation than antibodies. Therefore, target specific-MIP nanoparticles are aimed to develop and implemented to biosensors for the detection of biological toxic agents such as viruses, bacteria, and fungi toxins that cause many diseases and death due to the environmental contamination. For the first time, a molecularly imprinted polymer (MIP) targeting the bacteriophage MS2 as the template was investigated using a novel solid-phase synthesis method to obtain the artificial affinity ligand for the detection and removal of waterborne viruses through optical-based sensors. A high affinity between the artificial ligand and the target was found, and a regenerative MIP-based virus detection assay was successfully developed using a new surface plasmon resonance (SPR)-biosensor which provides an alternative technology for the specific detection and removal of waterborne viruses that lead to high disease and death rates all over the world.

Polymer Fluid Dynamics: Continuum and Molecular Approaches.

PubMed

Bird, R B; Giacomin, A J

2016-06-07

To solve problems in polymer fluid dynamics, one needs the equations of continuity, motion, and energy. The last two equations contain the stress tensor and the heat-flux vector for the material. There are two ways to formulate the stress tensor: (a) One can write a continuum expression for the stress tensor in terms of kinematic tensors, or (b) one can select a molecular model that represents the polymer molecule and then develop an expression for the stress tensor from kinetic theory. The advantage of the kinetic theory approach is that one gets information about the relation between the molecular structure of the polymers and the rheological properties. We restrict the discussion primarily to the simplest stress tensor expressions or constitutive equations containing from two to four adjustable parameters, although we do indicate how these formulations may be extended to give more complicated expressions. We also explore how these simplest expressions are recovered as special cases of a more general framework, the Oldroyd 8-constant model. Studying the simplest models allows us to discover which types of empiricisms or molecular models seem to be worth investigating further. We also explore equivalences between continuum and molecular approaches. We restrict the discussion to several types of simple flows, such as shearing flows and extensional flows, which are of greatest importance in industrial operations. Furthermore, if these simple flows cannot be well described by continuum or molecular models, then it is not necessary to lavish time and energy to apply them to more complex flow problems.

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

Endotoxin hitchhiking on polymer nanoparticles

NASA Astrophysics Data System (ADS)

Donnell, Mason L.; Lyon, Andrew J.; Mormile, Melanie R.; Barua, Sutapa

2016-07-01

The control of microbial infections is critical for the preparation of biological media including water to prevent lethal septic shock. Sepsis is one of the leading causes of death in the United States. More than half a million patients suffer from sepsis every year. Both gram-positive and gram-negative bacteria are responsible for septic infection by the most common organisms i.e., Escherichia coli and Pseuodomonas aeruginosa. The bacterial cell membrane releases negatively charged endotoxins upon death and enzymatic destruction, which stimulate antigenic response in humans to gram-negative infections. Several methods including distillation, ethylene oxide treatment, filtration and irradiation have been employed to remove endotoxins from contaminated samples, however, the reduction efficiency remains low, and presents a challenge. Polymer nanoparticles can be used to overcome the current inability to effectively sequester endotoxins from water. This process is termed endotoxin hitchhiking. The binding of endotoxin on polymer nanoparticles via electrostatic and hydrophobic interactions offers efficient removal from water. However, the effect of polymer nanoparticles and its surface areas has not been investigated for removal of endotoxins. Poly(ε-caprolactone) (PCL) polymer was tested for its ability to effectively bind and remove endotoxins from water. By employing a simple one-step phase separation technique, we were able to synthesize PCL nanoparticles of 398.3 ± 95.13 nm size and a polydispersity index of 0.2. PCL nanoparticles showed ∼78.8% endotoxin removal efficiency, the equivalent of 3.9 × 105 endotoxin units (EU) per ml. This is 8.34-fold more effective than that reported for commercially available membranes. Transmission electron microscopic images confirmed binding of multiple endotoxins to the nanoparticle surface. The concept of using nanoparticles may be applicable not only to eliminate gram-negative bacteria, but also for any gram

Constitutional aneuploidy and cancer predisposition.

PubMed

Ganmore, Ithamar; Smooha, Gil; Izraeli, Shai

2009-04-15

Constitutional aneuploidies are rare syndromes associated with multiple developmental abnormalities and the alterations in the risk for specific cancers. Acquired somatic chromosomal aneuploidies are the most common genetic aberrations in sporadic cancers. Thus studies of these rare constitutional aneuploidy syndromes are important not only for patient counseling and clinical management, but also for deciphering the mechanisms by which chromosomal aneuploidy affect cancer initiation and progression. Here we review the major constitutional aneuploidy syndromes and suggest some general mechanisms for the associated cancer predisposition.

What is biological physics?

NASA Astrophysics Data System (ADS)

Moss, Frank

1997-11-01

The question arises in a number of contexts from the editorial policies of our journals to the decisions and priorities of agencies that financially support scientific research. What kinds of papers should Physical Review E and Physical Review Letters accept within this category? What constitutes success in choosing which projects to fund? Do biological physicists discover new physics, or new biology, or do they simply make their considerable instrumental and analytical talents available to the biologists(see for example, V.A. Parsegian, Physics Today), July 1997 p. 23 and a Counterpoint by R. H. Austin, ibid p. 27.? And are there bridges to medical science? Are there now some questions in biological and medical science that cannot be creditably addressed without contemporary physics? And what does it mean that the president has ventured that the next five decades will be the age of biology as opposed to the last (which he described as the age of physics)? These questions seem interesting (at least to those who call themselves biological physicists) and may be gaining significance in view of the fact that what we loosely describe as biological physics as a field seems to be growing.

Polymers and biopolymers at interfaces

NASA Astrophysics Data System (ADS)

Hall, A. R.; Geoghegan, M.

2018-03-01

This review updates recent progress in the understanding of the behaviour of polymers at surfaces and interfaces, highlighting examples in the areas of wetting, dewetting, crystallization, and ‘smart’ materials. Recent developments in analysis tools have yielded a large increase in the study of biological systems, and some of these will also be discussed, focussing on areas where surfaces are important. These areas include molecular binding events and protein adsorption as well as the mapping of the surfaces of cells. Important techniques commonly used for the analysis of surfaces and interfaces are discussed separately to aid the understanding of their application.

Dispersion of the Photosensitizer 5,10,15,20-Tetrakis(4-Sulfonatophenyl)-porphyrin by the Amphiphilic Polymer Poly(vinylpirrolidone) in Highly Porous Solid Materials Designed for Photodynamic Therapy.

PubMed

Díaz, Claudia; Catalán-Toledo, José; Flores, Mario E; Orellana, Sandra L; Pesenti, Héctor; Lisoni, Judit; Moreno-Villoslada, Ignacio

2017-08-03

The ability of the amphiphilic and biocompatible poly(vinylpyrrolidone) to avoid self-aggregation of the photosensitizer 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous solution in the presence of the biocompatible polycation chitosan, polymer that induces the dye self-aggregation, is shown. This is related to the tendency of the dye to undergo preferential solvation by the amphiphilic polymer. Importantly, the dispersant ability of this polymer is transferred to the solid state. Thus, aerogels made of the biocompatible polymers chitosan and chondroitin sulfate, and containing the photosensitizer dispersed by the amphiphilic polymer have been synthesized. Production of reactive oxygen species by the aerogel containing the amphiphilic polymer was faster than when the polymer was absent, correlating with the relative concentration of dyes dispersed as monomers. The aerogels presented here constitute low cost biocompatible materials bearing a conventional photosensitizer for photodynamic therapy, easy to produce, store, transport, and manage in clinical practice.

A New Self-Consistent Field Model of Polymer/Nanoparticle Mixture

NASA Astrophysics Data System (ADS)

Chen, Kang; Li, Hui-Shu; Zhang, Bo-Kai; Li, Jian; Tian, Wen-De

2016-02-01

Field-theoretical method is efficient in predicting assembling structures of polymeric systems. However, it’s challenging to generalize this method to study the polymer/nanoparticle mixture due to its multi-scale nature. Here, we develop a new field-based model which unifies the nanoparticle description with the polymer field within the self-consistent field theory. Instead of being “ensemble-averaged” continuous distribution, the particle density in the final morphology can represent individual particles located at preferred positions. The discreteness of particle density allows our model to properly address the polymer-particle interface and the excluded-volume interaction. We use this model to study the simplest system of nanoparticles immersed in the dense homopolymer solution. The flexibility of tuning the interfacial details allows our model to capture the rich phenomena such as bridging aggregation and depletion attraction. Insights are obtained on the enthalpic and/or entropic origin of the structural variation due to the competition between depletion and interfacial interaction. This approach is readily extendable to the study of more complex polymer-based nanocomposites or biology-related systems, such as dendrimer/drug encapsulation and membrane/particle assembly.

Modifications of Glycans: Biological Significance and Therapeutic Opportunities

PubMed Central

Muthana, Saddam M.; Campbell, Christopher; Gildersleeve, Jeffrey C.

2012-01-01

Carbohydrates play a central role in a wide range of biological processes. As with nucleic acids and proteins, modifications of specific sites within the glycan chain can modulate a carbohydrate’s overall biological function. For example, acylation, methylation, sulfation, epimerization, and phosphorylation can occur at various positions within a carbohydrate to modulate bioactivity. Therefore, there is significant interest in identifying discrete carbohydrate modifications and understanding their biological effects. Additionally, enzymes that catalyze those modifications and proteins that bind modified glycans provide numerous targets for therapeutic intervention. This review will focus on modifications of glycans that occur after the oligomer/polymer has been assembled, generally referred to as postglycosylational modifications. PMID:22195988

Biological measurement beyond the quantum limit

NASA Astrophysics Data System (ADS)

Taylor, Michael; Janousek, Jiri; Daria, Vincent; Knittel, Joachim; Hage, Boris; Bachor, Hans; Bowen, Warwick

2013-05-01

Biology is an important frontier for quantum metrology, with quantum enhanced sensitivity allowing optical intensities to be lowered, and a consequent reduction in specimen damage and photochemical intrusion upon biological processes. Here we demonstrate the first biological measurement with precision surpassing the quantum noise limit. Naturally occurring lipid granules within living yeast cells were tracked in real time with sensitivity surpassing the quantum noise limit by 42% as they diffuse through the cytoplasm and interact with embedded polymer networks. This allowed dynamic mechanical properties of the cytoplasm to be determined with a 64% higher measurement rate than possible classically. To enable this, a new microscopy system was developed which is compatible with squeezed light, and which utilized a novel optical lock-in technique to allow quantum enhancement down to 10 Hz. This method is widely applicable, extending the reach of quantum enhanced measurement to many dynamic biological processes.

Constituting children's bodily integrity.

PubMed

Hill, B Jessie

2015-04-01

Children have a constitutional right to bodily integrity. Courts do not hesitate to vindicate that right when children are abused by state actors. Moreover, in at least some cases, a child's right to bodily integrity applies within the family, giving the child the right to avoid unwanted physical intrusions regardless of the parents' wishes. Nonetheless, the scope of this right vis-à-vis the parents is unclear; the extent to which it applies beyond the narrow context of abortion and contraception has been almost entirely unexplored and untheorized. This Article is the first in the legal literature to analyze the constitutional right of minors to bodily integrity within the family by spanning traditionally disparate doctrinal categories such as abortion rights; corporal punishment; medical decisionmaking; and nontherapeutic physical interventions such as tattooing, piercing, and circumcision. However, the constitutional right of minors to bodily integrity raises complex philosophical questions concerning the proper relationship between family and state, as well as difficult doctrinal and theoretical issues concerning the ever-murky idea of state action. This Article canvasses those issues with the ultimate goal of delineating a constitutional right of bodily security and autonomy for children.

[Comparative research into the process of forming the theory of constitution in ancient western medicine and that of four trigrams constitution in Korean medicine and contents of two theories of constitution].

PubMed

Park, Joo-Hong

2009-06-01

After conducting comparative research into the process of forming the Theory of Constitution in Ancient Western Medicine and that of Four Trigrams Constitution(Sasang Constitution) in Korean Medicine and contents of two Theories of Constitution in terms of medical history, both theories were found to be formed by an interaction between philosophy and medicine, followed by a combination of the two, on a philosophical basis. The Theory of Constitution in Ancient Western Medicine began with the Theory of Four Elements presented by Empedocles, followed by the Theory of Four Humors presented by Hippocrates and the Theory of Four Temperaments by Galenos, forming and developing the Theory of Constitution. After the Middle Ages, there was no significant advance in the Theory of Constitution by modern times ; however, it developed into the theory of constitution type of Kretschmer and others after the 19th century and into the scientific theory of constitution based on genetics presented by Garrod and others early in the 20th century. The Theory of Four Trigrams Constitution began with the Theory of Constitution in Huangdi Neijing, followed by developments and influences of existing medicine called beginning, restoration, and revival periods and DongeuisoosebowonSaSangChoBonGwon based on the original philosophy of Four Trigrams presented by Lee Je-ma, which is found in GyeokChiGo, DongMuYuGo and so on, ultimately forming and developing into the Theory of Four Trigrams Constitution in Dongeuisoosebowon. Recently, a lot of research is being conducted into making it objective in order to achieve reproducibility in diagnosis and so forth of Four Trigrams Constitution.

Fused electron deficient semiconducting polymers for air stable electron transport.

PubMed

Onwubiko, Ada; Yue, Wan; Jellett, Cameron; Xiao, Mingfei; Chen, Hung-Yang; Ravva, Mahesh Kumar; Hanifi, David A; Knall, Astrid-Caroline; Purushothaman, Balaji; Nikolka, Mark; Flores, Jean-Charles; Salleo, Alberto; Bredas, Jean-Luc; Sirringhaus, Henning; Hayoz, Pascal; McCulloch, Iain

2018-01-29

Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.

Computational systems chemical biology.

PubMed

Oprea, Tudor I; May, Elebeoba E; Leitão, Andrei; Tropsha, Alexander

2011-01-01

There is a critical need for improving the level of chemistry awareness in systems biology. The data and information related to modulation of genes and proteins by small molecules continue to accumulate at the same time as simulation tools in systems biology and whole body physiologically based pharmacokinetics (PBPK) continue to evolve. We called this emerging area at the interface between chemical biology and systems biology systems chemical biology (SCB) (Nat Chem Biol 3: 447-450, 2007).The overarching goal of computational SCB is to develop tools for integrated chemical-biological data acquisition, filtering and processing, by taking into account relevant information related to interactions between proteins and small molecules, possible metabolic transformations of small molecules, as well as associated information related to genes, networks, small molecules, and, where applicable, mutants and variants of those proteins. There is yet an unmet need to develop an integrated in silico pharmacology/systems biology continuum that embeds drug-target-clinical outcome (DTCO) triplets, a capability that is vital to the future of chemical biology, pharmacology, and systems biology. Through the development of the SCB approach, scientists will be able to start addressing, in an integrated simulation environment, questions that make the best use of our ever-growing chemical and biological data repositories at the system-wide level. This chapter reviews some of the major research concepts and describes key components that constitute the emerging area of computational systems chemical biology.

Computational Systems Chemical Biology

PubMed Central

Oprea, Tudor I.; May, Elebeoba E.; Leitão, Andrei; Tropsha, Alexander

2013-01-01

There is a critical need for improving the level of chemistry awareness in systems biology. The data and information related to modulation of genes and proteins by small molecules continue to accumulate at the same time as simulation tools in systems biology and whole body physiologically-based pharmacokinetics (PBPK) continue to evolve. We called this emerging area at the interface between chemical biology and systems biology systems chemical biology, SCB (Oprea et al., 2007). The overarching goal of computational SCB is to develop tools for integrated chemical-biological data acquisition, filtering and processing, by taking into account relevant information related to interactions between proteins and small molecules, possible metabolic transformations of small molecules, as well as associated information related to genes, networks, small molecules and, where applicable, mutants and variants of those proteins. There is yet an unmet need to develop an integrated in silico pharmacology / systems biology continuum that embeds drug-target-clinical outcome (DTCO) triplets, a capability that is vital to the future of chemical biology, pharmacology and systems biology. Through the development of the SCB approach, scientists will be able to start addressing, in an integrated simulation environment, questions that make the best use of our ever-growing chemical and biological data repositories at the system-wide level. This chapter reviews some of the major research concepts and describes key components that constitute the emerging area of computational systems chemical biology. PMID:20838980

Constitutional aneuploidy and cancer predisposition†

PubMed Central

Ganmore, Ithamar; Smooha, Gil; Izraeli, Shai

2009-01-01

Constitutional aneuploidies are rare syndromes associated with multiple developmental abnormalities and the alterations in the risk for specific cancers. Acquired somatic chromosomal aneuploidies are the most common genetic aberrations in sporadic cancers. Thus studies of these rare constitutional aneuploidy syndromes are important not only for patient counseling and clinical management, but also for deciphering the mechanisms by which chromosomal aneuploidy affect cancer initiation and progression. Here we review the major constitutional aneuploidy syndromes and suggest some general mechanisms for the associated cancer predisposition. PMID:19297405

Environmental durability diagnostic for printed identification codes of polymer insulation for distribution pipelines

NASA Astrophysics Data System (ADS)

Zhuravleva, G. N.; Nagornova, I. V.; Kondratov, A. P.; Bablyuk, E. B.; Varepo, L. G.

2017-08-01

A research and modelling of weatherability and environmental durability of multilayer polymer insulation of both cable and pipelines with printed barcodes or color identification information were performed. It was proved that interlayer printing of identification codes in distribution pipelines insulation coatings provides high marking stability to light and atmospheric condensation. This allows to carry out their distant damage control. However, microbiological fouling of upper polymer layer hampers the distant damage pipelines identification. The color difference values and density changes of PE and PVC printed insolation due to weather and biological factors were defined.

Probing the Biomimetic Ice Nucleation Inhibition Activity of Poly(vinyl alcohol) and Comparison to Synthetic and Biological Polymers.

PubMed

Congdon, Thomas; Dean, Bethany T; Kasperczak-Wright, James; Biggs, Caroline I; Notman, Rebecca; Gibson, Matthew I

2015-09-14

Nature has evolved many elegant solutions to enable life to flourish at low temperatures by either allowing (tolerance) or preventing (avoidance) ice formation. These processes are typically controlled by ice nucleating proteins or antifreeze proteins, which act to either promote nucleation, prevent nucleation or inhibit ice growth depending on the specific need, respectively. These proteins can be expensive and their mechanisms of action are not understood, limiting their translation, especially into biomedical cryopreservation applications. Here well-defined poly(vinyl alcohol), synthesized by RAFT/MADIX polymerization, is investigated for its ice nucleation inhibition (INI) activity, in contrast to its established ice growth inhibitory properties and compared to other synthetic polymers. It is shown that ice nucleation inhibition activity of PVA has a strong molecular weight dependence; polymers with a degree of polymerization below 200 being an effective inhibitor at just 1 mg.mL(-1). Other synthetic and natural polymers, both with and without hydroxyl-functional side chains, showed negligible activity, highlighting the unique ice/water interacting properties of PVA. These findings both aid our understanding of ice nucleation but demonstrate the potential of engineering synthetic polymers as new biomimetics to control ice formation/growth processes.

Probing the Biomimetic Ice Nucleation Inhibition Activity of Poly(vinyl alcohol) and Comparison to Synthetic and Biological Polymers

PubMed Central

2015-01-01

Nature has evolved many elegant solutions to enable life to flourish at low temperatures by either allowing (tolerance) or preventing (avoidance) ice formation. These processes are typically controlled by ice nucleating proteins or antifreeze proteins, which act to either promote nucleation, prevent nucleation or inhibit ice growth depending on the specific need, respectively. These proteins can be expensive and their mechanisms of action are not understood, limiting their translation, especially into biomedical cryopreservation applications. Here well-defined poly(vinyl alcohol), synthesized by RAFT/MADIX polymerization, is investigated for its ice nucleation inhibition (INI) activity, in contrast to its established ice growth inhibitory properties and compared to other synthetic polymers. It is shown that ice nucleation inhibition activity of PVA has a strong molecular weight dependence; polymers with a degree of polymerization below 200 being an effective inhibitor at just 1 mg.mL–1. Other synthetic and natural polymers, both with and without hydroxyl-functional side chains, showed negligible activity, highlighting the unique ice/water interacting properties of PVA. These findings both aid our understanding of ice nucleation but demonstrate the potential of engineering synthetic polymers as new biomimetics to control ice formation/growth processes PMID:26258729

21 CFR 888.3660 - Shoulder joint metal/polymer semi-constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3660... device are: (1) FDA's: (i) “Use of International Standard ISO 10993 ‘Biological Evaluation of Medical... metal/polymer semi-constrained cemented prosthesis is a device intended to be implanted to replace a...

21 CFR 888.3650 - Shoulder joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Prosthetic Devices § 888.3650... are: (1) FDA's: (i) “Use of International Standard ISO 10993 ‘Biological Evaluation of Medical Devices... metal/polymer non-constrained cemented prosthesis is a device intended to be implanted to replace a...

Comparison of two laryngeal tissue fiber constitutive models

NASA Astrophysics Data System (ADS)

Hunter, Eric J.; Palaparthi, Anil Kumar Reddy; Siegmund, Thomas; Chan, Roger W.

2014-02-01

Biological tissues are complex time-dependent materials, and the best choice of the appropriate time-dependent constitutive description is not evident. This report reviews two constitutive models (a modified Kelvin model and a two-network Ogden-Boyce model) in the characterization of the passive stress-strain properties of laryngeal tissue under tensile deformation. The two models are compared, as are the automated methods for parameterization of tissue stress-strain data (a brute force vs. a common optimization method). Sensitivity (error curves) of parameters from both models and the optimized parameter set are calculated and contrast by optimizing to the same tissue stress-strain data. Both models adequately characterized empirical stress-strain datasets and could be used to recreate a good likeness of the data. Nevertheless, parameters in both models were sensitive to measurement errors or uncertainties in stress-strain, which would greatly hinder the confidence in those parameters. The modified Kelvin model emerges as a potential better choice for phonation models which use a tissue model as one component, or for general comparisons of the mechanical properties of one type of tissue to another (e.g., axial stress nonlinearity). In contrast, the Ogden-Boyce model would be more appropriate to provide a basic understanding of the tissue's mechanical response with better insights into the tissue's physical characteristics in terms of standard engineering metrics such as shear modulus and viscosity.

Materials and methods for delivery of biological drugs

NASA Astrophysics Data System (ADS)

Zelikin, Alexander N.; Ehrhardt, Carsten; Healy, Anne Marie

2016-11-01

Biological drugs generated via recombinant techniques are uniquely positioned due to their high potency and high selectivity of action. The major drawback of this class of therapeutics, however, is their poor stability upon oral administration and during subsequent circulation. As a result, biological drugs have very low bioavailability and short therapeutic half-lives. Fortunately, tools of chemistry and biotechnology have been developed into an elaborate arsenal, which can be applied to improve the pharmacokinetics of biological drugs. Depot-type release systems are available to achieve sustained release of drugs over time. Conjugation to synthetic or biological polymers affords long circulating formulations. Administration of biological drugs through non-parenteral routes shows excellent performance and the first products have reached the market. This Review presents the main accomplishments in this field and illustrates the materials and methods behind existing and upcoming successful formulations and delivery strategies for biological drugs.

A Comparison of Curing Process-Induced Residual Stresses and Cure Shrinkage in Micro-Scale Composite Structures with Different Constitutive Laws

NASA Astrophysics Data System (ADS)

Li, Dongna; Li, Xudong; Dai, Jianfeng; Xi, Shangbin

2018-02-01

In this paper, three kinds of constitutive laws, elastic, "cure hardening instantaneously linear elastic (CHILE)" and viscoelastic law, are used to predict curing process-induced residual stress for the thermoset polymer composites. A multi-physics coupling finite element analysis (FEA) model implementing the proposed three approaches is established in COMSOL Multiphysics-Version 4.3b. The evolution of thermo-physical properties with temperature and degree of cure (DOC), which improved the accuracy of numerical simulations, and cure shrinkage are taken into account for the three models. Subsequently, these three proposed constitutive models are implemented respectively in a 3D micro-scale composite laminate structure. Compared the differences between these three numerical results, it indicates that big error in residual stress and cure shrinkage generates by elastic model, but the results calculated by the modified CHILE model are in excellent agreement with those estimated by the viscoelastic model.

29 CFR 452.18 - Constitutional officers.

Code of Federal Regulations, 2013 CFR

2013-07-01

... officer refers to a person holding a position identified as an officer by the constitution and bylaws of... constitution identifies the holder of such a position as an officer. On the other hand, legislative representatives who are required to be elected by the constitution and bylaws of a labor organization are not...

7 CFR 718.201 - Farm constitution.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 7 Agriculture 7 2010-01-01 2010-01-01 false Farm constitution. 718.201 Section 718.201 Agriculture... Reconstitution of Farms, Allotments, Quotas, and Bases § 718.201 Farm constitution. (a) In order to implement... this section. The constitution and identification of land as a farm for the first time and the...

29 CFR 452.18 - Constitutional officers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... officer refers to a person holding a position identified as an officer by the constitution and bylaws of... constitution identifies the holder of such a position as an officer. On the other hand, legislative representatives who are required to be elected by the constitution and bylaws of a labor organization are not...

7 CFR 718.201 - Farm constitution.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 7 Agriculture 7 2012-01-01 2012-01-01 false Farm constitution. 718.201 Section 718.201 Agriculture... Reconstitution of Farms, Allotments, Quotas, and Bases § 718.201 Farm constitution. (a) In order to implement... this section. The constitution and identification of land as a farm for the first time and the...

7 CFR 718.201 - Farm constitution.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 7 Agriculture 7 2013-01-01 2013-01-01 false Farm constitution. 718.201 Section 718.201 Agriculture... Reconstitution of Farms, Allotments, Quotas, and Bases § 718.201 Farm constitution. (a) In order to implement... this section. The constitution and identification of land as a farm for the first time and the...

29 CFR 452.18 - Constitutional officers.

Code of Federal Regulations, 2012 CFR

2012-07-01

... officer refers to a person holding a position identified as an officer by the constitution and bylaws of... constitution identifies the holder of such a position as an officer. On the other hand, legislative representatives who are required to be elected by the constitution and bylaws of a labor organization are not...

7 CFR 718.201 - Farm constitution.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 7 Agriculture 7 2011-01-01 2011-01-01 false Farm constitution. 718.201 Section 718.201 Agriculture... Reconstitution of Farms, Allotments, Quotas, and Bases § 718.201 Farm constitution. (a) In order to implement... this section. The constitution and identification of land as a farm for the first time and the...

7 CFR 718.201 - Farm constitution.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 7 Agriculture 7 2014-01-01 2014-01-01 false Farm constitution. 718.201 Section 718.201 Agriculture... Reconstitution of Farms, Allotments, Quotas, and Bases § 718.201 Farm constitution. (a) In order to implement... this section. The constitution and identification of land as a farm for the first time and the...

29 CFR 452.18 - Constitutional officers.

Code of Federal Regulations, 2014 CFR

2014-07-01

... officer refers to a person holding a position identified as an officer by the constitution and bylaws of... constitution identifies the holder of such a position as an officer. On the other hand, legislative representatives who are required to be elected by the constitution and bylaws of a labor organization are not...

Dynamic covalent polymers

PubMed Central

García, Fátima

2016-01-01

ABSTRACT This Highlight presents an overview of the rapidly growing field of dynamic covalent polymers. This class of polymers combines intrinsic reversibility with the robustness of covalent bonds, thus enabling formation of mechanically stable, polymer‐based materials that are responsive to external stimuli. It will be discussed how the inherent dynamic nature of the dynamic covalent bonds on the molecular level can be translated to the macroscopic level of the polymer, giving access to a range of applications, such as stimuli‐responsive or self‐healing materials. A primary distinction will be made based on the type of dynamic covalent bond employed, while a secondary distinction will be based on the consideration whether the dynamic covalent bond is used in the main chain of the polymer or whether it is used to allow side chain modification of the polymer. Emphasis will be on the chemistry of the dynamic covalent bonds present in the polymer, in particular in relation to how the specific (dynamic) features of the bond impart functionality to the polymer material, and to the conditions under which this dynamic behavior is manifested. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3551–3577. PMID:27917019

Light Responsive Polymer Membranes: A Review

PubMed Central

Nicoletta, Fiore Pasquale; Cupelli, Daniela; Formoso, Patrizia; De Filpo, Giovanni; Colella, Valentina; Gugliuzza, Annarosa

2012-01-01

In recent years, stimuli responsive materials have gained significant attention in membrane separation processes due to their ability to change specific properties in response to small external stimuli, such as light, pH, temperature, ionic strength, pressure, magnetic field, antigen, chemical composition, and so on. In this review, we briefly report recent progresses in light-driven materials and membranes. Photo-switching mechanisms, valved-membrane fabrication and light-driven properties are examined. Advances and perspectives of light responsive polymer membranes in biotechnology, chemistry and biology areas are discussed. PMID:24957966

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…

Synthetic biology between technoscience and thing knowledge.

PubMed

Gelfert, Axel

2013-06-01

Synthetic biology presents a challenge to traditional accounts of biology: Whereas traditional biology emphasizes the evolvability, variability, and heterogeneity of living organisms, synthetic biology envisions a future of homogeneous, humanly engineered biological systems that may be combined in modular fashion. The present paper approaches this challenge from the perspective of the epistemology of technoscience. In particular, it is argued that synthetic-biological artifacts lend themselves to an analysis in terms of what has been called 'thing knowledge'. As such, they should neither be regarded as the simple outcome of applying theoretical knowledge and engineering principles to specific technological problems, nor should they be treated as mere sources of new evidence in the general pursuit of scientific understanding. Instead, synthetic-biological artifacts should be viewed as partly autonomous research objects which, qua their material-biological constitution, embody knowledge about the natural world-knowledge that, in turn, can be accessed via continuous experimental interrogation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Polymer compositions, polymer films and methods and precursors for forming same

DOEpatents

Klaehn, John R; Peterson, Eric S; Orme, Christopher J

2013-09-24

Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.