WorldWideScience

Sample records for terminally-branched polymeric linkers

  1. Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

    Science.gov (United States)

    Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

    2014-06-27

    A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Celecoxib coupled to dextran via a glutamic acid linker yields a polymeric prodrug suitable for colonic delivery.

    Science.gov (United States)

    Lee, Yonghyun; Kim, Jungyun; Kim, Wooseong; Nam, Joon; Jeong, Seongkeun; Lee, Sunyoung; Yoo, Jin-Wook; Kim, Min-Soo; Jung, Yunjin

    2015-01-01

    Celecoxib, a selective cyclooxygenase-2 inhibitor, is potentially useful for the treatment of colonic diseases such as colorectal cancer and colitis. However, the cardiovascular toxicity of celecoxib limits its routine use in the clinic. Generally, colon-specific delivery of a drug both increases the therapeutic availability in the large intestine and decreases the systemic absorption of the drug, most likely resulting in enhanced therapeutic effects against colonic diseases such as colitis and reduced systemic side effects. To develop a colon-specific prodrug of celecoxib that could reduce its cardiovascular toxicity and improve its therapeutic activity, dextran-glutamic acid-celecoxib conjugate (glutam-1-yl celecoxib-dextran ester [G1CD]) was prepared and evaluated. While stable in pH 1.2 and 6.8 buffer solutions and small-intestinal contents, G1CD efficiently released celecoxib in cecal contents. Oral administration of G1CD to rats delivered a larger amount of celecoxib to the large intestine than free celecoxib. G1CD prevented the systemic absorption of celecoxib and did not decrease the serum level of 6-ketoprostaglandin F1α, an inverse indicator of cardiovascular toxicity of celecoxib. Collectively, G1CD may be a polymeric colon-specific celecoxib prodrug with therapeutic and toxicological advantages.

  3. Computer-assisted 3D reconstruction of the terminal branches of th cerebral arteries. Pt. 2. Middle cerebral artery

    International Nuclear Information System (INIS)

    Gloger, S.; Gloger, A.; Vogt, H.; Kretschmann, H.J.

    1994-01-01

    We present a three-dimensional anatomical computer model of the terminal branches of the middle cerebral artery, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries, which can help to identify them on conventional angiography and magnetic resonance angiography. The arteries can also be matched with CT, MR or PET images to indicate the areas of extension of individual branches, allowing neuromorphological and functional correlations. (orig.)

  4. Computer-assisted 3D reconstruction of the terminal branches of the cerebral arteries. Pt. 1. Anterior cerebral artery

    International Nuclear Information System (INIS)

    Gloger, S.; Gloger, A.; Vogt, H.; Kretschmann, H.J.

    1994-01-01

    We present a three-dimensional anatomical computer model of the terminal branches of the anterior cerebral artery, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries, which can help to identify them on conventional and magnetic resonance angiography. Our rendition of the cerebral arteries can also be matched with CT, MR or PET images to indicate the areas of extension of individual branches, allowing neuromorphological and functional correlation. (orig.)

  5. Computer-assisted 3D reconstruction of the terminal branches of th cerebral arteries. Pt. 2. Middle cerebral artery

    Energy Technology Data Exchange (ETDEWEB)

    Gloger, S. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Gloger, A. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Vogt, H. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Kretschmann, H.J. (Dept. of Neuroanatomy, Hannover Medical School (Germany))

    1994-04-01

    We present a three-dimensional anatomical computer model of the terminal branches of the middle cerebral artery, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries, which can help to identify them on conventional angiography and magnetic resonance angiography. The arteries can also be matched with CT, MR or PET images to indicate the areas of extension of individual branches, allowing neuromorphological and functional correlations. (orig.)

  6. Computer-assisted 3D reconstruction of the terminal branches of the cerebral arteries. Pt. 1. Anterior cerebral artery

    Energy Technology Data Exchange (ETDEWEB)

    Gloger, S. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Gloger, A. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Vogt, H. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Kretschmann, H.J. (Dept. of Neuroanatomy, Hannover Medical School (Germany))

    1994-04-01

    We present a three-dimensional anatomical computer model of the terminal branches of the anterior cerebral artery, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries, which can help to identify them on conventional and magnetic resonance angiography. Our rendition of the cerebral arteries can also be matched with CT, MR or PET images to indicate the areas of extension of individual branches, allowing neuromorphological and functional correlation. (orig.)

  7. Essential oil composition of terminal branches, cones and roots of Tetraclinis articulata from Tunisia.

    Science.gov (United States)

    Tékaya-Karoui, Ahlem; Ben Jannet, Hichem; Mighri, Zine

    2007-08-01

    The volatiles obtained separately from the terminal branches (woody and non-woody), cones and roots of Tetraclinis articulata gathered from the area of Zaghouan (Tunisia) have been analyzed by GC and GC-MS. Remarkable differences were found between the constituent percentages of the different studied organs. The main components in the non-woody branches volatile oil were naphtalen (6.6%), Z-muurolene (29.0%) while Camphene (43.2%), Z-beta-ocimene (11.7%), nonanol (5.3%) and a non identified compound (12%) were the main components in the wood branches volatile concentrate. In the cones oil, the most important compounds found were trans-pinacarveol (6.1%), p-cymene-8-ol (10.4%), fenchyl acetate (5.1%), beta-phellandrene (8.1%) and carvone (5.3%). The major constituent in the oil of roots was found to be Camphene (70.2%). A comparison of these data with previous results reported in the literature showed surprising differences.

  8. Two polymeric nickel(II) complexes with aromatic benzene-1,2,4,5-tetracarboxylate and pyridine-2,5-dicarboxylate linkers.

    Science.gov (United States)

    Atria, Ana María; Corsini, Gino; González, Lissette; Garland, Maria Teresa; Baggio, Ricardo

    2009-07-01

    (Mu-benzene-1,2,4,5-tetracarboxylato-kappa(2)O(1):O(4))bis[aquabis(2,2-methylpropane-1,3-diamine-kappa(2)N,N')nickel(II)] methanol disolvate tetrahydrate, [Ni(2)(C(10)H(2)O(8))(C(5)H(14)N(2))(4)(H(2)O)(2)].2CH(4)O.4H(2)O, (I), is dinuclear, with elemental units built up around an inversion centre halving the benzene-1,2,4,5-tetracarboxylate (btc) anion, which bridges two symmetry-related Ni(II) cations. The octahedral Ni polyhedron is completed by two chelating 2,2-methylpropane-1,3-diamine (dmpda) groups and a terminal aqua ligand. Two methanol and four water solvent molecules are involved in a number of N-H...O and O-H...O hydrogen bonds which define a strongly bound two-dimensional supramolecular structure. The structure of catena-poly[[[bis(2,2-methylpropane-1,3-diamine-kappa(2)N,N')nickel(II)]-mu-pyridine-2,5-dicarboxylato-kappa(3)O(5):N,O(2)-[(2,2-methylpropane-1,3-diamine-kappa(2)N,N')nickel(II)]-mu-pyridine-2,5-dicarboxylato-kappa(3)N,O(2):O(5)] octahydrate], {[Ni(2)(C(7)H(3)NO(4))(2)(C(5)H(14)N(2))(3)].8H(2)O}(n), (II), is polymeric, forming twisted chains around three independent Ni centres, two of which lie on inversion centres and the third in a general position. There are three chelating dmpda ligands (one disordered over two equally populated positions), which are each attached to a different cation, and two pyridine-2,5-dicarboxylate (pdc) anions, both chelating the Ni centre in general positions through an -O-C-C-N- loop, while acting as bridges to the remaining two centrosymmetric Ni atoms. There are, in addition, eight noncoordinated water molecules in the structure, some of which are disordered.

  9. DC-Evoked Modulation of Excitability of Myelinated Nerve Fibers and Their Terminal Branches; Differences in Sustained Effects of DC.

    Science.gov (United States)

    Kaczmarek, Dominik; Jankowska, Elzbieta

    2018-03-15

    Direct current (DC) evokes long-lasting changes in neuronal networks both presynaptically and postsynaptically and different mechanisms were proposed to be involved in them. Different mechanisms were also suggested to account for the different dynamics of presynaptic DC actions on myelinated nerve fibers stimulated before they entered the spinal gray matter and on their terminal branches. The aim of the present study was to examine whether these different dynamics might be related to differences in the involvement of K + channels. To this end, we compared effects of the K + channel blocker 4-amino-pyridine (4-AP) on DC-evoked changes in the excitability of afferent fibers stimulated within the dorsal columns (epidurally) and within their projection areas in the dorsal horn and motor nuclei (intraspinally). 4-AP was applied systemically in deeply anesthetized rats. DC-evoked increases in the excitability of epidurally stimulated afferent nerve fibers, and increases in field potentials evoked by these fibers, were not affected by 4-AP. In contrast, sustained decreases rather than increases in the excitability of intraspinally stimulated terminal nerve branches were evoked by local application of DC in conjunction with 4-AP. The study leads to the conclusion that 4-AP-sensitive K + channels contribute to the sustained DC-evoked post-polarization increases in the excitability at the level of terminal branches of nerve fibers but not of the nodes of Ranvier nor within the juxta-paranodal regions where other mechanisms would be involved in inducing the sustained DC-evoked changes. Copyright © 2018 IBRO. Published by Elsevier Ltd. All rights reserved.

  10. Computer-assisted 3D reconstruction of the terminal branches of the cerebral arteries. Pt. 3. Posterior cerebral artery and circle of Willis

    International Nuclear Information System (INIS)

    Gloger, S.; Gloger, A.; Vogt, H.; Kretschmann, H.J.

    1994-01-01

    We present a three-dimensional anatomical computer model of the terminal branches of the posterior cerebral artery and circle of Willis, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries. This can help to identify the arteries in conventional and magnetic resonance angiography. Our rendition of the cerebral arteries can be matched with CT, MR and PET images to indicate the areas of extension of the individual branches, allowing neuromorphological and functional correlations. (orig.)

  11. Computer-assisted 3D reconstruction of the terminal branches of the cerebral arteries. Pt. 3. Posterior cerebral artery and circle of Willis

    Energy Technology Data Exchange (ETDEWEB)

    Gloger, S. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Gloger, A. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Vogt, H. (Dept. of Neuroanatomy, Hannover Medical School (Germany)); Kretschmann, H.J. (Dept. of Neuroanatomy, Hannover Medical School (Germany))

    1994-05-01

    We present a three-dimensional anatomical computer model of the terminal branches of the posterior cerebral artery and circle of Willis, acquired from equidistant serial anatomical slices of three brains. The reconstructions provide a clear picture from all angles of the complicated course of the terminal branches of the cerebral arteries. This can help to identify the arteries in conventional and magnetic resonance angiography. Our rendition of the cerebral arteries can be matched with CT, MR and PET images to indicate the areas of extension of the individual branches, allowing neuromorphological and functional correlations. (orig.)

  12. Formation and function of synapses with respect to Schwann cells at the end of motor nerve terminal branches on mature amphibian (Bufo marinus) muscle.

    Science.gov (United States)

    Macleod, G T; Dickens, P A; Bennett, M R

    2001-04-01

    A study has been made of the formation and regression of synapses with respect to Schwann cells at the ends of motor nerve terminal branches in mature toad (Bufo marinus) muscle. Synapse formation and regression, as inferred from the appearance and loss of N-(3-triethylammoniumpropyl)-4-(4-(dibutylamino)styryl) pyridinium dibromide (FM1-43)-stained vesicle clusters, occurred at the ends of terminal branches over a 16 hr period. Multiple microelectrodes placed in an array about FM1-43 blobs at the ends of terminal branches detected the electrical signs of neurotransmitter being released onto receptors. Injection of a calcium indicator (Oregon Green 488 BAPTA-1) into the motor nerve with subsequent imaging of the calcium transients, in response to stimulation, often showed a reduced calcium influx in the ends of terminal branches. Injection of a fluorescent dye into motor nerves revealed the full extent of their terminal branches and growing processes. Injection of the terminal Schwann cells (TSCs) often revealed pseudopodial TSC processes up to 10-microm-long. Imaging of these TSC processes over minutes or hours showed that they were highly labile and capable of extending several micrometers in a few minutes. Injection of motor nerve terminals with a different dye to that injected into their TSCs revealed that terminal processes sometimes followed the TSC processes over a few hours. It is suggested that the ends of motor nerve terminals in vivo are in a constant state of remodeling through the formation and regression of processes, that TSC processes guide the remodeling, and that it can occur over a relatively short period of time.

  13. Quantifying morphological parameters of the terminal branching units in a mouse lung by phase contrast synchrotron radiation computed tomography.

    Directory of Open Access Journals (Sweden)

    Jeongeun Hwang

    Full Text Available An effective technique of phase contrast synchrotron radiation computed tomography was established for the quantitative analysis of the microstructures in the respiratory zone of a mouse lung. Heitzman's method was adopted for the whole-lung sample preparation, and Canny's edge detector was used for locating the air-tissue boundaries. This technique revealed detailed morphology of the respiratory zone components, including terminal bronchioles and alveolar sacs, with sufficiently high resolution of 1.74 µm isotropic voxel size. The technique enabled visual inspection of the respiratory zone components and comprehension of their relative positions in three dimensions. To check the method's feasibility for quantitative imaging, morphological parameters such as diameter, surface area and volume were measured and analyzed for sixteen randomly selected terminal branching units, each consisting of a terminal bronchiole and a pair of succeeding alveolar sacs. The four types of asymmetry ratios concerning alveolar sac mouth diameter, alveolar sac surface area, and alveolar sac volume are measured. This is the first ever finding of the asymmetry ratio for the terminal bronchioles and alveolar sacs, and it is noteworthy that an appreciable degree of branching asymmetry was observed among the alveolar sacs at the terminal end of the airway tree, despite the number of samples was small yet. The series of efficient techniques developed and confirmed in this study, from sample preparation to quantification, is expected to contribute to a wider and exacter application of phase contrast synchrotron radiation computed tomography to a variety of studies.

  14. Backbone amide linker strategy

    DEFF Research Database (Denmark)

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

    2013-01-01

    In the backbone amide linker (BAL) strategy, the peptide is anchored not at the C-terminus but through a backbone amide, which leaves the C-terminal available for various modifications. This is thus a very general strategy for the introduction of C-terminal modifications. The BAL strategy...

  15. Structure and Functions of Linker Histones.

    Science.gov (United States)

    Lyubitelev, A V; Nikitin, D V; Shaytan, A K; Studitsky, V M; Kirpichnikov, M P

    2016-03-01

    Linker histones such as variants H1, H5, and other similar proteins play an important role in regulation of chromatin structure and dynamics. However, interactions of linker histones with DNA and proteins, as well as specific functions of their different variants, are poorly studied. This is because they acquire tertiary structure only when interacting with a nucleosome, and because of limitations of currently available methods. However, deeper investigation of linker histones and their interactions with other proteins will address a number of important questions - from structure of compacted chromatin to regulation of early embryogenesis. In this review, structures of histone H1 variants and its interaction with chromatin DNA are considered. A possible functional significance of different H1 variants, a role of these proteins in maintaining interphase chromatin structure, and interactions of linker histones with other cellular proteins are also discussed.

  16. Hydroquinone–pyrrole dyads with varied linkers

    Directory of Open Access Journals (Sweden)

    Hao Huang

    2016-01-01

    Full Text Available A series of pyrroles functionalized in the 3-position with p-dimethoxybenzene via various linkers (CH2, CH2CH2, CH=CH, C≡C has been synthesized. Their electronic properties have been deduced from 1H NMR, 13C NMR, and UV–vis spectra to detect possible interactions between the two aromatic subunits. The extent of conjugation between the subunits is largely controlled by the nature of the linker, with the largest conjugation found with the trans-ethene linker and the weakest with the aliphatic linkers. DFT calculations revealed substantial changes in the HOMO–LUMO gap that correlated with the extent of conjugation found experimentally. The results of this work are expected to open up for use of the investigated compounds as components of redox-active materials in sustainable, organic electrical energy storage devices.

  17. Solid colloids with surface-mobile linkers

    International Nuclear Information System (INIS)

    Van der Meulen, Stef A J; Helms, Gesa; Dogterom, Marileen

    2015-01-01

    In this report we review the possibilities of using colloids with surface mobile linkers for the study of colloidal self-assembly processes. A promising route to create systems with mobile linkers is the use of lipid (bi-)layers. These lipid layers can be either used in the form of vesicles or as coatings for hard colloids and emulsion droplets. Inside the lipid bilayers molecules can be inserted via membrane anchors. Due to the fluidity of the lipid bilayer, the anchored molecules remain mobile. The use of different lipid mixtures even allows creating Janus-like particles that exhibit directional bonding if linkers are used which have a preference for a certain lipid phase. In nature mobile linkers can be found e.g. as receptors in cells. Therefore, towards the end of the review, we also briefly address the possibility of using colloids with surface mobile linkers as model systems to mimic cell–cell interactions and cell adhesion processes. (topical review)

  18. Development of Bioorthogonally Degradable Linkers and Polymers Using alpha-Azidoethers

    Science.gov (United States)

    Rajagopalan, Chandrasekhar Ramasubramanian

    Degradable polymers have gained a lot of attention in recent years for applications in biotechnology and medicine. External control over polymer degradation can be obtained by incorporating functional groups that cleave in the presence of triggers that would normally be absent in biological environments, i.e. are bioorthogonal. This thesis explores the use of chemically cleavable alpha-azidoethers as a new method to obtain external control over the degradation behavior of polymers. My first goal is to illustrate the potential of alpha-azidoethers toward developing cleavable linkers. We have studied the relationship between alpha-azidoether structure and hydrolytic stability, to prepare linkers that withstand background hydrolytic cleavage until they are exposed to the cleaving trigger. The cleavage kinetics of the alpha-azidoether functional group was quantified. In addition to the conventionally used tris(2-carboxyethyl)phosphine (TCEP), dihydrolipoic acid (DHLA), a previously unexplored, biocompatible reducing agent, was also evaluated as a cleaving trigger. Based on these results, we have proposed design rules for utilizing alpha-azidoethers as cleavable linkers in applications that require bioorthogonal control over linker cleavage. Secondly, the alpha-azidoether cleavable linker chemistry was implemented into the development of polymeric materials. Two different types of polymers were developed. Polyamides incorporating alpha-azidoethers along the backbone were synthesized, and their physical properties and chemically triggered degradation behavior were characterized. The degradation timescale of these polymers can be tuned simply by manipulating the concentration of the externally applied chemical trigger. The alpha-azidoether functional group was then utilized to develop a unique triggered-release polymeric adhesive for potential applications in dental adhesive formulations. A methacrylamide-phosphonate adhesive monomer incorporating an alpha

  19. Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for aggressive CO2 separation from natural gas

    KAUST Repository

    Thompson, Joshua A.

    2014-07-01

    Zeolitic imidazolate framework (ZIF) materials are a promising subclass of metal-organic frameworks (MOF) for gas separations. However, due to the deleterious effects of gate-opening phenomena associated with organic linker rotation near the limiting pore apertures of ZIFs, there have been few demonstrations of improved gas separation properties over pure polymer membranes when utilizing ZIF materials in composite membranes for CO2-based gas separations. Here, we report a study of composite ZIF/polymer membranes, containing mixed-linker ZIF materials with ZIF-8 crystal topologies but composed of different organic linker compositions. Characterization of the mixed-linker ZIFs shows that the mixed linker approach offers control over the porosity and pore size distribution of the materials, as determined from nitrogen physisorption and Horváth-Kawazoe analysis. Single gas permeation measurements on mixed-matrix membranes reveal that inclusion of mixed-linker ZIFs yields membranes with better ideal CO2/CH4 selectivity than membranes containing ZIF-8. This improvement is shown to likely occur from enhancement in the diffusion selectivity of the membranes associated with controlling the pore size distribution of the ZIF filler. Mixed-gas permeation experiments show that membranes with mixed-linker ZIFs display an effective plasticization resistance that is not typical of the pure polymeric matrix. Overall, we demonstrate that mixed-linker ZIFs can improve the gas separation properties in composite membranes and may be applicable to aggressive CO2 concentrations in natural gas feeds. © 2013 Elsevier Inc. All rights reserved.

  20. Water-soluble heterobifunctional fluorescent linkers

    Czech Academy of Sciences Publication Activity Database

    Bartoň, Jan; Cígler, Petr

    2017-01-01

    Roč. 15, č. 1 (2017), s. 4 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /17./. 30.05.2017-01.06.2017, Milovy] Institutional support: RVO:61388963 Keywords : fluorescent probes * heterobifunctional linkers Subject RIV: CA - Inorganic Chemistry

  1. Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2010-01-01

    A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibility...

  2. Desmosine-Inspired Cross-Linkers for Hyaluronan Hydrogels

    Science.gov (United States)

    Hagel, Valentin; Mateescu, Markus; Southan, Alexander; Wegner, Seraphine V.; Nuss, Isabell; Haraszti, Tamás; Kleinhans, Claudia; Schuh, Christian; Spatz, Joachim P.; Kluger, Petra J.; Bach, Monika; Tussetschläger, Stefan; Tovar, Günter E. M.; Laschat, Sabine; Boehm, Heike

    2013-06-01

    We designed bioinspired cross-linkers based on desmosine, the cross-linker in natural elastin, to prepare hydrogels with thiolated hyaluronic acid. These short, rigid cross-linkers are based on pyridinium salts (as in desmosine) and can connect two polymer backbones. Generally, the obtained semi-synthetic hydrogels are form-stable, can withstand repeated stress, have a large linear-elastic range, and show strain stiffening behavior typical for biopolymer networks. In addition, it is possible to introduce a positive charge to the core of the cross-linker without affecting the gelation efficiency, or consequently the network connectivity. However, the mechanical properties strongly depend on the charge of the cross-linker. The properties of the presented hydrogels can thus be tuned in a range important for engineering of soft tissues by controlling the cross-linking density and the charge of the cross-linker.

  3. Elektroaktive polymerer

    DEFF Research Database (Denmark)

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

  4. Biomimetic polymeric membranes for water treatment

    DEFF Research Database (Denmark)

    Habel, Joachim Erich Otto

    This project is about the interplay of the three major components of aquaporin based biomimetic polymeric membranes (ABPMs): Aquaporins (AQPs), amphiphilic block copolymers, serving as a vesicular matrix for the hydrophobic AQP exterior (proteopolymersomes) and a polymeric membrane as embedment....... The interplay of proteopolymersomes and polymeric mesh support (in this case polyethersulfone, PES) was examined via integration of proteopolymersomes in an active layer (AL) formed by interfacial polymerisation between a linker molecule in aqueous phase and another in organic phase on top of the PES....... The resulting thin-film composite (TFC) membrane was analyzed via cross-flow forward osmosis (FO), scanning electron microscopy (SEM), fourier-transformed infrared spectroscopy (FTIR), as well as in the non-supported form over FTIR and a specialized microfluidic visualization approach. Where no clear dierences...

  5. Photolabile linker for the synthesis of hydroxamic acids

    DEFF Research Database (Denmark)

    2013-01-01

    a hydroxylamine - functionalized photolabile linker, and the so produced hydroxylamine - functionalized photolabile solid support. The invention further provides a method for synthesizing a one-bead-one compound library of hydroxamic acid derivatives on a photolabile linker, as well as a method for screening...

  6. A Helix-Stabilizing Linker Improves Subcutaneous Bioavailability of a Helical Peptide Independent of Linker Lipophilicity

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Thurber, Greg M.

    2016-01-01

    Stabilized peptides address several limitations to peptide-based imaging agents and therapeutics such as poor stability and low affinity due to conformational flexibility. There is also active research in developing these compounds for intracellular drug targeting, and significant efforts have been invested to determine the effects of helix stabilization on intracellular delivery. However, much less is known about the impact on other pharmacokinetic parameters such as plasma clearance and bioavailability. We investigated the effect of different fluorescent helix-stabilizing linkers with varying lipophilicity on subcutaneous (SC) bioavailability using the glucagon-like peptide-1 (GLP-1) receptor ligand exendin as a model system. The stabilized peptides showed significantly higher protease resistance and increased bioavailability independent of linker hydrophilicity, and all subcutaneously delivered conjugates were able to successfully target the islets of Langerhans with high specificity. The lipophilic peptide variants had slower absorption and plasma clearance than their respective hydrophilic conjugates, and the absolute bioavailability was also lower likely due to the longer residence times in the skin. The ease and efficiency of double-click helix stabilization chemistries is a useful tool for increasing the bioavailability of peptide therapeutics, many of which suffer from rapid in vivo protease degradation. Helix stabilization using linkers of varying lipophilicity can further control SC absorption and clearance rates to customize plasma pharmacokinetics. PMID:27327034

  7. Structural Mechanisms of Nucleosome Recognition by Linker Histones.

    Science.gov (United States)

    Zhou, Bing-Rui; Jiang, Jiansheng; Feng, Hanqiao; Ghirlando, Rodolfo; Xiao, T Sam; Bai, Yawen

    2015-08-20

    Linker histones bind to the nucleosome and regulate the structure of chromatin and gene expression. Despite more than three decades of effort, the structural basis of nucleosome recognition by linker histones remains elusive. Here, we report the crystal structure of the globular domain of chicken linker histone H5 in complex with the nucleosome at 3.5 Å resolution, which is validated using nuclear magnetic resonance spectroscopy. The globular domain sits on the dyad of the nucleosome and interacts with both DNA linkers. Our structure integrates results from mutation analyses and previous cross-linking and fluorescence recovery after photobleach experiments, and it helps resolve the long debate on structural mechanisms of nucleosome recognition by linker histones. The on-dyad binding mode of the H5 globular domain is different from the recently reported off-dyad binding mode of Drosophila linker histone H1. We demonstrate that linker histones with different binding modes could fold chromatin to form distinct higher-order structures. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. Nanohashtag structures based on carbon nanotubes and molecular linkers

    Science.gov (United States)

    Frye, Connor W.; Rybolt, Thomas R.

    2018-03-01

    Molecular mechanics was used to study the noncovalent interactions between single-walled carbon nanotubes and molecular linkers. Groups of nanotubes have the tendency to form tight, parallel bundles (||||). Molecular linkers were introduced into our models to stabilize nanostructures with carbon nanotubes held in perpendicular orientations. Molecular mechanics makes it possible to estimate the strength of noncovalent interactions holding these structures together and to calculate the overall binding energy of the structures. A set of linkers were designed and built around a 1,3,5,7-cyclooctatetraene tether with two corannulene containing pincers that extend in opposite directions from the central cyclooctatetraene portion. Each pincer consists of a pairs of "arms." These molecular linkers were modified so that the "hand" portions of each pair of "arms" could close together to grab and hold two carbon nanotubes in a perpendicular arrangement. To illustrate the possibility of more complicated and open perpendicular CNTs structures, our primary goal was to create a model of a nanohashtag (#) CNT conformation that is more stable than any parallel CNT arrangements with bound linker molecules forming clumps of CNTs and linkers in non-hashtag arrangements. This goal was achieved using a molecular linker (C280H96) that utilizes van der Waals interactions to two perpendicular oriented CNTs. Hydrogen bonding was then added between linker molecules to augment the stability of the hashtag structure. In the hashtag structure with hydrogen bonding, four (5,5) CNTs of length 4.46 nm (18 rings) and four linkers (C276H92N8O8) stabilized the hashtag so that the average binding energy per pincer was 118 kcal/mol.

  9. Crystallization of Galectin-8 Linker Reveals Intricate Relationship between the N-terminal Tail and the Linker

    Directory of Open Access Journals (Sweden)

    Yunlong Si

    2016-12-01

    Full Text Available Galectin-8 (Gal-8 plays a significant role in normal immunological function as well as in cancer. This lectin contains two carbohydrate recognition domains (CRD connected by a peptide linker. The N-terminal CRD determines ligand binding specificity, whereas the linker has been proposed to regulate overall Gal-8 function, including multimerization and biological activity. Here, we crystallized the Gal-8 N-terminal CRD with the peptide linker using a crystallization condition that contains Ni2+. The Ni2+ ion was found to be complexed between two CRDs via crystal packing contacts. The coordination between Ni2+ and Asp25 plays an indirect role in determining the structure of β-strand F0 and in influencing the linker conformation which could not be defined due to its dynamic nature. The linker was also shortened in situ and crystallized under a different condition, leading to a higher resolution structure refined to 1.08 Å. This crystal structure allowed definition of a short portion of the linker interacting with the Gal-8 N-terminal tail via ionic interactions and hydrogen bonds. Observation of two Gal-8 N-terminal CRD structures implies that the N-terminal tail and the linker may influence each other’s conformation. In addition, under specific crystallization conditions, glycerol could replace lactose and was observed at the carbohydrate binding site. However, glycerol did not show inhibition activity in hemagglutination assay.

  10. Novel mixing method for cross linker introduction into droplet emulsions

    CSIR Research Space (South Africa)

    Land, KJ

    2013-10-01

    Full Text Available the introduction of cross linker after droplet formation, together with the utilisation of topological microfluidic channel structures, allowing for the novel manufacture of particles. Flow over these structures has been simulated in order to choose the most...

  11. Linker-mediated assembly of gold nanoparticles into multimeric motifs

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, Mateusz; Cieplak, Marek [Institute of Physics, Polish Academy of Sciences, Aleja Lotnikow 32/46, 02-668 Warsaw (Poland); Szymczak, Piotr [Institute of Theoretical Physics, Faculty of Physics, University of Warsaw, ulica Hoza 69, 00-681 Warsaw (Poland); Thompson, Damien, E-mail: mc@ifpan.edu.pl [Tyndall National Institute, Lee Maltings, University College Cork, Cork (Ireland)

    2011-11-04

    We present a theoretical description of linker-mediated self-assembly of gold nanoparticles (Au-NP). Using mesoscale simulations with a coarse-grained model for the Au NPs and dirhenium-based linker molecules, we investigate the conditions under which large clusters can grow and construct a phase diagram that identifies favorable growth conditions in terms of floating and bound linker concentrations. The findings can be considered as generic, as we expect other NP-linker systems to behave in a qualitatively similar way. In particular, we also discuss the case of antibody-functionalised Au NPs connected by the C-reactive proteins (CRPs). We extract some general rules for NP linking that may aid the production of size- and shape-specific NP clusters for technology applications.

  12. The Effect of Double Crosslinker on Precipitation Polymerization of Poly(acrylic acid

    Directory of Open Access Journals (Sweden)

    Hajar Es-haghi

    2014-06-01

    Full Text Available Cross-linked poly(acrylic acids were prepared by dual cross-linkers via precipitation polymerization method in a binary organic solvent. Polyethylene glycol diacrylate (PEGDA-400 as a long-chain cross-linker and di(trimethylol propane tetraacrylate (DTMPTA as multifunctional cross-linker were used. PEGDA-400 was utilized to increase thickening properties and DTMPTA was used to improve the gel strength. The dual cross-linkers effect on the sample features (i.e., equilibrium swelling, thickening properties and rheological properties was investigated. Maximum amount of swelling was obtained by a high percentage of long-chain cross-linker. The apparent viscosity of the microgels was measured to determine their thickening properties for aqueous media. Maximum viscosity occurred at DT25-PE75 which was dependent on the type of cross-linkers in the polymer structure. The Flory-Rehner equation (from swelling ratio data and rubber elasticity theory (from rheometry data were used to discuss the network structure of the polymer. Increasing density of the network was shown by a sample containing high percentage of a four-functional cross-linker. The rheological properties of the cross-linked polymers were measured to determine storage modulus (strength network. The rheological behaviors demonstrated that the synthesized polymer containing a high amount of four-functional cross-linker had higher storage modulus (G′ than other samples. In addition the consistency coefficient (m and flow behavior index (n parameters of Ostwald equation were investigated as well. As a result, n values in each sample were found to be smaller than 1 and these results were fitted clearly with the pseudoplastic model. Apparent and rotational viscosities were used to determine the optimal cross-linker type (synthesized sample contained a high percentage of long-chain cross-linker.

  13. Novel polymeric nanocomposites and porous materials prepared using organogels

    Energy Technology Data Exchange (ETDEWEB)

    Lai, Wei-Chi; Tseng, Shen-Chen, E-mail: wclai@mail.tku.edu.t [Department of Chemical and Materials Engineering, Tamkang University, 151 Ying-chuan Road, Tamsui, Taipei 25137, Taiwan (China)

    2009-11-25

    We propose a new method for preparing polymeric nanocomposites and porous materials using self-assembled templates formed by 1,3:2,4-dibenzylidene sorbitol (DBS) organogels. DBS is capable of self-assembling into a 3D nanofibrillar network at relatively low concentrations in some organic solvents to produce organogels. In this study, we induced the formation of such physical cross-linked networks in styrene. Subsequently, we polymerized the styrene in the presence of chemical cross-linkers, divinyl benzene (DVB), with different amounts of DBS using thermal-initiated polymerization. The resulting materials were transparent, homogeneous polystyrene (PS) nanocomposites with both physical and chemical cross-links. The porous polymeric materials were obtained by solvent extraction of the DBS nanofibrils from the PS. Brunauer-Emmett-Teller (BET) measurements show that the amounts of DBS and DVB influenced the specific surface area after the removal of the DBS fibrils.

  14. Novel polymeric nanocomposites and porous materials prepared using organogels

    International Nuclear Information System (INIS)

    Lai, Wei-Chi; Tseng, Shen-Chen

    2009-01-01

    We propose a new method for preparing polymeric nanocomposites and porous materials using self-assembled templates formed by 1,3:2,4-dibenzylidene sorbitol (DBS) organogels. DBS is capable of self-assembling into a 3D nanofibrillar network at relatively low concentrations in some organic solvents to produce organogels. In this study, we induced the formation of such physical cross-linked networks in styrene. Subsequently, we polymerized the styrene in the presence of chemical cross-linkers, divinyl benzene (DVB), with different amounts of DBS using thermal-initiated polymerization. The resulting materials were transparent, homogeneous polystyrene (PS) nanocomposites with both physical and chemical cross-links. The porous polymeric materials were obtained by solvent extraction of the DBS nanofibrils from the PS. Brunauer-Emmett-Teller (BET) measurements show that the amounts of DBS and DVB influenced the specific surface area after the removal of the DBS fibrils.

  15. Improved sensitivity of a graphene FET biosensor using porphyrin linkers

    Science.gov (United States)

    Kawata, Takuya; Ono, Takao; Kanai, Yasushi; Ohno, Yasuhide; Maehashi, Kenzo; Inoue, Koichi; Matsumoto, Kazuhiko

    2018-06-01

    Graphene FET (G-FET) biosensors have considerable potential due to the superior characteristics of graphene. Realizing this potential requires judicious choice of the linker molecule connecting the target-specific receptor molecule to the graphene surface, yet there are few reports comparing linker molecules for G-FET biosensors. In this study, tetrakis(4-carboxyphenyl)porphyrin (TCPP) was used as a linker for surface modification of a G-FET and the properties of the device were compared to those of a G-FET device modified with the conventional linker 1-pyrenebutanoic acid succinimidyl ester (PBASE). TCPP modification resulted in a higher density of receptor immunoglobulin E (IgE) aptamer molecules on the G-FET. The detection limit of the target IgE was enhanced from 13 nM for the PBASE-modified G-FET to 2.2 nM for the TCPP-modified G-FET, suggesting that the TCPP linker is a powerful candidate for G-FET modification.

  16. Initial conformation of kinesin's neck linker

    International Nuclear Information System (INIS)

    Geng Yi-Zhao; Yan Shi-Wei; Ji Qing; Liu Shu-Xia

    2014-01-01

    How ATP binding initiates the docking process of kinesin's neck linker is a key question in understanding kinesin mechanisms. By exploiting a molecular dynamics method, we investigate the initial conformation of kinesin's neck linker in its docking process. We find that, in the initial conformation, the neck linker has interactions with β0 and forms a ‘cover-neck bundle’ structure with β0. From this initial structure, the formation of extra turns and the docking of the cover-neck bundle structure can be achieved. The motor head provides a forward force on the initial cover-neck bundle structure through ATP-induced rotation. This force, together with the hydrophobic interaction of ILE327 with the hydrophobic pocket on the motor head, drives the formation of the extra turn and initiates the neck linker docking process. Based on these findings, a pathway from ATP binding-induced motor head rotation to neck linker docking is proposed. (interdisciplinary physics and related areas of science and technology)

  17. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

    2015-01-01

    microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  18. Lignin-Based Materials Through Thiol-Maleimide "Click" Polymerization.

    Science.gov (United States)

    Buono, Pietro; Duval, Antoine; Averous, Luc; Habibi, Youssef

    2017-03-09

    In the present report an environmentally friendly approach to transforming renewable feedstocks into value-added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11-maleimidoundecylenic acid (11-MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11-maleimidoundecanoyl chloride (11-MUC). Different degrees of substitution were achieved by using various amounts of the 11-MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide-lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol-ene "click" polymerization with thiol-containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A streptavidin linker layer that functions after drying.

    Science.gov (United States)

    Xia, Nan; Shumaker-Parry, Jennifer S; Zareie, M Hadi; Campbell, Charles T; Castner, David G

    2004-04-27

    The ability of streptavidin (SA) to simultaneously bind four biotins is often used in linker layers, where a biotinylated molecule is linked to a biotin-functionalized surface via SA. For biosensor and array applications, it is desirable that the SA linker layer be stable to drying and rehydration. In this study it was observed that a significant decrease in binding capacity of a SA layer occurred when that layer was dried. For this study a SA linker layer was constructed by binding SA to a biotin-containing alkylthiolate monolayer (BAT/OEG) self-assembled onto gold. Its stability after drying was investigated using surface plasmon resonance (SPR). Approximately a quarter of the SA layer was removed from the BAT/OEG surface upon drying and rehydration, suggesting disruption of SA-biotin binding when dry. This resulted in the dried SA layer losing approximately 40% of its biotinylated ferritin (BF) binding capacity. Coating the layer with trehalose before drying was found to inhibit the loss of SA from the BAT/OEG surface. SPR showed that the trehalose-protected SA linker layer retained approximately 91% of its original BF binding capacity after drying and rehydration. Atomic force microscopy, which was used to image individual surface-bound SA and BF molecules, qualitatively confirmed these observations.

  20. Polymeric salt bridges for conducting electric current in microfluidic devices

    Science.gov (United States)

    Shepodd, Timothy J [Livermore, CA; Tichenor, Mark S [San Diego, CA; Artau, Alexander [Humacao, PR

    2009-11-17

    A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

  1. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J.; Zhou, Hong-Cai

    2018-01-01

    strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores

  2. Open and Closed: The Roles of Linker Histones in Plants and Animals

    OpenAIRE

    Over, Ryan S.; Michaels, Scott D.

    2014-01-01

    Linker histones play key roles alongside core histones in the regulation and maintenance of chromatin. Here, we illustrate our current understanding of the contributions of linker histones to the cell cycle, development, and chromatin structure in plants and animals.

  3. "Click" i polymerer 2

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  4. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  5. Dipolar cross-linkers for PDMS networks with enhanced dielectric permittivity and low dielectric loss

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Daugaard, Anders Egede; Hvilsted, Søren

    2013-01-01

    -(4-((4-nitrophenyl)diazenyl)phenoxy)-prop-1-yn-1-ylium, with a synthesized silicone compatible azide-functional cross-linker by click chemistry. The thermal, mechanical and electromechanical properties were investigated for PDMS films with 0 to 3.6 wt% of dipole-cross-linker. The relative dielectric permittivity......Dipole grafted cross-linkers were utilized to prepare polydimethylsiloxane (PDMS) elastomers with various chain lengths and with various concentrations of functional cross-linker. The grafted cross-linkers were prepared by reaction of two alkyne-functional dipoles, 1-ethynyl-4-nitrobenzene and 3...

  6. Polymeric Micelles with Ionic Cores Containing Biodegradable Crosslinks for Delivery of Chemotherapeutic Agents

    OpenAIRE

    Kim, Jong Oh; Sahay, Gaurav; Kabanov, Alexander V.; Bronich, Tatiana K.

    2010-01-01

    Novel functional polymeric nanocarriers with ionic cores containing biodegradable cross-links were developed for delivery of chemotherapeutic agents. Block ionomer complexes (BIC) of poly(ethylene oxide)-b-poly(methacylic acid) (PEO-b-PMA) and divalent metal cations (Ca2+) were utilized as templates. Disulfide bonds were introduced into the ionic cores by using cystamine as a biodegradable cross-linker. The resulting cross-linked micelles with disulfide bonds represented soft, hydrogel-like n...

  7. The flexibility of modified-linker MIL-53 materials.

    Science.gov (United States)

    Munn, Alexis S; Pillai, Renjith S; Biswas, Shyam; Stock, Norbert; Maurin, Guillaume; Walton, Richard I

    2016-03-14

    The flexibility of eight aluminium hydroxo terephthalates [Al(OH)(BDC-X)]·n(guest) (BDC = 1,4-benzene-dicarboxylate; X = -H, -CH3, -Cl, -Br, -NH2, -NO2, -(OH)2, -CO2H) crystallising in the MIL-53-type structure was investigated upon thermal dehydration of as-made samples, superhydration and methanol adsorption/desorption using in situ powder X-ray diffraction (PXRD). Profile fitting was used to determine lattice parameters as a function of time and/or temperature to describe their structural evolution. It has thus been shown that while methanol vapour adsorption induces an opening of all the modified frameworks, except the -NH2 material, superhydration only leads to open structures for Al-MIL-53-NO2, -Br and -(OH)2. All the MIL-53 solids, except Al-MIL-53-(OH)2 are present in the open structures upon thermal dehydration. In addition to the exploration of the breathing behavior of this MIL-53 series, the issue of disorder in the distribution of the functional groups between the organic linkers was explored. As a typical illustration, density functional theory calculations were carried out on different structures of Al-MIL-53-Cl, in which the distribution of -Cl within two adjacent BDC linkers is varied. The results show that the most energetically stable configuration leads to the best agreement with the experimental PXRD pattern. This observation supports that the distribution of the selected linker substituent in the functionalised solid is governed by energetics and that there is a preference for an ordering of this arrangement.

  8. Investigation of the Linker Swing Motion in the Zeolitic Imidazolate Framework ZIF-90

    KAUST Repository

    Zheng, Bin

    2018-03-13

    The linker swing motion in the zeolitic imidazolate framework ZIF-90 is investigated by density functional theory (DFT) calculation, molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations. The relation between the terminal aldehyde group rotation and the linker swing motion is revealed. The extremely high activation energy of the linker swing motion in ZIF-90 can be attributed to the asymmetric geometry and electron distribution of aldehyde groups. The change in the gate structure resulting from the linker rotation is used to understand the guest adsorption in ZIF-90. This study shows that it is possible to tune the linker swing motion and then the properties of ZIF-90 by manipulating the terminal group rotation. The results highlight the importance of considering the internal freedom effects to correctly describe the linker swing motion and the flexibility of metal-organic frameworks (MOFs).

  9. Open and closed: the roles of linker histones in plants and animals.

    Science.gov (United States)

    Over, Ryan S; Michaels, Scott D

    2014-03-01

    Histones package DNA in all eukaryotes and play key roles in regulating gene expression. Approximately 150 base pairs of DNA wraps around an octamer of core histones to form the nucleosome, the basic unit of chromatin. Linker histones compact chromatin further by binding to and neutralizing the charge of the DNA between nucleosomes. It is well established that chromatin packing is regulated by a complex pattern of posttranslational modifications (PTMs) to core histones, but linker histone function is less well understood. In this review, we describe the current understanding of the many roles that linker histones play in cellular processes, including gene regulation, cell division, and development, while putting the linker histone in the context of other nuclear proteins. Although intriguing roles for plant linker histones are beginning to emerge, much of our current understanding comes from work in animal systems. Many unanswered questions remain and additional work is required to fully elucidate the complex processes mediated by linker histones in plants.

  10. Specific distribution of the Saccharomyces cerevisiae linker histone homolog HHO1p in the chromatin

    OpenAIRE

    Freidkin, Ilya; Katcoff, Don J.

    2001-01-01

    In virtually all eukaryotic organisms, linker DNA between nucleosomes is associated with a histone termed linker histone or histone H1. In Saccharomyces cerevisiae, HHO1 encodes a putative linker histone with very significant homology to histone H1. The encoded protein is expressed in the nucleus, but has not been shown to affect global chromatin structure, nor has its deletion shown any detectable phenotype. In vitro chromatin assembly experiments with recombinant HHO1p have shown that it is...

  11. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng

    2015-09-01

    In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

  12. Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks

    KAUST Repository

    Thompson, Joshua A.

    2013-04-25

    The incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.

  13. Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks

    KAUST Repository

    Thompson, Joshua A.; Brunelli, Nicholas A.; Lively, Ryan P.; Johnson, J. R.; Jones, Christopher W.; Nair, Sankar

    2013-01-01

    The incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.

  14. Germline-specific H1 variants: the "sexy" linker histones.

    Science.gov (United States)

    Pérez-Montero, Salvador; Carbonell, Albert; Azorín, Fernando

    2016-03-01

    The eukaryotic genome is packed into chromatin, a nucleoprotein complex mainly formed by the interaction of DNA with the abundant basic histone proteins. The fundamental structural and functional subunit of chromatin is the nucleosome core particle, which is composed by 146 bp of DNA wrapped around an octameric protein complex formed by two copies of each core histone H2A, H2B, H3, and H4. In addition, although not an intrinsic component of the nucleosome core particle, linker histone H1 directly interacts with it in a monomeric form. Histone H1 binds nucleosomes near the exit/entry sites of linker DNA, determines nucleosome repeat length and stabilizes higher-order organization of nucleosomes into the ∼30 nm chromatin fiber. In comparison to core histones, histone H1 is less well conserved through evolution. Furthermore, histone H1 composition in metazoans is generally complex with most species containing multiple variants that play redundant as well as specific functions. In this regard, a characteristic feature is the presence of specific H1 variants that replace somatic H1s in the germline and during early embryogenesis. In this review, we summarize our current knowledge about their structural and functional properties.

  15. Cellulase linkers are optimized based on domain type and function: insights from sequence analysis, biophysical measurements, and molecular simulation.

    Directory of Open Access Journals (Sweden)

    Deanne W Sammond

    Full Text Available Cellulase enzymes deconstruct cellulose to glucose, and are often comprised of glycosylated linkers connecting glycoside hydrolases (GHs to carbohydrate-binding modules (CBMs. Although linker modifications can alter cellulase activity, the functional role of linkers beyond domain connectivity remains unknown. Here we investigate cellulase linkers connecting GH Family 6 or 7 catalytic domains to Family 1 or 2 CBMs, from both bacterial and eukaryotic cellulases to identify conserved characteristics potentially related to function. Sequence analysis suggests that the linker lengths between structured domains are optimized based on the GH domain and CBM type, such that linker length may be important for activity. Longer linkers are observed in eukaryotic GH Family 6 cellulases compared to GH Family 7 cellulases. Bacterial GH Family 6 cellulases are found with structured domains in either N to C terminal order, and similar linker lengths suggest there is no effect of domain order on length. O-glycosylation is uniformly distributed across linkers, suggesting that glycans are required along entire linker lengths for proteolysis protection and, as suggested by simulation, for extension. Sequence comparisons show that proline content for bacterial linkers is more than double that observed in eukaryotic linkers, but with fewer putative O-glycan sites, suggesting alternative methods for extension. Conversely, near linker termini where linkers connect to structured domains, O-glycosylation sites are observed less frequently, whereas glycines are more prevalent, suggesting the need for flexibility to achieve proper domain orientations. Putative N-glycosylation sites are quite rare in cellulase linkers, while an N-P motif, which strongly disfavors the attachment of N-glycans, is commonly observed. These results suggest that linkers exhibit features that are likely tailored for optimal function, despite possessing low sequence identity. This study suggests

  16. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  17. Hemidesmosomal linker proteins regulate cell motility, invasion and tumorigenicity in oral squamous cell carcinoma derived cells.

    Science.gov (United States)

    Chaudhari, Pratik Rajeev; Charles, Silvania Emlit; D'Souza, Zinia Charlotte; Vaidya, Milind Murlidhar

    2017-11-15

    BPAG1e and Plectin are hemidesmosomal linker proteins which anchor intermediate filament proteins to the cell surface through β4 integrin. Recent reports indicate that these proteins play a role in various cellular processes apart from their known anchoring function. However, the available literature is inconsistent. Further, the previous study from our laboratory suggested that Keratin8/18 pair promotes cell motility and tumor progression by deregulating β4 integrin signaling in oral squamous cell carcinoma (OSCC) derived cells. Based on these findings, we hypothesized that linker proteins may have a role in neoplastic progression of OSCC. Downregulation of hemidesmosomal linker proteins in OSCC derived cells resulted in reduced cell migration accompanied by alterations in actin organization. Further, decreased MMP9 activity led to reduced cell invasion in linker proteins knockdown cells. Moreover, loss of these proteins resulted in reduced tumorigenic potential. SWATH analysis demonstrated upregulation of N-Myc downstream regulated gene 1 (NDRG1) in linker proteins downregulated cells as compared to vector control cells. Further, the defects in phenotype upon linker proteins ablation were rescued upon loss of NDRG1 in linker proteins knockdown background. These data together indicate that hemidesmosomal linker proteins regulate cell motility, invasion and tumorigenicity possibly through NDRG1 in OSCC derived cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Description of a cellulose-binding domain and a linker sequence from Aspergillus fungi

    NARCIS (Netherlands)

    Quentin, M; Ebbelaar, M; Derksen, J; Mariani, C; van der Valk, H

    A family I cellulose-binding domain (CBD) and a serine- and threonine-rich linker peptide were cloned from the fungi Aspergillus japonicus and Aspergillus aculeatus. A glutathione S-transferase (GST) fusion protein comprising GST and a peptide linker with the CBD fused to its C-terminus, was

  19. Novel silicone compatible cross-linkers for controlled functionalization of PDMS networks

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Daugaard, Anders Egede; Hvilsted, Søren

    2013-01-01

    . In order to improve the dielectric properties of PDMS a novel system is developed where push-pull dipoles are grafted to a new silicone compatible cross-linker. The grafted cross-linkers are prepared by reaction of two different push-pull dipole alkynes as well as a fluorescent alkyne with the new azide...

  20. P-Link: A method for generating multicomponent cytochrome P450 fusions with variable linker length

    DEFF Research Database (Denmark)

    Belsare, Ketaki D.; Ruff, Anna Joelle; Martinez, Ronny

    2014-01-01

    Fusion protein construction is a widely employed biochemical technique, especially when it comes to multi-component enzymes such as cytochrome P450s. Here we describe a novel method for generating fusion proteins with variable linker lengths, protein fusion with variable linker insertion (P...

  1. Library of biphenyl privileged substructures using a safety-catch linker approach

    DEFF Research Database (Denmark)

    Severinsen, Rune; Bourne, Gregory T; Tran, Tran T

    2008-01-01

    A biphenyl privileged structure library containing three attachment points were synthesized using a catechol-based safety-catch linker strategy. The method requires the attachment of a bromo-acid to the linker, followed by a Pd-catalyzed Suzuki cross-coupling reaction. Further derivatization...

  2. The Abl SH2-kinase linker naturally adopts a conformation competent for SH3 domain binding.

    Science.gov (United States)

    Chen, Shugui; Brier, Sébastien; Smithgall, Thomas E; Engen, John R

    2007-04-01

    The core of the Abelson tyrosine kinase (c-Abl) is structurally similar to Src-family kinases where SH3 and SH2 domains pack against the backside of the kinase domain in the down-regulated conformation. Both kinase families depend upon intramolecular association of SH3 with the linker joining the SH2 and kinase domains for suppression of kinase activity. Hydrogen deuterium exchange (HX) and mass spectrometry (MS) were used to probe intramolecular interaction of the c-Abl SH3 domain with the linker in recombinant constructs lacking the kinase domain. Under physiological conditions, the c-Abl SH3 domain undergoes partial unfolding, which is stabilized by ligand binding, providing a unique assay for SH3:linker interaction in solution. Using this approach, we observed dynamic association of the SH3 domain with the linker in the absence of the kinase domain. Truncation of the linker before W254 completely prevented cis-interaction with SH3, while constructs containing amino acids past this point showed SH3:linker interactions. The observation that the Abl linker sequence exhibits SH3-binding activity in the absence of the kinase domain is unique to Abl and was not observed with Src-family kinases. These results suggest that SH3:linker interactions may have a more prominent role in Abl regulation than in Src kinases, where the down-regulated conformation is further stabilized by a second intramolecular interaction between the C-terminal tail and the SH2 domain.

  3. Linkers, resins, and general procedures for solid-phase peptide synthesis

    DEFF Research Database (Denmark)

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

    2013-01-01

    and linkers for solid-phase synthesis is a key parameter for successful peptide synthesis. This chapter provides an overview of the most common and useful resins and linkers for the synthesis of peptides with C-terminal amides, carboxylic acids, and more. The chapter finishes with robust protocols for general...

  4. Construction of hierarchically porous metal-organic frameworks through linker labilization

    Science.gov (United States)

    Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

    2017-05-01

    A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

  5. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.; Poater, Albert; Childers, M. Ian; Widger, Peter C B; Lapointe, Anne M.; Lobkovsky, Emil B.; Coates, Geoffrey W.; Cavallo, Luigi

    2013-01-01

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  6. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  7. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt...

  8. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

    2015-01-01

    . In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

  9. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  10. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  11. Effect of the linkers between the zinc fingers in zinc finger protein 809 on gene silencing and nuclear localization

    Energy Technology Data Exchange (ETDEWEB)

    Ichida, Yu, E-mail: ichida-y@ncchd.go.jp; Utsunomiya, Yuko; Onodera, Masafumi

    2016-03-18

    Zinc finger protein 809 (ZFP809) belongs to the Kruppel-associated box-containing zinc finger protein (KRAB-ZFP) family and functions in repressing the expression of Moloney murine leukemia virus (MoMLV). ZFP809 binds to the primer-binding site (PBS)located downstream of the MoMLV-long terminal repeat (LTR) and induces epigenetic modifications at integration sites, such as repressive histone modifications and de novo DNA methylation. KRAB-ZFPs contain consensus TGEKP linkers between C2H2 zinc fingers. The phosphorylation of threonine residues within linkers leads to the inactivation of zinc finger binding to target sequences. ZFP809 also contains consensus linkers between zinc fingers. However, the function of ZFP809 linkers remains unknown. In the present study, we constructed ZFP809 proteins containing mutated linkers and examined their ability to silence transgene expression driven by MLV, binding ability to MLV PBS, and cellular localization. The results of the present study revealed that the linkers affected the ability of ZFP809 to silence transgene expression. Furthermore, this effect could be partly attributed to changes in the localization of ZFP809 proteins containing mutated linkers. Further characterization of ZFP809 linkers is required for understanding the functions and features of KRAB-ZFP-containing linkers. - Highlights: • ZFP809 has three consensus linkers between the zinc fingers. • Linkers are required for ZFP809 to silence transgene expression driven by MLV-LTR. • Linkers affect the precise nuclear localization of ZFP809.

  12. Charged Triazole Cross-Linkers for Hyaluronan-Based Hybrid Hydrogels

    Directory of Open Access Journals (Sweden)

    Maike Martini

    2016-09-01

    Full Text Available Polyelectrolyte hydrogels play an important role in tissue engineering and can be produced from natural polymers, such as the glycosaminoglycan hyaluronan. In order to control charge density and mechanical properties of hyaluronan-based hydrogels, we developed cross-linkers with a neutral or positively charged triazole core with different lengths of spacer arms and two terminal maleimide groups. These cross-linkers react with thiolated hyaluronan in a fast, stoichiometric thio-Michael addition. Introducing a positive charge on the core of the cross-linker enabled us to compare hydrogels with the same interconnectivity, but a different charge density. Positively charged cross-linkers form stiffer hydrogels relatively independent of the size of the cross-linker, whereas neutral cross-linkers only form stable hydrogels at small spacer lengths. These novel cross-linkers provide a platform to tune the hydrogel network charge and thus the mechanical properties of the network. In addition, they might offer a wide range of applications especially in bioprinting for precise design of hydrogels.

  13. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks.

    Science.gov (United States)

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J; Zhou, Hong-Cai

    2018-02-14

    Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. Herein, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal-organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  14. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang

    2018-01-18

    Sufficient pore size, appropriate stability and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization and catalysis involving large molecules. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxyla-tion process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  15. A Traceless Aryl-Triazene Linker for DNA-Directed Chemistry

    DEFF Research Database (Denmark)

    Hejesen, Christian; Pedersen, Lars Kolster; Gothelf, Kurt Vesterager

    2013-01-01

    DNA-directed synthesis of encoded combinatorial libraries of small organic compounds most often involves transfer of organic building blocks from one DNA strand to another. This requires cleavable linkers to enable cleavage of the link to the original DNA strand from which the building block...... is transferred. Relatively few cleavable linkers are available for DNA-directed synthesis and most often they leave an amino group at the organic molecule. Here we have extended the application of 10 aryltriazenes as traceless linkers for DNA-directed synthesis. After reaction of one building block...

  16. Radiation induced emulsion polymerization

    International Nuclear Information System (INIS)

    Stannett, V.T.; Stahel, E.P.

    1990-01-01

    High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

  17. Dose response characteristics of polymethacrylic acid gel (PMAAG) for a polymerization-based dosimeter using NMR.

    Science.gov (United States)

    Iskandar, S M; Elias, S; Jumiah, H; Asri, M T M; Masrianis, A; Ab Rahman, M Z; Taiman, K; Abdul Rashid, M Y

    2004-05-01

    The radiation-response characteristics of polymetharylic acid gel dosimeter prepared with different concentrations of monomer and cross-linker is described in these studies. The dosimeters were prepared under the hypoxic condition in a glove box and were then irradiated with gamma-rays produced by Co-60 radionuclide that was generated at 1.25MeV energy. The irradiation took place at different doses ranged from 0Gy to 19Gy. Due to the radiation activities, chain-reaction polymerisation processes had taken place in the formation of polymethacrylic acid (PMAA) gel, which cause the dose response mechanism increased in the NMR relaxation rates of protons. It has been observed that for higher concentration of monomer and cross-linker, the polymerization rate was increased.

  18. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-19

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili; Isimjan, Tayirjan T.; Del Gobbo, Silvano; Anjum, Dalaver Hussain; Abdel-Azeim, Safwat; Cavallo, Luigi; Garcia Esparza, Angel T.; Domen, Kazunari; Xu, Wei; Takanabe, Kazuhiro

    2014-01-01

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. High-Flux Zeolitic Imidazolate Framework Membranes for Propylene/Propane Separation by Postsynthetic Linker Exchange.

    Science.gov (United States)

    Lee, Moon Joo; Kwon, Hyuk Taek; Jeong, Hae-Kwon

    2018-01-02

    While zeolitic imidazolate framework, ZIF-8, membranes show impressive propylene/propane separation, their throughput needs to be greatly improved for practical applications. A method is described that drastically reduces the effective thickness of ZIF-8 membranes, thereby substantially improving their propylene permeance (that is, flux). The new strategy is based on a controlled single-crystal to single-crystal linker exchange of 2-methylimidazole in ZIF-8 membrane grains with 2-imidazolecarboxaldehyde (ZIF-90 linker), thereby enlarging the effective aperture size of ZIF-8. The linker-exchanged ZIF-8 membranes showed a drastic increase in propylene permeance by about four times, with a negligible loss in propylene/propane separation factor when compared to as-prepared membranes. The linker-exchange effect depends on the membrane synthesis method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Investigation of the Linker Swing Motion in the Zeolitic Imidazolate Framework ZIF-90

    KAUST Repository

    Zheng, Bin; Fu, Fang; Wang, Lian Li; Yang, Limin; Zhu, Yihan; Du, Huiling

    2018-01-01

    The linker swing motion in the zeolitic imidazolate framework ZIF-90 is investigated by density functional theory (DFT) calculation, molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations. The relation between the terminal

  2. Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

    Science.gov (United States)

    Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

    2014-12-16

    Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

  3. LRRC45 Is a Centrosome Linker Component Required for Centrosome Cohesion

    Directory of Open Access Journals (Sweden)

    Runsheng He

    2013-09-01

    Full Text Available During interphase, centrosomes are connected by a proteinaceous linker between the proximal ends of the centrioles, which is important for the centrosomes to function as a single microtubule-organizing center. However, the composition and regulation of centrosomal linker remain largely unknown. Here, we show that LRRC45 is a centrosome linker that localizes at the proximal ends of the centrioles and forms fiber-like structures between them. Depletion of LRRC45 results in centrosome splitting during interphase. Moreover, LRRC45 interacts with both C-Nap1 and rootletin and is phosphorylated by Nek2A at S661 during mitosis. After phosphorylation, both LRRC45 centrosomal localization and fiber-like structures are significantly reduced, which subsequently leads to centrosome separation. Thus, LRRC45 is a critical component of the proteinaceous linker between two centrioles and is required for centrosome cohesion.

  4. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

    Jiang, J.; Wu, Zhenning; Benter, Maike

    2008-01-01

    , external electrode, and electrodeless microwave or high frequency reactors. [3] Softplasma™ is an internal electrode plasma setup powered by low frequenc~ gower supply. It was developed in late 90s for surface treatment of silicone rubber. [ ]- 5] It is a low pressure, low electron density, 3D homogenous......In the late 19th century, the first depositions - known today as plasma polymers, were reported. In the last century, more and more research has been put into plasma polymers. Many different deposition systems have been developed. [1, 2] Shi F. F. broadly classified them into internal electrode...... plasma. In this study, we are presenting the surface modification"pf polymers by plasma polymerization using Softplasma™. Softplasma™ can be used for two major types of polymerization: polymerization of vinyl monomers, where plasma acts as initiator; chemical vapour deposition, where plasma acts...

  5. Identification of novel post-translational modifications in linker histones from chicken erythrocytes.

    Science.gov (United States)

    Sarg, Bettina; Lopez, Rita; Lindner, Herbert; Ponte, Inma; Suau, Pedro; Roque, Alicia

    2015-01-15

    Chicken erythrocyte nuclei were digested with micrococcal nuclease and fractionated by centrifugation in low-salt buffer into soluble and insoluble fractions. Post-translational modifications of the purified linker histones of both fractions were analyzed by LC-ESI-MS/MS. All six histone H1 subtypes (H1.01, H1.02, H1.03, H1.10, H1.1L and H1.1R) and histone H5 were identified. Mass spectrometry analysis enabled the identification of a wide range of PTMs, including N(α)-terminal acetylation, acetylation, formylation, phosphorylation and oxidation. A total of nine new modifications in chicken linker histones were mapped, most of them located in the N-terminal and globular domains. Relative quantification of the modified peptides showed that linker histone PTMs were differentially distributed among both chromatin fractions, suggesting their relevance in the regulation of chromatin structure. The analysis of our results combined with previously reported data for chicken and some mammalian species showed that most of the modified positions were conserved throughout evolution, highlighting their importance in specific linker histone functions and epigenetics. Post-translational modifications of linker histones could have a role in the regulation of gene expression through the modulation of chromatin higher-order structure and chromatin remodeling. Finding new PTMs in linker histones is the first step to elucidate their role in the histone code. In this manuscript we report nine new post-translational modifications of the linker histones from chicken erythrocytes, one in H5 and eight in the H1 subtypes. Chromatin fractionated by centrifugation in low-salt buffer resulted in two fractions with different contents and compositions of linker histones and enriched in specific core histone PTMs. Of particular interest is the fact that linker histone PTMs were differentially distributed in both chromatin fractions, suggesting specific functions. Future studies are needed to

  6. Monte Carlo analysis of neck linker extension in kinesin molecular motors.

    Directory of Open Access Journals (Sweden)

    Matthew L Kutys

    2010-11-01

    Full Text Available Kinesin stepping is thought to involve both concerted conformational changes and diffusive movement, but the relative roles played by these two processes are not clear. The neck linker docking model is widely accepted in the field, but the remainder of the step--diffusion of the tethered head to the next binding site--is often assumed to occur rapidly with little mechanical resistance. Here, we investigate the effect of tethering by the neck linker on the diffusive movement of the kinesin head, and focus on the predicted behavior of motors with naturally or artificially extended neck linker domains. The kinesin chemomechanical cycle was modeled using a discrete-state Markov chain to describe chemical transitions. Brownian dynamics were used to model the tethered diffusion of the free head, incorporating resistive forces from the neck linker and a position-dependent microtubule binding rate. The Brownian dynamics and chemomechanical cycle were coupled to model processive runs consisting of many 8 nm steps. Three mechanical models of the neck linker were investigated: Constant Stiffness (a simple spring, Increasing Stiffness (analogous to a Worm-Like Chain, and Reflecting (negligible stiffness up to a limiting contour length. Motor velocities and run lengths from simulated paths were compared to experimental results from Kinesin-1 and a mutant containing an extended neck linker domain. When tethered by an increasingly stiff spring, the head is predicted to spend an unrealistically short amount of time within the binding zone, and extending the neck is predicted to increase both the velocity and processivity, contrary to experiments. These results suggest that the Worm-Like Chain is not an adequate model for the flexible neck linker domain. The model can be reconciled with experimental data if the neck linker is either much more compliant or much stiffer than generally assumed, or if weak kinesin-microtubule interactions stabilize the diffusing

  7. Effective generation of transgenic pigs and mice by linker based sperm-mediated gene transfer.

    OpenAIRE

    Chang, Keejong; Qian, Jin; Jiang, MeiSheng; Liu, Yi-Hsin; Wu, Ming-Che; Chen, Chi-Dar; Lai, Chao-Kuen; Lo, Hsin-Lung; Hsiao, Chin-Ton; Brown, Lucy; Bolen, James; Huang, Hsiao-I; Ho, Pei-Yu; Shih, Ping Yao; Yao, Chen-Wen

    2002-01-01

    Abstract Background Transgenic animals have become valuable tools for both research and applied purposes. The current method of gene transfer, microinjection, which is widely used in transgenic mouse production, has only had limited success in producing transgenic animals of larger or higher species. Here, we report a linker based sperm-mediated gene transfer method (LB-SMGT) that greatly improves the production efficiency of large transgenic animals. Results The linker protein, a monoclonal ...

  8. Lecithin-linker formulations for self-emulsifying delivery of nutraceuticals.

    Science.gov (United States)

    Chu, Jacquelene; Cheng, Yu-Ling; Rao, A Venketeshwer; Nouraei, Mehdi; Zarate-Muñoz, Silvia; Acosta, Edgar J

    2014-08-25

    Lecithin-linker microemulsions are formulations produced with soybean lecithin in combination with a highly lipophilic (lipophilic linker) and highly hydrophilic (hydrophilic linkers) surfactant-like additives. In this work, lecithin-linker systems were formulated to produce self-emulsifying delivery systems for β-carotene and β-sitosterol. The concentration of the lipophilic linker, sorbitan monooleate, was adjusted to minimize the formation of liquid crystals. The concentration of hydrophilic linkers, decaglyceryl caprylate/caprate and PEG-6-caprylic/capric glycerides, was gradually increased (scanned) until single phase clear microemulsions were obtained. For these scans, the oil (ethyl caprate) to water ratio was set to 1. The single phase, clear microemulsions were diluted with fed-state simulated intestinal fluid (FeSSIF) and produced stable emulsions, with drop sizes close to 200 nm. Using pseudo-ternary phase diagrams to evaluate the process of dilution of microemulsion preconcentrates (mixtures of oil, lecithin and linkers with little or no water) with FeSSIF, it was determined that self-emulsifying systems are obtained when the early stages of the dilution produce single phase microemulsions. If liquid crystals or multiple phase systems are obtained during those early stages, then the emulsification yields unstable emulsions with large drop sizes. An in vitro permeability study conducted using a Flow-Thru Dialyzer revealed that stable emulsions with drop sizes of 150-300 nm produce large and irreversible permeation of β-carotene to sheep intestine. On the other hand, unstable emulsions produced without the linker combination separated in the dialyzer chamber. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Stability and function of interdomain linker variants of glucoamylase 1 from Aspergillus niger.

    Science.gov (United States)

    Sauer, J; Christensen, T; Frandsen, T P; Mirgorodskaya, E; McGuire, K A; Driguez, H; Roepstorff, P; Sigurskjold, B W; Svensson, B

    2001-08-07

    Several variants of glucoamylase 1 (GA1) from Aspergillus niger were created in which the highly O-glycosylated peptide (aa 468--508) connecting the (alpha/alpha)(6)-barrel catalytic domain and the starch binding domain was substituted at the gene level by equivalent segments of glucoamylases from Hormoconis resinae, Humicola grisea, and Rhizopus oryzae encoding 5, 19, and 36 amino acid residues. Variants were constructed in which the H. resinae linker was elongated by proline-rich sequences as this linker itself apparently was too short to allow formation of the corresponding protein variant. Size and isoelectric point of GA1 variants reflected differences in linker length, posttranslational modification, and net charge. While calculated polypeptide chain molecular masses for wild-type GA1, a nonnatural proline-rich linker variant, H. grisea, and R. oryzae linker variants were 65,784, 63,777, 63,912, and 65,614 Da, respectively, MALDI-TOF-MS gave values of 82,042, 73,800, 73,413, and 90,793 Da, respectively, where the latter value could partly be explained by an N-glycosylation site introduced near the linker C-terminus. The k(cat) and K(m) for hydrolysis of maltooligodextrins and soluble starch, and the rate of hydrolysis of barley starch granules were essentially the same for the variants as for wild-type GA1. beta-Cyclodextrin, acarbose, and two heterobidentate inhibitors were found by isothermal titration calorimetry to bind to the catalytic and starch binding domains of the linker variants, indicating that the function of the active site and the starch binding site was maintained. The stability of GA1 linker variants toward GdnHCl and heat, however, was reduced compared to wild-type.

  10. Rational design of molecularly imprinted polymer: the choice of cross-linker.

    Science.gov (United States)

    Muhammad, Turghun; Nur, Zohre; Piletska, Elena V; Yimit, Osmanjan; Piletsky, Sergey A

    2012-06-07

    The paper describes a rational approach for the selection of cross-linkers during the development of molecularly imprinted polymers (MIPs). As a model system for this research MIPs specific for the drug zidovudine (AZT) were designed and tested. Three cross-linkers trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) were studied. The analogue of zidovudine (AZT) ester (AZT-ES) was used as a dummy template. The imprinting factors for all of the polymers in the static adsorption experiments were calculated. The data on the AZT adsorption by control polymers (CP), which were prepared with different cross-linkers without a functional monomer, was also analyzed. DVB was found to be more inert towards zidovudine than EGDMA and TRIM, which was confirmed by both molecular modelling and adsorption experiments. It was demonstrated that DVB-based polymers had a higher imprinting factor (I = 1.85) compared with other tested cross-linked polymers. It was suggested that the selection of the cross-linker should be based on the strength of the interaction with the template: the cross-linker which displays lower binding of the template should be preferential because it generates MIPs with lower non-specific binding and a higher imprinting factor, and therefore specificity. Which cross-linker to use for the preparation of any particular MIP can be determined by analysis of the interactions between the cross-linker and template. This could be done either virtually using computational modelling or by template adsorption using a small library of polymers prepared using different cross-linkers.

  11. Novel Concepts of MS-Cleavable Cross-linkers for Improved Peptide Structure Analysis

    Science.gov (United States)

    Hage, Christoph; Falvo, Francesco; Schäfer, Mathias; Sinz, Andrea

    2017-10-01

    The chemical cross-linking/mass spectrometry (MS) approach is gaining increasing importance as an alternative method for studying protein conformation and for deciphering protein interaction networks. This study is part of our ongoing efforts to develop innovative cross-linking principles for a facile and efficient assignment of cross-linked products. We evaluate two homobifunctional, amine-reactive, and MS-cleavable cross-linkers regarding their potential for automated analysis of cross-linked products. We introduce the bromine phenylurea (BrPU) linker that possesses a unique structure yielding a distinctive fragmentation pattern on collisional activation. Moreover, BrPU delivers the characteristic bromine isotope pattern and mass defect for all cross-linker-decorated fragments. We compare the fragmentation behavior of the BrPU linker with that of our previously described MS-cleavable TEMPO-Bz linker (which consists of a 2,2,6,6-tetramethylpiperidine-1-oxy moiety connected to a benzyl group) that was developed to perform free-radical-initiated peptide sequencing. Comparative collisional activation experiments (collision-induced dissociation and higher-energy collision-induced dissociation) with both cross-linkers were conducted in negative electrospray ionization mode with an Orbitrap Fusion mass spectrometer using five model peptides. As hypothesized in a previous study, the presence of a cross-linked N-terminal aspartic acid residue seems to be the prerequisite for the loss of an intact peptide from the cross-linked products. As the BrPU linker combines a characteristic mass shift with an isotope signature, it presents a more favorable combination for automated assignment of cross-linked products compared with the TEMPO-Bz linker. [Figure not available: see fulltext.

  12. Multi-component polymeric system for tumour cell-specific gene delivery using a universal bungarotoxin linker

    Czech Academy of Sciences Publication Activity Database

    Willemsen, R. A.; Pechar, Michal; Carlisle, R. C.; Schooten, E.; Pola, Robert; Thompson, A. J.; Seymour, L. W.; Ulbrich, Karel

    2010-01-01

    Roč. 27, č. 11 (2010), s. 2274-2282 ISSN 0724-8741 R&D Projects: GA ČR GA203/08/0543; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40500505 Keywords : adenovirus * hydrophilic polymers * tumour targeting Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.456, year: 2010

  13. Inflation of a Polymeric Menbrane

    DEFF Research Database (Denmark)

    Kristensen, Susanne B.; Larsen, Johannes R.; Hassager, Ole

    1998-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane.......We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane....

  14. Guided in Situ Polymerization of MEH-PPV in Mesoporous Titania Photoanodes.

    Science.gov (United States)

    Minar, Norma K; Docampo, Pablo; Fattakhova-Rohlfing, Dina; Bein, Thomas

    2015-05-20

    Incorporation of conjugated polymers into porous metal oxide networks is a challenging task, which is being pursued via many different approaches. We have developed the guided in situ polymerization of poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) in porous titania films by means of surface functionalization. The controlled polymerization via the Gilch route was induced by an alkoxide base and by increasing the temperature. The selected and specially designed surface-functionalizing linker molecules mimic the monomer or its activated form, respectively. In this way, we drastically enhanced the amount of MEH-PPV incorporated into the porous titania phase compared to nonfunctionalized samples by a factor of 6. Additionally, photovoltaic measurements were performed. The devices show shunting or series resistance limitations, depending on the surface functionalization prior to in situ polymerization of MEH-PPV. We suggest that the reason for this behavior can be found in the orientation of the grown polymer chains with respect to the titania surface. Therefore, the geometry of the anchoring via the linker molecules is relevant for exploiting the full electronic potential of the conjugated polymer in the resulting hybrid composite. This observation will help to design future synthesis methods for new hybrid materials from conjugated polymers and n-type semiconductors to take full advantage of favorable electronic interactions between the two phases.

  15. Polymerized and functionalized triglycerides

    Science.gov (United States)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  16. Polymerization by radiation. Application

    International Nuclear Information System (INIS)

    Romero, M.; Fernandez Miranda, J.

    1997-01-01

    Achieved results of the research work done in the field of radiation polymerization are summarized. Developing new chromatographic matrices, the radiation grafting of Glycidyl methacrylate on the surface of Low Density Polyethylene beads was studied. The dependence of both, the grafted degree and width of the grafted layer, with the radiation dose applied, is presented

  17. RAFT polymerization mediated bioconjugation strategies

    OpenAIRE

    Bulmuş, Volga

    2011-01-01

    This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

  18. Structural properties of the linkers connecting the N- and C- terminal domains in the MocR bacterial transcriptional regulators

    Directory of Open Access Journals (Sweden)

    Teresa Milano

    2016-12-01

    Full Text Available Peptide inter-domain linkers are peptide segments covalently linking two adjacent domains within a protein. Linkers play a variety of structural and functional roles in naturally occurring proteins. In this work we analyze the sequence properties of the predicted linker regions of the bacterial transcriptional regulators belonging to the recently discovered MocR subfamily of the GntR regulators. Analyses were carried out on the MocR sequences taken from the phyla Actinobacteria, Firmicutes, Alpha-, Beta- and Gammaproteobacteria. The results suggest that MocR linkers display phylum-specific characteristics and unique features different from those already described for other classes of inter-domain linkers. They show an average length significantly higher: 31.8 ± 14.3 residues reaching a maximum of about 150 residues. Compositional propensities displayed general and phylum-specific trends. Pro is dominating in all linkers. Dyad propensity analysis indicate Pro–Pro as the most frequent amino acid pair in all linkers. Physicochemical properties of the linker regions were assessed using amino acid indices relative to different features: in general, MocR linkers are flexible, hydrophilic and display propensity for β-turn or coil conformations. Linker sequences are hypervariable: only similarities between MocR linkers from organisms related at the level of species or genus could be found with sequence searches. The results shed light on the properties of the linker regions of the new MocR subfamily of bacterial regulators and may provide knowledge-based rules for designing artificial linkers with desired properties.

  19. Antimicrobial bacterial cellulose nanocomposites prepared by in situ polymerization of 2-aminoethyl methacrylate.

    Science.gov (United States)

    Figueiredo, Ana R P; Figueiredo, Andrea G P R; Silva, Nuno H C S; Barros-Timmons, Ana; Almeida, Adelaide; Silvestre, Armando J D; Freire, Carmen S R

    2015-06-05

    Antimicrobial bacterial cellulose/poly(2-aminoethyl methacrylate) (BC/PAEM) nanocomposites were prepared by in situ radical polymerization of 2-aminoethyl methacrylate, using variable amounts of N,N-methylenebis(acrylamide) (MBA) as cross-linker. The obtained nanocomposites were characterized in terms of their structure, morphology, thermal stability, mechanical properties and antibacterial activity. The ensuing composite membranes were significantly more transparent than those of pure BC and showed improved thermal and mechanical properties. The antibacterial activity of the obtained nanocomposites was assessed towards a recombinant bioluminescent Escherichia coli and only the non-crosslinked nanocomposite (BC/PAEM) proved to have antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Chemical and enzymatic stability of amino acid prodrugs containing methoxy, ethoxy and propylene glycol linkers.

    Science.gov (United States)

    Gupta, Deepak; Gupta, Sheeba Varghese; Lee, Kyung-Dall; Amidon, Gordon L

    2009-01-01

    We evaluated the chemical and enzymatic stabilities of prodrugs containing methoxy, ethoxy and propylene glycol linkers in order to find a suitable linker for prodrugs of carboxylic acids with amino acids. l-Valine and l-phenylalanine prodrugs of model compounds (benzoic acid and phenyl acetic acid) containing methoxy, ethoxy and propylene glycol linkers were synthesized. The hydrolysis rate profile of each compound was studied at physiologically relevant pHs (1.2, 4, 6 and 7.4). Enzymatic hydrolysis of propylene glycol containing compounds was studied using Caco-2 homogenate as well as purified enzyme valacyclovirase. It was observed that the stability of the prodrugs increases with the linker length (propyl > ethyl > methyl). The model prodrugs were stable at acidic pH as compared to basic pH. It was observed that the prodrug with the aliphatic amino acid promoiety was more stable compared to its aromatic counterpart. The comparison between benzyl and the phenyl model compounds revealed that the amino acid side chain is significant in determining the stability of the prodrug whereas the benzyl or phenyl carboxylic acid had little or no effect on the stability. The enzymatic activation studies of propylene glycol linker prodrug in the presence of valacyclovirase and cell homogenate showed faster generation of the parent drug at pH 7.4. The half-life of prodrugs at pH 7.4 was more than 12 h, whereas in the presence of cell homogenate the half-lives were less than 1 h. Hydrolysis by Caco-2 homogenate generated the parent compound in two steps, where the prodrug was first converted to the intermediate, propylene glycol benzoate, which was then converted to the parent compound (benzoic acid). Enzymatic hydrolysis of propylene glycol containing prodrugs by valacyclovirase showed hydrolysis of the amino acid ester part to generate the propylene glycol ester of model compound (propylene glycol benzoate) as the major product. The amino acid prodrugs containing methoxy

  1. The measles virus phosphoprotein interacts with the linker domain of STAT1

    International Nuclear Information System (INIS)

    Devaux, Patricia; Priniski, Lauren; Cattaneo, Roberto

    2013-01-01

    The measles virus (MV) phosphoprotein (P) and V proteins block the interferon (IFN) response by impeding phosphorylation of the signal transducer and activator of transcription 1 (STAT1) by the Janus kinase 1 (JAK1). We characterized how STAT1 mutants interact with P and JAK1 phosphorylation. Certain mutants of the linker, the Src-homology 2 domain (SH2), or the transactivation domain had reduced or abolished phosphorylation through JAK1 after IFN treatment. Other mutants, mainly localized in the linker, failed to interact with P as documented by the lack of interference with nuclear translocation. Thus the functional footprint of P on STAT1 localizes mainly to the linker domain; there is also some overlap with the STAT1 phosphorylation functional footprint on the SH2 domain. Based on these observations, we discuss how the MV-P might operate to inhibit the JAK/STAT pathway. - Highlights: • Residue in the linker and SH2 domains of STAT1 are important for MV-P interaction. • Residue in the linker and SH2 domains of STAT1 are important for STAT1 phosphorylation. • Residues interferring with both functions have similar location on STAT1. • The viral P and V proteins may operate in concert to inhibit the JAK/STAT pathway

  2. The measles virus phosphoprotein interacts with the linker domain of STAT1

    Energy Technology Data Exchange (ETDEWEB)

    Devaux, Patricia, E-mail: devaux.patricia@mayo.edu; Priniski, Lauren; Cattaneo, Roberto

    2013-09-15

    The measles virus (MV) phosphoprotein (P) and V proteins block the interferon (IFN) response by impeding phosphorylation of the signal transducer and activator of transcription 1 (STAT1) by the Janus kinase 1 (JAK1). We characterized how STAT1 mutants interact with P and JAK1 phosphorylation. Certain mutants of the linker, the Src-homology 2 domain (SH2), or the transactivation domain had reduced or abolished phosphorylation through JAK1 after IFN treatment. Other mutants, mainly localized in the linker, failed to interact with P as documented by the lack of interference with nuclear translocation. Thus the functional footprint of P on STAT1 localizes mainly to the linker domain; there is also some overlap with the STAT1 phosphorylation functional footprint on the SH2 domain. Based on these observations, we discuss how the MV-P might operate to inhibit the JAK/STAT pathway. - Highlights: • Residue in the linker and SH2 domains of STAT1 are important for MV-P interaction. • Residue in the linker and SH2 domains of STAT1 are important for STAT1 phosphorylation. • Residues interferring with both functions have similar location on STAT1. • The viral P and V proteins may operate in concert to inhibit the JAK/STAT pathway.

  3. A High-Throughput Small Molecule Screen for C. elegans Linker Cell Death Inhibitors.

    Directory of Open Access Journals (Sweden)

    Andrew R Schwendeman

    Full Text Available Programmed cell death is a ubiquitous process in metazoan development. Apoptosis, one cell death form, has been studied extensively. However, mutations inactivating key mammalian apoptosis regulators do not block most developmental cell culling, suggesting that other cell death pathways are likely important. Recent work in the nematode Caenorhabditis elegans identified a non-apoptotic cell death form mediating the demise of the male-specific linker cell. This cell death process (LCD, linker cell-type death is morphologically conserved, and its molecular effectors also mediate axon degeneration in mammals and Drosophila. To develop reagents to manipulate LCD, we established a simple high-throughput screening protocol for interrogating the effects of small molecules on C. elegans linker cell death in vivo. From 23,797 compounds assayed, 11 reproducibly block linker cell death onset. Of these, five induce animal lethality, and six promote a reversible developmental delay. These results provide proof-of principle validation of our screening protocol, demonstrate that developmental progression is required for linker cell death, and suggest that larger scale screens may identify LCD-specific small-molecule regulators that target the LCD execution machinery.

  4. Effect of the SH3-SH2 domain linker sequence on the structure of Hck kinase.

    Science.gov (United States)

    Meiselbach, Heike; Sticht, Heinrich

    2011-08-01

    The coordination of activity in biological systems requires the existence of different signal transduction pathways that interact with one another and must be precisely regulated. The Src-family tyrosine kinases, which are found in many signaling pathways, differ in their physiological function despite their high overall structural similarity. In this context, the differences in the SH3-SH2 domain linkers might play a role for differential regulation, but the structural consequences of linker sequence remain poorly understood. We have therefore performed comparative molecular dynamics simulations of wildtype Hck and of a mutant Hck in which the SH3-SH2 domain linker is replaced by the corresponding sequence from the homologous kinase Lck. These simulations reveal that linker replacement not only affects the orientation of the SH3 domain itself, but also leads to an alternative conformation of the activation segment in the Hck kinase domain. The sequence of the SH3-SH2 domain linker thus exerts a remote effect on the active site geometry and might therefore play a role in modulating the structure of the inactive kinase or in fine-tuning the activation process itself.

  5. Disruption of the IS6-AID linker affects voltage-gated calcium channel inactivation and facilitation.

    Science.gov (United States)

    Findeisen, Felix; Minor, Daniel L

    2009-03-01

    Two processes dominate voltage-gated calcium channel (Ca(V)) inactivation: voltage-dependent inactivation (VDI) and calcium-dependent inactivation (CDI). The Ca(V)beta/Ca(V)alpha(1)-I-II loop and Ca(2+)/calmodulin (CaM)/Ca(V)alpha(1)-C-terminal tail complexes have been shown to modulate each, respectively. Nevertheless, how each complex couples to the pore and whether each affects inactivation independently have remained unresolved. Here, we demonstrate that the IS6-alpha-interaction domain (AID) linker provides a rigid connection between the pore and Ca(V)beta/I-II loop complex by showing that IS6-AID linker polyglycine mutations accelerate Ca(V)1.2 (L-type) and Ca(V)2.1 (P/Q-type) VDI. Remarkably, mutations that either break the rigid IS6-AID linker connection or disrupt Ca(V)beta/I-II association sharply decelerate CDI and reduce a second Ca(2+)/CaM/Ca(V)alpha(1)-C-terminal-mediated process known as calcium-dependent facilitation. Collectively, the data strongly suggest that components traditionally associated solely with VDI, Ca(V)beta and the IS6-AID linker, are essential for calcium-dependent modulation, and that both Ca(V)beta-dependent and CaM-dependent components couple to the pore by a common mechanism requiring Ca(V)beta and an intact IS6-AID linker.

  6. Radiation polymerization of tetrafluoroethylene

    International Nuclear Information System (INIS)

    Kadoi, H.; Lugao, A.B.; Oikawa, H.

    1984-01-01

    Tetrafluoroethylene (TFE) monomer was obtained by means of the pyrolysis of chlorodifluoromethane (R-22). The experiments were carried out in quartz tube with temperature between 700 0 and 800 0 C. The principal reaction of the pyrolysis is considered to be: 2CHClF2 ----> C 2 F 4 +2HCl. However, by-products such as HF, C 3 F 6 , C 2 HClF 4 , C 4 F 8 etc are also produced in the pyrolysis process. The conversions of R-22 varied from 30 to 50%, depending upon the temperature, pressure and flow rate of R-22 in the furnace. Finally the TFE monomer of purity higher than 99.98% was obtained by fractional distillation in low temperatures ranging from -10 0 to -30 0 C. The bulk polymerization of this monomer induced by γ-rays from 3000Ci cobalt-60 source was studied at various temperatures (room temperature, 0 0 , -23 0 and -78 0 C). The monomers were introduced into stainless steel vessels of 15 and 60 ml volume under vacuum. The control of polymerization reaction was rather hard at temperatures higher than -23 0 C due to the difficulty of removing the heat of reaction. However, the polymerization at -78 0 C was very easy to control. The white polymer particles were obtained in agglomerated state. The IR spectra of the polymers were consistent with those of commercial products. The melting points of samples were between 326 0 and 331 0 C. (Author) [pt

  7. Radiation chemistry of polymeric system

    International Nuclear Information System (INIS)

    Machi, Sueo; Ishigaki, Isao

    1978-01-01

    Among wide application of radiation in the field of polymer chemistry, practices of polymerization, graft polymerization, bridging, etc. are introduced hereinafter. As for the radiation sources of radiation polymerization, in addition to the 60 Co-γ ray with long permeation distance which has been usually applied, electron beam accelerators with high energy, large current and high reliability have come to be produced, and the liquid phase polymerization by electron beam has attracted attention industrially. Concerning polymerizing reactions, explanations were given to electron beam polymerization under high dose rate, the polymerization in supercooling state or under high pressure, and emulsifying polymerization. As for radiation bridging, radiation is applied for the bridging of hydrogel, acceleration of bridging and improvement of radiation resistance. It is also utilized for reforming membranes by graft polymerization, and synthesis of polymers for medical use. Application of fixed enzymes in the medical field has been investigated by fixing various enzymes by low temperature γ-ray polymerization with glassy monomers such as HEMA. (Kobatake, H.)

  8. Versatile supramolecular reactivity of zinc-tetra(4-pyridylporphyrin in crystalline solids: Polymeric grids with zinc dichloride and hydrogen-bonded networks with mellitic acid

    Directory of Open Access Journals (Sweden)

    Sophia Lipstman

    2009-12-01

    Full Text Available Crystal engineering studies confirm that the zinc-tetra(4-pyridylporphyrin building block reveals versatile supramolecular chemistry. In this work, it was found to be reactive in the assembly of both (a a 2D polymeric array by a unique combination of self-coordination and coordination through external zinc dichloride linkers and (b an extended heteromolecular hydrogen-bonded network with mellitic acid sustained by multiple connectivity between the component species.

  9. Linker Histone Phosphorylation Regulates Global Timing of Replication Origin Firing*S⃞

    Science.gov (United States)

    Thiriet, Christophe; Hayes, Jeffrey J.

    2009-01-01

    Despite the presence of linker histone in all eukaryotes, the primary function(s) of this histone have been difficult to clarify. Knock-out experiments indicate that H1s play a role in regulation of only a small subset of genes but are an essential component in mouse development. Here, we show that linker histone (H1) is involved in the global regulation of DNA replication in Physarum polycephalum. We find that genomic DNA of H1 knock-down cells is more rapidly replicated, an effect due at least in part to disruption of the native timing of replication fork firing. Immunoprecipitation experiments demonstrate that H1 is transiently lost from replicating chromatin via a process facilitated by phosphorylation. Our results suggest that linker histones generate a chromatin environment refractory to replication and that their transient removal via protein phosphorylation during S phase is a critical step in the epigenetic regulation of replication timing. PMID:19015270

  10. The centrosomal linker and microtubules provide dual levels of spatial coordination of centrosomes.

    Directory of Open Access Journals (Sweden)

    Marko Panic

    2015-05-01

    Full Text Available The centrosome is the principal microtubule organizing center in most animal cells. It consists of a pair of centrioles surrounded by pericentriolar material. The centrosome, like DNA, duplicates exactly once per cell cycle. During interphase duplicated centrosomes remain closely linked by a proteinaceous linker. This centrosomal linker is composed of rootletin filaments that are anchored to the centrioles via the protein C-Nap1. At the onset of mitosis the linker is dissolved by Nek2A kinase to support the formation of the bipolar mitotic spindle. The importance of the centrosomal linker for cell function during interphase awaits characterization. Here we assessed the phenotype of human RPE1 C-Nap1 knockout (KO cells. The absence of the linker led to a modest increase in the average centrosome separation from 1 to 2.5 μm. This small impact on the degree of separation is indicative of a second level of spatial organization of centrosomes. Microtubule depolymerisation or stabilization in C-Nap1 KO cells dramatically increased the inter-centrosomal separation (> 8 μm. Thus, microtubules position centrosomes relatively close to one another in the absence of linker function. C-Nap1 KO cells had a Golgi organization defect with a two-fold expansion of the area occupied by the Golgi. When the centrosomes of C-Nap1 KO cells showed considerable separation, two spatially distinct Golgi stacks could be observed. Furthermore, migration of C-Nap1 KO cells was slower than their wild type RPE1 counterparts. These data show that the spatial organization of centrosomes is modulated by a combination of centrosomal cohesion and microtubule forces. Furthermore a modest increase in centrosome separation has major impact on Golgi organization and cell migration.

  11. In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

    Science.gov (United States)

    Kloust, Hauke; Schmidtke, Christian; Feld, Artur; Schotten, Theo; Eggers, Robin; Fittschen, Ursula E A; Schulz, Florian; Pöselt, Elmar; Ostermann, Johannes; Bastús, Neus G; Weller, Horst

    2013-04-16

    Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

  12. Controlled Fab installation onto polymeric micelle nanoparticles for tuned bioactivity

    Science.gov (United States)

    Chen, Shaoyi; Florinas, Stelios; Teitgen, Abigail; Xu, Ze-Qi; Gao, Changshou; Wu, Herren; Kataoka, Kazunori; Cabral, Horacio; Christie, R. James

    2017-12-01

    Antibodies and antigen-binding fragments (Fabs) can be used to modify the surface of nanoparticles for enhanced target binding. In our previous work, site-specific conjugation of Fabs to polymeric micelles using conventional methods was limited to approximately 30% efficiency, possibly due to steric hindrance related to macromolecular reactants. Here, we report a new method that enables conjugation of Fabs onto a micelle surface in a controlled manner with up to quantitative conversion of nanoparticle reactive groups. Variation of (i) PEG spacer length in a heterofunctionalized cross-linker and (ii) Fab/polymer feed ratios resulted in production of nanoparticles with a range of Fab densities on the surface up to the theoretical maximum value. The biological impact of variable Fab density was evaluated in vitro with respect to cell uptake and cytotoxicity of a drug-loaded (SN38) targeted polymeric micelle bearing anti-EphA2 Fabs. Fab conjugation increased cell uptake and potency compared with non-targeted micelles, although a Fab density of 60% resulted in decreased uptake and potency of the targeted micelles. Altogether, our findings demonstrate that conjugation strategies can be optimized to allow control of Fab density on the surface of nanoparticles and also that Fab density may need to be optimized for a given cell-surface target to achieve the highest bioactivity.

  13. A New Achiral Linker Reagent for the Incorporation of Multiple Amino Groups Into Oligonucleotides

    DEFF Research Database (Denmark)

    1997-01-01

    The present invention relates to a new functionalized achiral linker reagent for incorporating multiple primary amino groups or reporter groups into oligonucleotides following the phosphoramidite methodology. It is possible to substitute any ribodeoxynucleotide, deoxynucleotide, or nucleotide......-oxyl-2,2,5,5-tetramethylpyrrolidine), TEMPO (N-oxyl-2,2,6,6-tetramethylpiperidine), dinitrophenyl, texas red, tetramethyl rhodamine, 7-nitrobenzo-2-oxa-1-diazole (NBD), or pyrene. The present invention also relates to a solid phase support, e.g. a Controlled Pore Glass (CPG), immobilized linker reagent...

  14. A Photolabile Linker for the Solid-Phase Synthesis of Peptide Hydrazides and Heterocycles

    DEFF Research Database (Denmark)

    Qvortrup, Katrine; Komnatnyy, Vitaly V.; Nielsen, Thomas Eiland

    2014-01-01

    A photolabile hydrazine linker for the solid-phase synthesis of peptide hydrazides and hydrazine-derived heterocycles is presented. The developed protocols enable the efficient synthesis of structurally diverse peptide hydrazides derived from the standard amino adds, including those with side......-chain protected residues at the C-terminal of the resulting peptide hydrazide, and are useful for the synthesis of dihydropyrano[2,3-c]pyrazoles. The linker is compatible with most commonly used coupling reagents and protecting groups for solid-phase peptide synthesis....

  15. Linker-dependent Junction Formation Probability in Single-Molecule Junctions

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Pil Sun; Kim, Taekyeong [HankukUniversity of Foreign Studies, Yongin (Korea, Republic of)

    2015-01-15

    We compare the junction formation probabilities of single-molecule junctions with different linker molecules by using a scanning tunneling microscope-based break-junction technique. We found that the junction formation probability varies as SH > SMe > NH2 for the benzene backbone molecule with different types of anchoring groups, through quantitative statistical analysis. These results are attributed to different bonding forces according to the linker groups formed with Au atoms in the electrodes, which is consistent with previous works. Our work allows a better understanding of the contact chemistry in the metal.molecule junction for future molecular electronic devices.

  16. Packaging based on polymeric materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2005-01-01

    Full Text Available In the past two years the consumption of common in the developed countries world wide (high tonnage polymers for packaging has approached a value of 50 wt.%. In the same period more than 50% of the packaging units on the world market were made of polymeric materials despite the fact that polymeric materials present 17 wt.% of all packaging materials. The basic properties of polymeric materials and their environmental and economical advantages, providing them such a position among packaging materials, are presented in this article. Recycling methods, as well as the development trends of polymeric packaging materials are also presented.

  17. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  18. Synthesis of magnetic polymeric microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I [M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow (Russian Federation)

    2010-05-13

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  19. Synthesis of magnetic polymeric microspheres

    International Nuclear Information System (INIS)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I

    2010-01-01

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  20. Mechanocatalytic polymerization and cross-linking in a polymeric matrix

    NARCIS (Netherlands)

    Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

    2013-01-01

    A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

  1. A photolabile linker for the solid-phase synthesis of 4-substituted NH-1,2,3-triazoles

    DEFF Research Database (Denmark)

    Qvortrup, Katrine; Nielsen, Thomas Eiland

    2011-01-01

    A novel photolabile linker for solid-phase synthesis is presented. The linker displays an azido handle for copper-catalyzed azide–alkyne cycloaddition reactions with a variety of alkynes, remains intact under typical solid-phase reaction conditions, and enables a mild photolytic release of 4...

  2. Regulation of Cellular Dynamics and Chromosomal Binding Site Preference of Linker Histones H1.0 and H1.X.

    Science.gov (United States)

    Okuwaki, Mitsuru; Abe, Mayumi; Hisaoka, Miharu; Nagata, Kyosuke

    2016-11-01

    Linker histones play important roles in the genomic organization of mammalian cells. Of the linker histone variants, H1.X shows the most dynamic behavior in the nucleus. Recent research has suggested that the linker histone variants H1.X and H1.0 have different chromosomal binding site preferences. However, it remains unclear how the dynamics and binding site preferences of linker histones are determined. Here, we biochemically demonstrated that the DNA/nucleosome and histone chaperone binding activities of H1.X are significantly lower than those of other linker histones. This explains why H1.X moves more rapidly than other linker histones in vivo Domain swapping between H1.0 and H1.X suggests that the globular domain (GD) and C-terminal domain (CTD) of H1.X independently contribute to the dynamic behavior of H1.X. Our results also suggest that the N-terminal domain (NTD), GD, and CTD cooperatively determine the preferential binding sites, and the contribution of each domain for this determination is different depending on the target genes. We also found that linker histones accumulate in the nucleoli when the nucleosome binding activities of the GDs are weak. Our results contribute to understanding the molecular mechanisms of dynamic behaviors, binding site selection, and localization of linker histones. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  3. Onset of grain filling is associated with a change in properties of linker histone variants in maize kernels

    DEFF Research Database (Denmark)

    Kalamajka, R.; Finnie, Christine; Grasser, K.D.

    2010-01-01

    ) initiation of storage synthesis. Six linker histone gene products were identified by MALDI-TOF mass spectrometry. A marked shift of around 4 pH units was observed for the linker histone spot pattern after 2D-gel electrophoresis when comparing the proteins of 11 and 16 dap kernels. The shift from acidic...

  4. A Class of Rigid Linker-bearing Glucosides for Membrane Protein Structural Study

    DEFF Research Database (Denmark)

    Sadaf, Aiman; Mortensen, Jonas S; Capaldi, Stefano

    2016-01-01

    with a branched tail group and a triglucoside head group. These head and tail groups were connected via an amide or ether linkage by using a tris(hydroxylmethyl)aminomethane (TRIS) or neopentyl glycol (NPG) linker to produce TRIS-derived triglucosides (TDTs) and NPG-derived triglucosides (NDTs), respectively...

  5. Solid-phase synthesis of polyfunctional polylysine dendrons using aldehyde linkers

    DEFF Research Database (Denmark)

    Svenssen, Daniel K.; Mirsharghi, Sahar; Boas, Ulrik

    2014-01-01

    A straightforward method for the solid-phase synthesis of C-terminally modified polylysine dendrons has been developed by applying bisalkoxybenzaldehyde and trisalkoxybenzaldehyde linkers. The method has been used for the synthesis of polylysine dendrons with a variety of C-terminal ‘tail groups’...

  6. Identification of a minimal functional linker in human topoisomerase I by domain swapping with Cre recombinase

    DEFF Research Database (Denmark)

    Hougaard, Rikke Frøhlich; Juul, Sissel; Vinther, Maria

    2008-01-01

    . In this study we replace 86 amino acids including the linker domain of the cellular type IB topoisomerase, human topoisomerase I, with four, six, or eight amino acids from the corresponding short loop region in Cre recombinase. In vitro characterization of the resulting chimeras, denoted Cropos, reveals...

  7. SEVA Linkers: A Versatile and Automatable DNA Backbone Exchange Standard for Synthetic Biology

    DEFF Research Database (Denmark)

    Kim, Se Hyeuk; Cavaleiro, Mafalda; Rennig, Maja

    2016-01-01

    flexibility, and different researchers prefer and master different molecular technologies. Here, we describe a new, highly versatile and automatable standard “SEVA linkers” for vector exchange. SEVA linkers enable backbone swapping with 20 combinations of classical enzymatic restriction/ligation, Gibson...

  8. Rapid construction of mechanically- confined multi- cellular structures using dendrimeric intercellular linker.

    Science.gov (United States)

    Mo, Xuejun; Li, Qiushi; Yi Lui, Lena Wai; Zheng, Baixue; Kang, Chiang Huen; Nugraha, Bramasta; Yue, Zhilian; Jia, Rui Rui; Fu, Hong Xia; Choudhury, Deepak; Arooz, Talha; Yan, Jie; Lim, Chwee Teck; Shen, Shali; Hong Tan, Choon; Yu, Hanry

    2010-10-01

    Tissue constructs that mimic the in vivo cell-cell and cell-matrix interactions are especially useful for applications involving the cell- dense and matrix- poor internal organs. Rapid and precise arrangement of cells into functional tissue constructs remains a challenge in tissue engineering. We demonstrate rapid assembly of C3A cells into multi- cell structures using a dendrimeric intercellular linker. The linker is composed of oleyl- polyethylene glycol (PEG) derivatives conjugated to a 16 arms- polypropylenimine hexadecaamine (DAB) dendrimer. The positively charged multivalent dendrimer concentrates the linker onto the negatively charged cell surface to facilitate efficient insertion of the hydrophobic oleyl groups into the cellular membrane. Bringing linker- treated cells into close proximity to each other via mechanical means such as centrifugation and micromanipulation enables their rapid assembly into multi- cellular structures within minutes. The cells exhibit high levels of viability, proliferation, three- dimensional (3D) cell morphology and other functions in the constructs. We constructed defined multi- cellular structures such as rings, sheets or branching rods that can serve as potential tissue building blocks to be further assembled into complex 3D tissue constructs for biomedical applications. 2010 Elsevier Ltd. All rights reserved.

  9. Low Density Lipoprotein Receptor Class A Repeats Are O-Glycosylated in Linker Regions

    DEFF Research Database (Denmark)

    Pedersen, Nis Borbye; Wang, Shengjun; Narimatsu, Yoshiki

    2014-01-01

    , which in wild-type CHO cells is glycosylated with the typical sialylated core 1 structure. The glycosites in linker regions of LDLR class A repeats are conserved in LDLR from man to Xenopus and found in other homologous receptors. O-Glycosylation is controlled by a large family of polypeptide Gal...

  10. Release of 3-methyladenine from linker and core DNA of chromatin by a purified DNA glycosylase

    International Nuclear Information System (INIS)

    Heller, E.P.; Goldthwait, D.A.

    1983-01-01

    Oligonucleosomes were isolated from [ 14 C]thymidine-labeled HeLa cells by digestion of the nuclei with micrococcal nuclease and were then alkylated with [ 3 H]methylnitrosourea. Nucleosome core particles were also prepared by further digestion of the oligonucleosomes. The distribution of 3 H-labeled methyl groups in the linker versus the core DNA was established by a determination of 3 H: 14 C ratios in oligonucleosome and core DNA. The ratios in the core DNA of 145 and 165 base pair DNA fragments were 5.2 and 5.4, respectively, while the ratio in the oligonucleosomal DNA was 8.2. Assuming an equal mixture (as determined) of 145 and 165 base pair fragments of DNA in the 185 base pair repeat, the relative concentration of 3 H methyl groups in the linker versus the core DNA was 4.2. Thus, 45% of the 3 H methyl groups were in the linker DNA, and 55% were in the core DNA. Some shielding of the DNA was evident during alkylation. The concentrations of alkyl groups on the linker and core DNA were 67 and 12% of that found on free DNA alkylated under comparable conditions. No evidence for preferential shielding of the major or minor groove was observed. The purified 3-methyladenine DNA glycosylase I of Escherichia coli released approximately 37% of the 3-methyladenine from the linker DNA and 13% from the core DNA. The limited enzymatic removal of 3-methyladenine in vitro compared to the efficient removal in vivo suggests that conformational changes of the oligonucleosome and core structure must occur for total repair

  11. SH2-catalytic domain linker heterogeneity influences allosteric coupling across the SFK family.

    Science.gov (United States)

    Register, A C; Leonard, Stephen E; Maly, Dustin J

    2014-11-11

    Src-family kinases (SFKs) make up a family of nine homologous multidomain tyrosine kinases whose misregulation is responsible for human disease (cancer, diabetes, inflammation, etc.). Despite overall sequence homology and identical domain architecture, differences in SH3 and SH2 regulatory domain accessibility and ability to allosterically autoinhibit the ATP-binding site have been observed for the prototypical SFKs Src and Hck. Biochemical and structural studies indicate that the SH2-catalytic domain (SH2-CD) linker, the intramolecular binding epitope for SFK SH3 domains, is responsible for allosterically coupling SH3 domain engagement to autoinhibition of the ATP-binding site through the conformation of the αC helix. As a relatively unconserved region between SFK family members, SH2-CD linker sequence variability across the SFK family is likely a source of nonredundant cellular functions between individual SFKs via its effect on the availability of SH3 and SH2 domains for intermolecular interactions and post-translational modification. Using a combination of SFKs engineered with enhanced or weakened regulatory domain intramolecular interactions and conformation-selective inhibitors that report αC helix conformation, this study explores how SH2-CD sequence heterogeneity affects allosteric coupling across the SFK family by examining Lyn, Fyn1, and Fyn2. Analyses of Fyn1 and Fyn2, isoforms that are identical but for a 50-residue sequence spanning the SH2-CD linker, demonstrate that SH2-CD linker sequence differences can have profound effects on allosteric coupling between otherwise identical kinases. Most notably, a dampened allosteric connection between the SH3 domain and αC helix leads to greater autoinhibitory phosphorylation by Csk, illustrating the complex effects of SH2-CD linker sequence on cellular function.

  12. Collaborative Research: Polymeric Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Shenqiang [Temple Univ., Philadelphia, PA (United States). College of Engineering

    2017-04-20

    The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamental understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.

  13. Polymerization with freezing

    International Nuclear Information System (INIS)

    Ben-Naim, E; Krapivsky, P L

    2005-01-01

    Irreversible aggregation processes involving reactive and frozen clusters are investigated using the rate equation approach. In aggregation events, two clusters join irreversibly to form a larger cluster; additionally, reactive clusters may spontaneously freeze. Frozen clusters do not participate in merger events. Generally, freezing controls the nature of the aggregation process, as demonstrated by the final distribution of frozen clusters. The cluster mass distribution has a power-law tail, F k ∼k -γ , when the freezing process is sufficiently slow. Different exponents, γ = 1 and 3, are found for the constant and the product aggregation rates, respectively. For the latter case, the standard polymerization model, either no gels, or a single gel, or even multiple gels, may be produced

  14. Polymeric micelles for drug targeting.

    Science.gov (United States)

    Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh

    2007-11-01

    Polymeric micelles are nano-delivery systems formed through self-assembly of amphiphilic block copolymers in an aqueous environment. The nanoscopic dimension, stealth properties induced by the hydrophilic polymeric brush on the micellar surface, capacity for stabilized encapsulation of hydrophobic drugs offered by the hydrophobic and rigid micellar core, and finally a possibility for the chemical manipulation of the core/shell structure have made polymeric micelles one of the most promising carriers for drug targeting. To date, three generations of polymeric micellar delivery systems, i.e. polymeric micelles for passive, active and multifunctional drug targeting, have arisen from research efforts, with each subsequent generation displaying greater specificity for the diseased tissue and/or targeting efficiency. The present manuscript aims to review the research efforts made for the development of each generation and provide an assessment on the overall success of polymeric micellar delivery system in drug targeting. The emphasis is placed on the design and development of ligand modified, stimuli responsive and multifunctional polymeric micelles for drug targeting.

  15. Molecular dissection of the interaction between the SH3 domain and the SH2-Kinase Linker region in PTK6.

    Science.gov (United States)

    Kim, Han Ie; Jung, Jinwon; Lee, Eun-Saem; Kim, Yong-Chul; Lee, Weontae; Lee, Seung-Taek

    2007-11-03

    PTK6 (also known as Brk) is an intracellular tyrosine kinase that contains SH3, SH2, and tyrosine kinase catalytic (Kinase) domains. The SH3 domain of PTK6 interacts with the N-terminal half of the linker (Linker) region between the SH2 and Kinase domains. Site-directed mutagenesis and surface plasmon resonance studies showed that a tryptophan residue (Trp44) in the SH3 domain and proline residues in the Linker region, in the order of Pro177, Pro175, and Pro179, contribute to the interaction. The three-dimensional modeled structure of the SH3-Linker complex was in agreement with the biochemical data. Disruption of the intramolecular interaction between the SH3 domain and the Linker region by mutation of Trp44, Pro175, Pro177, and Pro179 markedly increased the catalytic activity of PTK6 in HEK 293 cells. These results demonstrate that Trp44 in the SH3 domain and Pro177, Pro175, and Pro179 in the N-terminal half of the Linker region play important roles in the SH3-Linker interaction to maintain the protein in an inactive conformation along with the phosphorylated Tyr447-SH2 interaction.

  16. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  17. cis-Apa: a practical linker for the microwave-assisted preparation of cyclic pseudopeptides via RCM cyclative cleavage.

    Science.gov (United States)

    Baron, Alice; Verdié, Pascal; Martinez, Jean; Lamaty, Frédéric

    2011-02-04

    A new linker cis-5-aminopent-3-enoic acid (cis-Apa) was prepared for the synthesis of cyclic pseudopeptides by cyclization-cleavage by using ring-closing methatesis (RCM). We developed a new synthetic pathway for the preparation of the cis-Apa linker that was tested in the cyclization-cleavage process of different RGD peptide sequences. Different macrocyclic peptidomimetics were prepared by using this integrated microwave-assisted method, showing that the readily available cis-Apa amino acid is well adapted as a linker in the cyclization-cleavage process.

  18. De fysica van polymere materialen

    NARCIS (Netherlands)

    Struik, L.C.E.

    1987-01-01

    Rede, uitgesproken ter gelegenheid van de aanvaarding van het ambt van buitengewoon hoogleraar in de fysica van polymere materialen aan de Universitelt Twente op donderdag 22 januarì 1987 door Dr.lr. L.C.E. Struik.

  19. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Gnanou, Yves

    2014-01-01

    .e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  20. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  1. Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

    NARCIS (Netherlands)

    Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

    2000-01-01

    Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

  2. The H1 linker histones: multifunctional proteins beyond the nucleosomal core particle.

    Science.gov (United States)

    Hergeth, Sonja P; Schneider, Robert

    2015-11-01

    The linker histone H1 family members are a key component of chromatin and bind to the nucleosomal core particle around the DNA entry and exit sites. H1 can stabilize both nucleosome structure and higher-order chromatin architecture. In general, H1 molecules consist of a central globular domain with more flexible tail regions at both their N- and C-terminal ends. The existence of multiple H1 subtypes and a large variety of posttranslational modifications brings about a considerable degree of complexity and makes studying this protein family challenging. Here, we review recent progress in understanding the function of linker histones and their subtypes beyond their role as merely structural chromatin components. We summarize current findings on the role of H1 in heterochromatin formation, transcriptional regulation and embryogenesis with a focus on H1 subtypes and their specific modifications. © 2015 The Authors.

  3. Destabilization of the Outer and Inner Mitochondrial Membranes by Core and Linker Histones

    Science.gov (United States)

    Cascone, Annunziata; Bruelle, Celine; Lindholm, Dan; Bernardi, Paolo; Eriksson, Ove

    2012-01-01

    Background Extensive DNA damage leads to apoptosis. Histones play a central role in DNA damage sensing and may mediate signals of genotoxic damage to cytosolic effectors including mitochondria. Methodology/Principal Findings We have investigated the effects of histones on mitochondrial function and membrane integrity. We demonstrate that both linker histone H1 and core histones H2A, H2B, H3, and H4 bind strongly to isolated mitochondria. All histones caused a rapid and massive release of the pro-apoptotic intermembrane space proteins cytochrome c and Smac/Diablo, indicating that they permeabilize the outer mitochondrial membrane. In addition, linker histone H1, but not core histones, permeabilized the inner membrane with a collapse of the membrane potential, release of pyridine nucleotides, and mitochondrial fragmentation. Conclusions We conclude that histones destabilize the mitochondrial membranes, a mechanism that may convey genotoxic signals to mitochondria and promote apoptosis following DNA damage. PMID:22523586

  4. Linker histones: novel insights into structure-specific recognition of the nucleosome.

    Science.gov (United States)

    Cutter, Amber R; Hayes, Jeffrey J

    2017-04-01

    Linker histones (H1s) are a primary component of metazoan chromatin, fulfilling numerous functions, both in vitro and in vivo, including stabilizing the wrapping of DNA around the nucleosome, promoting folding and assembly of higher order chromatin structures, influencing nucleosome spacing on DNA, and regulating specific gene expression. However, many molecular details of how H1 binds to nucleosomes and recognizes unique structural features on the nucleosome surface remain undefined. Numerous, confounding studies are complicated not only by experimental limitations, but the use of different linker histone isoforms and nucleosome constructions. This review summarizes the decades of research that has resulted in several models of H1 association with nucleosomes, with a focus on recent advances that suggest multiple modes of H1 interaction in chromatin, while highlighting the remaining questions.

  5. Polyolefin nanocomposites in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

    2011-07-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  6. Polyolefin nanocomposites in situ polymerization

    International Nuclear Information System (INIS)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul

    2011-01-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  7. Electroactivity in Polymeric Materials

    CERN Document Server

    2012-01-01

    Electroactivity in Polymeric Materials provides an in-depth view of the theory of electroactivity and explores exactly how and why various electroactive phenomena occur. The book explains the theory behind electroactive bending (including ion-polymer-metal-composites –IPMCs), dielectric elastomers, electroactive contraction, and electroactive contraction-expansion cycles.  The book also balances theory with applications – how electroactivity can be used – drawing inspiration from the manmade mechanical world and the natural world around us.  This book captures: A complete introduction to electroactive materials including examples and recent developments The theory and applications of numerous topics like electroactive bending of dielectric elastomers and electroactive contraction and expansion New topics, such as biomimetic applications and energy harvesting This is a must-read within the electroactive community, particularly for professionals and graduate students who are interested in the ...

  8. Construction of Multivalent Homo- and Heterofunctional ABO Blood Group Glycoconjugates Using a Trifunctional Linker Strategy.

    Science.gov (United States)

    Daskhan, Gour Chand; Tran, Hanh-Thuc Ton; Meloncelli, Peter J; Lowary, Todd L; West, Lori J; Cairo, Christopher W

    2018-02-21

    The design and synthesis of multivalent ligands displaying complex oligosaccharides is necessary for the development of therapeutics, diagnostics, and research tools. Here, we report an efficient conjugation strategy to prepare complex glycoconjugates with 4 copies of 1 or 2 separate glycan epitopes, providing 4-8 carbohydrate residues on a tetravalent poly(ethylene glycol) scaffold. This strategy provides complex glycoconjugates that approach the size of glycoproteins (15-18 kDa) while remaining well-defined. The synthetic strategy makes use of three orthogonal functional groups, including a reactive N-hydroxysuccinimide (NHS)-ester moiety on the linker to install the first carbohydrate epitope via reaction with an amine. A masked amine functionality on the linker is revealed after the removal of a fluorenylmethyloxycarbonyl (Fmoc)-protecting group, allowing the attachment to the NHS-activated poly(ethylene glycol) (PEG) scaffold. An azide group in the linker was then used to incorporate the second carbohydrate epitope via catalyzed alkyne-azide cycloaddition. Using a known tetravalent PEG scaffold (PDI, 1.025), we prepared homofunctional glycoconjugates that display four copies of lactose and the A-type II or the B-type II human blood group antigens. Using our trifunctional linker, we expanded this strategy to produce heterofunctional conjugates with four copies of two separate glycan epitopes. These heterofunctional conjugates included Neu5Ac, 3'-sialyllactose, or 6'-sialyllactose as a second antigen. Using an alternative strategy, we generated heterofunctional conjugates with three copies of the glycan epitope and one fluorescent group (on average) using a sequential dual-amine coupling strategy. These conjugation strategies should be easily generalized for conjugation of other complex glycans. We demonstrate that the glycan epitopes of heterofunctional conjugates engage and cluster target B-cell receptors and CD22 receptors on B cells, supporting the

  9. Elastin-like Polypeptide Linkers for Single-Molecule Force Spectroscopy.

    Science.gov (United States)

    Ott, Wolfgang; Jobst, Markus A; Bauer, Magnus S; Durner, Ellis; Milles, Lukas F; Nash, Michael A; Gaub, Hermann E

    2017-06-27

    Single-molecule force spectroscopy (SMFS) is by now well established as a standard technique in biophysics and mechanobiology. In recent years, the technique has benefitted greatly from new approaches to bioconjugation of proteins to surfaces. Indeed, optimized immobilization strategies for biomolecules and refined purification schemes are being steadily adapted and improved, which in turn has enhanced data quality. In many previously reported SMFS studies, poly(ethylene glycol) (PEG) was used to anchor molecules of interest to surfaces and/or cantilever tips. The limitation, however, is that PEG exhibits a well-known trans-trans-gauche to all-trans transition, which results in marked deviation from standard polymer elasticity models such as the worm-like chain, particularly at elevated forces. As a result, the assignment of unfolding events to protein domains based on their corresponding amino acid chain lengths is significantly obscured. Here, we provide a solution to this problem by implementing unstructured elastin-like polypeptides as linkers to replace PEG. We investigate the suitability of tailored elastin-like polypeptides linkers and perform direct comparisons to PEG, focusing on attributes that are critical for single-molecule force experiments such as linker length, monodispersity, and bioorthogonal conjugation tags. Our results demonstrate that by avoiding the ambiguous elastic response of mixed PEG/peptide systems and instead building the molecular mechanical systems with only a single bond type with uniform elastic properties, we improve data quality and facilitate data analysis and interpretation in force spectroscopy experiments. The use of all-peptide linkers allows alternative approaches for precisely defining elastic properties of proteins linked to surfaces.

  10. Computational engineering of cellulase Cel9A-68 functional motions through mutations in its linker region.

    Science.gov (United States)

    Costa, M G S; Silva, Y F; Batista, P R

    2018-03-14

    Microbial cellulosic degradation by cellulases has become a complementary approach for biofuel production. However, its efficiency is hindered by the recalcitrance of cellulose fibres. In this context, computational protein design methods may offer an efficient way to obtain variants with improved enzymatic activity. Cel9A-68 is a cellulase from Thermobifida fusca that is still active at high temperatures. In a previous work, we described a collective bending motion, which governs the overall cellulase dynamics. This movement promotes the approximation of its CBM and CD structural domains (that are connected by a flexible linker). We have identified two residues (G460 and P461) located at the linker that act as a hinge point. Herein, we applied a new level of protein design, focusing on the modulation of this collective motion to obtain cellulase variants with enhanced functional dynamics. We probed whether specific linker mutations would affect Cel9A-68 dynamics through computational simulations. We assumed that P461G and G460+ (with an extra glycine) constructs would present enhanced interdomain motions, while the G460P mutant would be rigid. From our results, the P461G mutation resulted in a broader exploration of the conformational space, as confirmed by clustering and free energy analyses. The WT enzyme was the most rigid system. However, G460P and P460+ explored distinct conformational states described by opposite directions of low-frequency normal modes; they sampled preferentially closed and open conformations, respectively. Overall, we highlight two significant findings: (i) all mutants explored larger conformational spaces than the WT; (ii) the selection of distinct conformational populations was intimately associated with the mutation considered. Thus, the engineering of Cel9A-68 motions through linker mutations may constitute an efficient way to improve cellulase activity, facilitating the disruption of cellulose fibres.

  11. Bifunctional bridging linker-assisted synthesis and characterization of TiO{sub 2}/Au nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Žunič, Vojka, E-mail: vojka.zunic@ijs.si, E-mail: vojka13@gmail.com; Kurtjak, Mario; Suvorov, Danilo [Jožef Stefan Institute, Advanced Materials Department (Slovenia)

    2016-11-15

    Using a simple organic bifunctional bridging linker, titanium dioxide (TiO{sub 2}) nanoparticles were coupled with the Au nanoparticles to form TiO{sub 2}/Au nanocomposites with a variety of Au loadings. This organic bifunctional linker, meso-2,3-dimercaptosuccinic acid, contains two types of functional groups: (i) the carboxyl group, which enables binding to the TiO{sub 2}, and (ii) the thiol group, which enables binding to the Au. In addition, the organic bifunctional linker acts as a stabilizing agent to prevent the agglomeration and growth of the Au particles, resulting in the formation of highly dispersed Au nanoparticles. To form the TiO{sub 2}/Au nanocomposites in a simple way, we deliberately applied a synthetic method that simultaneously ensures: (i) the capping of the Au nanoparticles and (ii) the binding of different amounts of Au to the TiO{sub 2}. The TiO{sub 2}/Au nanocomposites formed with this method show enhanced UV and Vis photocatalytic activities when compared to the pure TiO{sub 2} nanopowders.Graphical Abstract.

  12. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei

    2016-11-04

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  13. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei; Rose, Bradley Daniel; Liu, Yao; Nahid, Masrur M.; Gann, Eliot; Ly, Jack; Zhao, Wei; Rosa, Stephen J.; Russell, Thomas P.; Facchetti, Antonio; McNei, Christopher R.; Bredas, Jean-Luc; Briseno, Alejandro L.

    2016-01-01

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  14. 5-fold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Thonhauser, T.; Zuluaga, S.; Harrison, D.; Welchman, E.; Arter, C.

    We present ab initio results for linker decorations in Mg-MOF74-i.e. attaching various metals  = Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker-creating new strong adsorption sites and thus maximizing small molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening we chose metals that bind favorably to the linker and further investigate adsorption of H2, CO2, and H2O for  = Li, Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the MOF unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a 5-fold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular-where the gravimetric hydrogen density increases from 1 . 63 mass% to 7 . 28 mass% and the volumetric density from 15.10 g H2 L-1 to 75.50 g H2 L-1. This work was supported by NSF Grant No. DMR-1145968.

  15. Fivefold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Arter, C. A.; Zuluaga, S.; Harrison, D.; Welchman, E.; Thonhauser, T.

    2016-10-01

    We present ab initio results for linker decorations in Mg-MOF74, i.e., attaching various metals M =Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker, creating new strong adsorption sites and thus maximizing small-molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening, we chose metals that bind favorably to the linker and further investigated adsorption of H2,CO2, and H2O for M =Li , Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the metal-organic framework (MOF) unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a fivefold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular, where the gravimetric hydrogen density increases from 1.63 to 7.28 mass % and the volumetric density increases from 15.10 to 75.50 g H2L-1 .

  16. Saccharomyces cerevisiae Linker Histone—Hho1p Maintains Chromatin Loop Organization during Ageing

    Directory of Open Access Journals (Sweden)

    Katya Uzunova

    2013-01-01

    Full Text Available Intricate, dynamic, and absolutely unavoidable ageing affects cells and organisms through their entire lifetime. Driven by diverse mechanisms all leading to compromised cellular functions and finally to death, this process is a challenge for researchers. The molecular mechanisms, the general rules that it follows, and the complex interplay at a molecular and cellular level are yet little understood. Here, we present our results showing a connection between the linker histones, the higher-order chromatin structures, and the process of chronological lifespan of yeast cells. By deleting the gene for the linker histone in Saccharomyces cerevisiae we have created a model for studying the role of chromatin structures mainly at its most elusive and so far barely understood higher-order levels of compaction in the processes of yeast chronological lifespan. The mutant cells demonstrated controversial features showing slower growth than the wild type combined with better survival during the whole process. The analysis of the global chromatin organization during different time points demonstrated certain loss of the upper levels of chromatin compaction in the cells without linker histone. The results underlay the importance of this histone for the maintenance of the chromatin loop structures during ageing.

  17. Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for aggressive CO2 separation from natural gas

    KAUST Repository

    Thompson, Joshua A.; Vaughn, Justin T.; Brunelli, Nicholas A.; Koros, William J.; Jones, Christopher W.; Nair, Sankar

    2014-01-01

    Zeolitic imidazolate framework (ZIF) materials are a promising subclass of metal-organic frameworks (MOF) for gas separations. However, due to the deleterious effects of gate-opening phenomena associated with organic linker rotation near

  18. Charged residues in the H-NS linker drive DNA binding and gene silencing in single cells.

    Science.gov (United States)

    Gao, Yunfeng; Foo, Yong Hwee; Winardhi, Ricksen S; Tang, Qingnan; Yan, Jie; Kenney, Linda J

    2017-11-21

    Nucleoid-associated proteins (NAPs) facilitate chromosome organization in bacteria, but the precise mechanism remains elusive. H-NS is a NAP that also plays a major role in silencing pathogen genes. We used genetics, single-particle tracking in live cells, superresolution microscopy, atomic force microscopy, and molecular dynamics simulations to examine H-NS/DNA interactions in single cells. We discovered a role for the unstructured linker region connecting the N-terminal oligomerization and C-terminal DNA binding domains. In the present work we demonstrate that linker amino acids promote engagement with DNA. In the absence of linker contacts, H-NS binding is significantly reduced, although no change in chromosome compaction is observed. H-NS is not localized to two distinct foci; rather, it is scattered all around the nucleoid. The linker makes DNA contacts that are required for gene silencing, while chromosome compaction does not appear to be an important H-NS function.

  19. How to remain nonfolded and pliable: the linkers in modular α-amylases as a case study.

    Science.gov (United States)

    Feller, Georges; Dehareng, Dominique; Lage, Jean-Luc Da

    2011-07-01

    The primary structure of linkers in a new class of modular α-amylases constitutes a paradigm of the structural basis that allows a polypeptide to remain nonfolded, extended and pliable. Unfolding is mediated through a depletion of hydrophobic residues and an enrichment of hydrophilic residues, amongst which Ser and Thr are over-represented. An extended and flexible conformation is promoted by the sequential arrangement of Pro and Gly, which are the most abundant residues in these linkers. This is complemented by charge repulsion, charge clustering and disulfide-bridged loops. Molecular dynamics simulations suggest the existence of conformational transitions resulting from a transient and localized hydrophobic collapse, arising from the peculiar composition of the linkers. Accordingly, these linkers should not be regarded as fully disordered, but rather as possessing various discrete structural patterns allowing them to fulfill their biological function as a free energy reservoir for concerted motions between structured domains. © 2011 The Authors Journal compilation © 2011 FEBS.

  20. Physicochemical Characteristics and Slow Release Performances of Chlorpyrifos Encapsulated by Poly(butyl acrylate-co-styrene) with the Cross-Linker Ethylene Glycol Dimethacrylate.

    Science.gov (United States)

    Wang, Yu; Gao, Zideng; Shen, Feng; Li, Yang; Zhang, Sainan; Ren, Xueqin; Hu, Shuwen

    2015-06-03

    Chlorpyrifos' application and delivery to the target substrate needs to be controlled to improve its use. Herein, poly(butyl acrylate-co-styrene) (poly(BA/St)) and poly(BA/St/ethylene glycol dimethacrylate (EGDMA)) microcapsules loaded with chlorpyrifos as a slow release formulation were prepared by emulsion polymerization. The effects of structural characteristics on the chlorpyrifos microcapsule particle size, entrapment rate (ER), pesticide loading (PL), and release behaviors in ethyl alcohol were investigated. Fourier transform infrared and thermogravimetric analysis confirmed the successful entrapment of chlorpyrifos. The ER and PL varied with the BA/St monomer ratio, chlorpyrifos/monomer core-to-shell ratio, and EGDMA cross-linker content with consequence that suitable PL was estimated to be smaller than 3.09% and the highest ER was observed as 96.74%. The microcapsule particle size (88.36-101.8 nm) remained mostly constant. The extent of sustainable release decreased with increasing content of BA, St, or chlorpyrifos in the oil phase. Specifically, an adequate degree of cross-linking with EGMDA (0.5-2.5%) increased the extent of sustainable release considerably. However, higher levels of cross-linking with EGDMA (5-10%) reduced the extent of sustainable release. Chlorpyrifos release from specific microcapsules (monomer ratio 1:2 with 0.5% EGDMA or 5 g chlopyrifos) tended to be a diffusion-controlled process, while for others, the kinetics probably indicated the initial rupture release.

  1. The unstructured linker arms of Mlh1-Pms1 are important for interactions with DNA during mismatch repair

    Science.gov (United States)

    Plys, Aaron J.; Rogacheva, Maria V.; Greene, Eric C.; Alani, Eric

    2012-01-01

    DNA mismatch repair (MMR) models have proposed that MSH proteins identify DNA polymerase errors while interacting with the DNA replication fork. MLH proteins (primarily Mlh1-Pms1 in baker’s yeast) then survey the genome for lesion-bound MSH proteins. The resulting MSH-MLH complex formed at a DNA lesion initiates downstream steps in repair. MLH proteins act as dimers and contain long (20 – 30 nanometers) unstructured arms that connect two terminal globular domains. These arms can vary between 100 to 300 amino acids in length, are highly divergent between organisms, and are resistant to amino acid substitutions. To test the roles of the linker arms in MMR, we engineered a protease cleavage site into the Mlh1 linker arm domain of baker’s yeast Mlh1-Pms1. Cleavage of the Mlh1 linker arm in vitro resulted in a defect in Mlh1-Pms1 DNA binding activity, and in vivo proteolytic cleavage resulted in a complete defect in MMR. We then generated a series of truncation mutants bearing Mlh1 and Pms1 linker arms of varying lengths. This work revealed that MMR is greatly compromised when portions of the Mlh1 linker are removed, whereas repair is less sensitive to truncation of the Pms1 linker arm. Purified complexes containing truncations in Mlh1 and Pms1 linker arms were analyzed and found to have differential defects in DNA binding that also correlated with the ability to form a ternary complex with Msh2-Msh6 and mismatch DNA. These observations are consistent with the unstructured linker domains of MLH proteins providing distinct interactions with DNA during MMR. PMID:22659005

  2. Rapid One-Pot Microwave Synthesis of Mixed-Linker Hybrid Zeolitic-Imidazolate Framework Membranes for Tunable Gas Separations.

    Science.gov (United States)

    Hillman, Febrian; Brito, Jordan; Jeong, Hae-Kwon

    2018-02-14

    The relatively slow and complex fabrication processes of polycrystalline metal-organic framework (MOF) membranes often times restrict their way to commercialization, despite their potential for molecular separation applications. Herein, we report a rapid one-pot microwave synthesis of mixed-linker hybrid zeolitic-imidazolate framework (ZIF) membranes consisting of 2-methylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker) linkers, termed ZIF-7-8 membranes. The fast-volumetric microwave heating in conjunction with a unique counter diffusion of metal and linker solutions enabled unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes in ∼90 s, the fastest MOF membrane preparation up to date. Furthermore, we were able to tune the molecular sieving properties of the ZIF-7-8 membranes by varying the benzimidazole-to-2-methylimidazole (bIm-to-mIm) linker ratio in the hybrid frameworks. The tuning of their molecular sieving properties led to the systematic change in the permeance and selectivity of various small gases. The unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes with tunable molecular sieving properties is an important step forward for the commercial gas separation applications of ZIF membranes.

  3. Effect of linkers on the αvβ3 integrin targeting efficiency of cyclic RGD-conjugates

    Science.gov (United States)

    Karmakar, Partha; Grabowska, Dorota; Sudlow, Gail; Ziabrev, Kostiantyn; Sanyal, Nibedita; Achilefu, Samuel

    2018-02-01

    Cyclic arginine-glycine-aspartic acid (cRGD) peptides are well known to target ανβ3 integrin expressed on cancer cells and neovasculature. Conjugation of these peptides with dyes, drugs, antibodies and other biomolecules through covalent linkers provides a facile way to deliver these products to tumor cells for targeted cancer therapy and diagnosis. Click chemistry and acid-amine couplings are widely used conjugation strategies. However, the effects of different linkers and the distance between the cRGD and the conjugates on the binding of cRGD ligand with ανβ3 has been underexplored. In this present study, we prepared cRGD-conjugates using different linkers and determined how they altered the tumor targeting efficiency in vitro and in vivo. The results demonstrate that different linkers significantly altered the pharmacokinetics of the cRGD conjugates and the tumor uptake kinetics. Unlike large antibodies, this preliminary finding shows that linkers used to attach drugs and fluorescent molecular probes to small peptides play a major role in the accuracy of tumor targeting and treatment outcomes. As a result, considerable attention should be paid to the nature of linkers used in the design of molecular probes and targeted therapeutics.

  4. ATPase Domain and Interdomain Linker Play a Key Role in Aggregation of Mitochondrial Hsp70 Chaperone Ssc1*

    Science.gov (United States)

    Blamowska, Marta; Sichting, Martin; Mapa, Koyeli; Mokranjac, Dejana; Neupert, Walter; Hell, Kai

    2010-01-01

    The co-chaperone Hep1 is required to prevent the aggregation of mitochondrial Hsp70 proteins. We have analyzed the interaction of Hep1 with mitochondrial Hsp70 (Ssc1) and the determinants in Ssc1 that make it prone to aggregation. The ATPase and peptide binding domain (PBD) of Hsp70 proteins are connected by a linker segment that mediates interdomain communication between the domains. We show here that the minimal Hep1 binding entity of Ssc1 consists of the ATPase domain and the interdomain linker. In the absence of Hep1, the ATPase domain with the interdomain linker had the tendency to aggregate, in contrast to the ATPase domain with the mutated linker segment or without linker, and in contrast to the PBD. The closest homolog of Ssc1, bacterial DnaK, and a Ssc1 chimera, in which a segment of the ATPase domain of Ssc1 was replaced by the corresponding segment from DnaK, did not aggregate in Δhep1 mitochondria. The propensity to aggregate appears to be a specific property of the mitochondrial Hsp70 proteins. The ATPase domain in combination with the interdomain linker is crucial for aggregation of Ssc1. In conclusion, our results suggest that interdomain communication makes Ssc1 prone to aggregation. Hep1 counteracts aggregation by binding to this aggregation-prone conformer. PMID:20007714

  5. ATPase domain and interdomain linker play a key role in aggregation of mitochondrial Hsp70 chaperone Ssc1.

    Science.gov (United States)

    Blamowska, Marta; Sichting, Martin; Mapa, Koyeli; Mokranjac, Dejana; Neupert, Walter; Hell, Kai

    2010-02-12

    The co-chaperone Hep1 is required to prevent the aggregation of mitochondrial Hsp70 proteins. We have analyzed the interaction of Hep1 with mitochondrial Hsp70 (Ssc1) and the determinants in Ssc1 that make it prone to aggregation. The ATPase and peptide binding domain (PBD) of Hsp70 proteins are connected by a linker segment that mediates interdomain communication between the domains. We show here that the minimal Hep1 binding entity of Ssc1 consists of the ATPase domain and the interdomain linker. In the absence of Hep1, the ATPase domain with the interdomain linker had the tendency to aggregate, in contrast to the ATPase domain with the mutated linker segment or without linker, and in contrast to the PBD. The closest homolog of Ssc1, bacterial DnaK, and a Ssc1 chimera, in which a segment of the ATPase domain of Ssc1 was replaced by the corresponding segment from DnaK, did not aggregate in Delta hep1 mitochondria. The propensity to aggregate appears to be a specific property of the mitochondrial Hsp70 proteins. The ATPase domain in combination with the interdomain linker is crucial for aggregation of Ssc1. In conclusion, our results suggest that interdomain communication makes Ssc1 prone to aggregation. Hep1 counteracts aggregation by binding to this aggregation-prone conformer.

  6. Pyrogallol-imprinted polymers with methyl methacrylate via precipitation polymerization

    Science.gov (United States)

    Mehamod, Faizatul Shimal; Othman, Nor Amira; Bulat, Ku Halim Ku; Suah, Faiz Bukhari Mohd

    2018-06-01

    Molecular simulation techniques are important to study the understanding of chemical and physical properties of any material. Computational modeling is considered as time reducer in finding the best recipes for Molecularly-Imprinted Polymers (MIPs). In this study, Pyrogallol-imprinted polymers (PIP) and non-imprinted polymers (NIPs) were synthesized via precipitation polymerization using Pyrogallol (Py), methyl methacrylate (MMA), divinylbenzene (DVB) as template, functional monomer and cross-linker, respectively. The recipe was according to the results from computational techniques. The synthesized PIP and NIPs were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and UV-visible spectroscopy (UV-vis). Studies on adsorption isotherm showed that PIP and NIPs follow Scatchard isotherm models. Sorption kinetic study found that PIP and NIPs follow pseudo-second order which indicates the rate-limiting step is the surface adsorption. The imprinting factor of PIP was determined by selectivity study and showed the value of k >1, which proved that PIP was selective toward Pyrogallol compared to NIP.

  7. Polymeric media for tritium fixation

    International Nuclear Information System (INIS)

    Franz, J.A.; Burger, L.L.

    1975-01-01

    The synthesis and leach testing of several polymeric media for tritium fixation are presented. Tritiated bakelite, poly(acrylonitrile) and polystyrene successfully fixed tritium. Tritium leach rates at the tracer level appear to be negligible. Advantages and disadvantages of the processes are discussed, and further bench-scale investigations underway are reported. Rough cost estimates are presented for the different media and are compared with alternate approaches such as deep-well injection and long-term tank storage. Polymeric media costs are high compared to deep-well storage and are of the same order of magnitude per liter of water as for isotopic enrichment. With this limitation, polymeric media can be economically feasible only for highly concentrated tritiated wastes. It is recommended that the bakelite and polystyrene processes be examined on a larger scale to permit more accurate cost analysis and process design. (auth)

  8. Olefin metathesis and metathesis polymerization

    CERN Document Server

    Ivin, K J

    1997-01-01

    This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

  9. On-demand photoinitiated polymerization

    Science.gov (United States)

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  10. Pentafluorosulfanyl Substituents in Polymerization Catalysis.

    Science.gov (United States)

    Kenyon, Philip; Mecking, Stefan

    2017-10-04

    Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

  11. Radiation Induced Polymerization of Pyrrole

    International Nuclear Information System (INIS)

    Sarada Idris; Ratnam, C.T.; Ahmad Ashrif Abu Bakar

    2016-01-01

    We demonstrate the polymerization of pyrrole by gamma irradiation. The pyrrole films were exposed to gamma ray from cobalt 60 source at doses ranging from 0 to 150 kGy. The films were subjected to structural and morphological analyses by using FTIR, SEM and AFM techniques. Similar studies were also made on pristine pyrrole film which serve as control. Results revealed that pyrrole has been successfully polymerized through irradiation induced reactions. The SEM images depicted the formation of cauliflower shape upon gamma irradiation. The structural changes of pyrrole also evidenced by FTIR spectra. Surface topography and roughness of pyrrole before and after gamma irradiation found to show significant differences. (author)

  12. [Construction of cTnC-linker-TnI (P) Genes, Expression of Fusion Protein and Preparation of Lyophilized Protein].

    Science.gov (United States)

    Song, Xiaoli; Liu, Xiaoyun; Cai, Lei; Wu, Jianwei; Wang, Jihua

    2015-12-01

    In order to construct and express human cardiac troponin C-linker-troponin I(P) [ cTnC-linker-TnI(P)] fusion protein, detect its activity and prepare lyophilized protein, we searched the CDs of human cTnC and cTnI from GenBank, synthesized cTnC and cTnI(30-110aa) into cloning vector by a short DNA sequence coding for 15 neutral amino acid residues. pCold I-cTnC-linker-TnI(P) was constructed and transformed into E. coli BL21(DE3). Then, cTnC-linker-TnI(P) fusion protein was induced by isopropyl-β-D-thiogalactopyranoside (IPTG). Soluable expression of cTnC-linker-TnI(P) in prokaryotic system was successfully obtained. The fusion protein was purified by Ni²⁺ Sepharose 6 Fast Flow affinity chromatography with over 95% purity and prepared into lyophilized protein. The activity of purified cTnC-linker-TnI(P) and its lyophilized protein were detected by Wondfo Finecare™ cTnI Test. Lyophilized protein of cTnC-linker-TnI(P) was stable for 10 or more days at 37 °C and 4 or more months at 25 °C and 4 °C. The expression system established in this research is feasible and efficient. Lyophilized protein is stable enough to be provided as biological raw materials for further research.

  13. Dynamics of Linker Residues Modulate the Nucleic Acid Binding Properties of the HIV-1 Nucleocapsid Protein Zinc Fingers

    Science.gov (United States)

    Zargarian, Loussiné; Tisné, Carine; Barraud, Pierre; Xu, Xiaoqian; Morellet, Nelly; René, Brigitte; Mély, Yves; Fossé, Philippe; Mauffret, Olivier

    2014-01-01

    The HIV-1 nucleocapsid protein (NC) is a small basic protein containing two zinc fingers (ZF) separated by a short linker. It is involved in several steps of the replication cycle and acts as a nucleic acid chaperone protein in facilitating nucleic acid strand transfers occurring during reverse transcription. Recent analysis of three-dimensional structures of NC-nucleic acids complexes established a new property: the unpaired guanines targeted by NC are more often inserted in the C-terminal zinc finger (ZF2) than in the N-terminal zinc finger (ZF1). Although previous NMR dynamic studies were performed with NC, the dynamic behavior of the linker residues connecting the two ZF domains remains unclear. This prompted us to investigate the dynamic behavior of the linker residues. Here, we collected 15N NMR relaxation data and used for the first time data at several fields to probe the protein dynamics. The analysis at two fields allows us to detect a slow motion occurring between the two domains around a hinge located in the linker at the G35 position. However, the amplitude of motion appears limited in our conditions. In addition, we showed that the neighboring linker residues R29, A30, P31, R32, K33 displayed restricted motion and numerous contacts with residues of ZF1. Our results are fully consistent with a model in which the ZF1-linker contacts prevent the ZF1 domain to interact with unpaired guanines, whereas the ZF2 domain is more accessible and competent to interact with unpaired guanines. In contrast, ZF1 with its large hydrophobic plateau is able to destabilize the double-stranded regions adjacent to the guanines bound by ZF2. The linker residues and the internal dynamics of NC regulate therefore the different functions of the two zinc fingers that are required for an optimal chaperone activity. PMID:25029439

  14. A Novel MS-Cleavable Azo Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS)

    Science.gov (United States)

    Iacobucci, Claudio; Hage, Christoph; Schäfer, Mathias; Sinz, Andrea

    2017-10-01

    The chemical cross-linking/mass spectrometry (MS) approach is a growing research field in structural proteomics that allows gaining insights into protein conformations. It relies on creating distance constraints between cross-linked amino acid side chains that can further be used to derive protein structures. Currently, the most urgent task for designing novel cross-linking principles is an unambiguous and automated assignment of the created cross-linked products. Here, we introduce the homobifunctional, amine-reactive, and water soluble cross-linker azobisimidoester (ABI) as a prototype of a novel class of cross-linkers. The ABI-linker possesses an innovative modular scaffold combining the benefits of collisional activation lability with open shell chemistry. This MS-cleavable cross-linker can be efficiently operated via free radical initiated peptide sequencing (FRIPS) in positive ionization mode. Our proof-of-principle study challenges the gas phase behavior of the ABI-linker for the three amino acids, lysine, leucine, and isoleucine, as well as the model peptide thymopentin. The isomeric amino acids leucine and isoleucine could be discriminated by their characteristic side chain fragments. Collisional activation experiments were conducted via positive electrospray ionization (ESI) on two Orbitrap mass spectrometers. The ABI-mediated formation of odd electron product ions in MS/MS and MS3 experiments was evaluated and compared with a previously described azo-based cross-linker. All cross-linked products were amenable to automated analysis by the MeroX software, underlining the future potential of the ABI-linker for structural proteomics studies. [Figure not available: see fulltext.

  15. Preparation and in vivo evaluation of linkers for 211At labeling of humanized anti-Tac

    International Nuclear Information System (INIS)

    Yordanov, A.T.; Garmestani, K.; Zhang, M.; Zhang, Z.; Yao, Z.; Phillips, K.E.; Herring, B.; Horak, E.; Beitzel, M.P.; Schwarz, U.P.; Gansow, O.A.; Plascjak, P.S.; Eckelman, W.C.; Waldmann, T.A.; Brechbiel, M.W.

    2001-01-01

    The syntheses, radiolabeling, antibody conjugation, and in vivo evaluation of new linkers for 211 At labeling of humanized anti-Tac (Hu-anti-Tac), an antibody to the α-chain of the IL-2 receptor (IL-2Rα) shown to be a useful target for radioimmunotherapy are described. Synthesis of the organometallic linker precursors is accomplished by reaction of the corresponding bromo- or iodoaryl esters with bis(tributyltin) in the presence of a palladium catalyst. Subsequent conversion to the corresponding N-succinimidyl ester and labeling with 211 At of two new linkers, N-succinimidyl 4-[ 211 At]astato-3-methylbenzoate and N-succinimidyl N-(4-[ 211 At]astatophenethyl)succinamate (SAPS), together with the previously reported N-succinimidyl 4-[ 211 At]astatobenzoate and N-succinimidyl 3-[ 211 At]astato-4-methylbenzoate, are each conjugated to Hu-anti-Tac. The plasma survival times of these conjugates are compared to those of directly iodinated ( 125 I) Hu-anti-Tac. The N-succinimidyl N-(4-[ 211 At]astatophenethyl)succinamate compound (SAPS) emerged from this assay as the most viable candidate for 211 At-labeling of Hu-anti-Tac. SAPS, along with the directly analogous radio-iodinated reagent, N-succinimidyl N-(4-[ 125 I]astatophenethyl)succinamate (SIPS), are evaluated in a biodistribution study along with directly iodinated ( 125 I) Hu-anti-Tac. Blood clearance and biological accretion results indicate that SAPS is a viable candidate for further evaluation for radioimmunotherapy of cancer

  16. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

    In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

  17. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

  18. Preparation and study of tramadol imprinted micro-and nanoparticles by precipitation polymerization: microwave irradiation and conventional heating method.

    Science.gov (United States)

    Seifi, Mahmoud; Hassanpour Moghadam, Maryam; Hadizadeh, Farzin; Ali-Asgari, Safa; Aboli, Jafar; Mohajeri, Seyed Ahmad

    2014-08-25

    In the present work a series of tramadole imprinted micro- and nanoparticles were prepared and study their recognition properties. Methacrylic acid (MAA), as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker and different solvents (chloroform, toluene and acetonitrile (ACN)) were used for the preparation of molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs). Several factors such as template/monomer molar ratio, volume of polymerization solvent, total monomers/solvent volume ratio, polymerization condition (heating or microwave irradiation) were also investigated. Particle size of the polymers, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), rebinding, selectivity tests and release study were applied for evaluation of the polymers. The optimized polymers with smaller particle size and superior binding properties were obtained in acetonitrile under heating method. MIPA4 with a size of 42.6 nm and a binding factor (BF) of 6.79 was selected for selectivity and release tests. The polymerization was not successful in acetonitrile and toluene under microwave irradiation. The MIPA4 could selectively adsorb tramadol, compared to imipramine, naltrexone and gabapentin. The data showed that tramadol release from MIPA4 was significantly slower than that of its non-imprinted polymer. Therefore, MIP nanoparticles with high selectivity, binding capacity and ability to control tramadol release could be obtained in precipitation polymerization with optimized condition. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Novel polymeric materials from triglycerides

    Science.gov (United States)

    Triglycerides are good platforms for new polymeric products that can substitute for petroleum-based materials. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a number of reactions in efforts to produce a wide range of value-added products. In this ...

  20. Novel solid state polymeric batteries

    Energy Technology Data Exchange (ETDEWEB)

    Patrick, A.; Glasse, M.; Latham, R.; Linford, R.

    1986-01-01

    AC conductivity measurements have been performed on a number of polymeric electrolytes containing Mg, Ca, Sr and Zn perchlorates and Mg and Ca thiocyanates. The electrolytes were characterized using DSC. Results are reported of preliminary tests of cells incorporating anodes of the above metals. 11 refs.

  1. Reactive surfactants in heterophase polymerization

    NARCIS (Netherlands)

    Guyot, A.; Tauer, K.; Asua, J.M.; Es, van J.J.G.S.; Gauthier, C.; Hellgren, A.C.; Sherrington, D.C.; Montoya-Goni, A.; Sjöberg, M.; Sindt, O.; Vidal, F.F.M.; Unzue, M.; Schoonbrood, H.A.S.; Schipper, E.T.W.M.; Lacroix-Desmazes, P.

    1999-01-01

    This paper summarizes the work carried out during 3 years in a Network of the program "Human Capital and Mobility" of the European Union CHRX 93-0159 entitled "Reactive surfactants in heterophase polymerization for high performance polymers". A series of about 25 original papers will be published in

  2. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

    Bennet, D.B.; Li, X.; Adams, N.W.; Kim, S.W.; Hoes, C.J.T.; Hoes, C.J.T.; Feijen, Jan

    1991-01-01

    The development of a biodegradable polymeric drug delivery system for the narcotic antagonist naltrexone may improve patient compliance in the treatment of opiate addiction. Random copolymers consisting of the ¿-amino acids N5-(3-hydroxypropyl--glutamine and -leucine were synthesized with equimolar

  3. Accurate distance determination of nucleic acids via Förster resonance energy transfer: implications of dye linker length and rigidity.

    Science.gov (United States)

    Sindbert, Simon; Kalinin, Stanislav; Nguyen, Hien; Kienzler, Andrea; Clima, Lilia; Bannwarth, Willi; Appel, Bettina; Müller, Sabine; Seidel, Claus A M

    2011-03-02

    In Förster resonance energy transfer (FRET) experiments, the donor (D) and acceptor (A) fluorophores are usually attached to the macromolecule of interest via long flexible linkers of up to 15 Å in length. This causes significant uncertainties in quantitative distance measurements and prevents experiments with short distances between the attachment points of the dyes due to possible dye-dye interactions. We present two approaches to overcome the above problems as demonstrated by FRET measurements for a series of dsDNA and dsRNA internally labeled with Alexa488 and Cy5 as D and A dye, respectively. First, we characterize the influence of linker length and flexibility on FRET for different dye linker types (long, intermediate, short) by analyzing fluorescence lifetime and anisotropy decays. For long linkers, we describe a straightforward procedure that allows for very high accuracy of FRET-based structure determination through proper consideration of the position distribution of the dye and of linker dynamics. The position distribution can be quickly calculated with geometric accessible volume (AV) simulations, provided that the local structure of RNA or DNA in the proximity of the dye is known and that the dye diffuses freely in the sterically allowed space. The AV approach provides results similar to molecular dynamics simulations (MD) and is fully consistent with experimental FRET data. In a benchmark study for ds A-RNA, an rmsd value of 1.3 Å is achieved. Considering the case of undefined dye environments or very short DA distances, we introduce short linkers with a propargyl or alkenyl unit for internal labeling of nucleic acids to minimize position uncertainties. Studies by ensemble time correlated single photon counting and single-molecule detection show that the nature of the linker strongly affects the radius of the dye's accessible volume (6-16 Å). For short propargyl linkers, heterogeneous dye environments are observed on the millisecond time scale. A

  4. Preparations of spherical polymeric particles from Tanzanian ...

    African Journals Online (AJOL)

    Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

  5. Bioinformatic Analysis Reveals Conservation of Intrinsic Disorder in the Linker Sequences of Prokaryotic Dual-family Immunophilin Chaperones.

    Science.gov (United States)

    Barik, Sailen

    2018-01-01

    The two classical immunophilin families, found essentially in all living cells, are: cyclophilin (CYN) and FK506-binding protein (FKBP). We previously reported a novel class of immunophilins that are natural chimera of these two, which we named dual-family immunophilin (DFI). The DFIs were found in either of two conformations: CYN-linker-FKBP (CFBP) or FKBP-3TPR-CYN (FCBP). While the 3TPR domain can serve as a flexible linker between the FKBP and CYN modules in the FCBP-type DFI, the linker sequences in the CFBP-type DFIs are relatively short, diverse in sequence, and contain no discernible motif or signature. Here, I present several lines of computational evidence that, regardless of their primary structure, these CFBP linkers are intrinsically disordered. This report provides the first molecular foundation for the model that the CFBP linker acts as an unstructured, flexible loop, allowing the two flanking chaperone modules function independently while linked in cis , likely to assist in the folding of multisubunit client complexes.

  6. Glycine Polymerization on Oxide Minerals

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  7. Glycine Polymerization on Oxide Minerals.

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  8. Neutral hydrophilic coatings for capillary electrophoresis prepared by controlled radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Navarro, Fabián H.; Gómez, Jorge E.; Espinal, José H.; Sandoval, Junior E., E-mail: junior.sandoval@correounivalle.edu.co

    2016-12-15

    In the present study, porous silica particles as well as impervious fused-silica wafers and capillary tubes were modified with hydrophilic polymers (hydroxylated polyacrylamides and polyacrylates), using a surface-confined grafting procedure based on atom transfer radical polymerization (ATRP) which was also surface-initiated from α-bromoisobutyryl groups. Initiator immobilization was achieved by hydrosilylation of allyl alcohol on hydride silica followed by esterification of the resulting propanol-bonded surface with α-bromoisobutyryl bromide. Elemental analysis, IR and NMR spectroscopies on silica micro-particles, atomic force microscopy, ellipsometry and profilometry on fused-silica wafers, as well as CE on fused-silica tubes were used to characterize the chemically modified silica substrate at different stages. We studied the effect of monomer concentration as well as cross-linker on the ability of the polymer film to reduce electroosmosis and to prevent protein adsorption (i. e., its non-fouling capabilities) and found that the former was rather insensitive to both parameters. Surface deactivation towards adsorption was somewhat more susceptible to monomer concentration and appeared also to be favored by a low concentration of the cross-linker. The results show that hydrophilic polyacrylamide and polyacrylate coatings of controlled thickness can be prepared by ATRP under very mild polymerization conditions (aqueous solvent, room temperature and short reaction times) and that the coated capillary tubes exhibit high efficiencies for protein separations (0.3–0.6 million theoretical plates per meter) as well as long-term hydrolytic stability under the inherently harsh conditions of capillary isoelectric focusing. Additionally, there was no adsorption of lysozyme on the coated surface as indicated by a complete recovery of the basic enzyme. Furthermore, since polymerization is confined to the inner capillary surface, simple precautions (e.g., solution

  9. Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by Mixed-Linker Synthesis

    KAUST Repository

    Thompson, Joshua A.

    2012-05-22

    Zeolitic imidazolate frameworks (ZIFs) are a subclass of nanoporous metal-organic frameworks (MOFs) that exhibit zeolite-like structural topologies and have interesting molecular recognition properties, such as molecular sieving and gate-opening effects associated with their pore apertures. The synthesis and characterization of hybrid ZIFs with mixed linkers in the framework are described in this work, producing materials with properties distinctly different from the parent frameworks (ZIF-8, ZIF-90, and ZIF-7). NMR spectroscopy is used to assess the relative amounts of the different linkers included in the frameworks, whereas nitrogen physisorption shows the evolution of the effective pore size distribution in materials resulting from the framework hybridization. X-ray diffraction shows these hybrid materials to be crystalline. In the case of ZIF-8-90 hybrids, the cubic space group of the parent frameworks is continuously maintained, whereas in the case of the ZIF-7-8 hybrids there is a transition from a cubic to a rhombohedral space group. Nitrogen physisorption data reveal that the hybrid materials exhibit substantial changes in gate-opening phenomena, either occurring at continuously tunable partial pressures of nitrogen (ZIF-8-90 hybrids) or loss of gate-opening effects to yield more rigid frameworks (ZIF-7-8 hybrids). With this synthetic approach, significant alterations in MOF properties may be realized to suit a desired separation or catalytic process. © 2012 American Chemical Society.

  10. Effective generation of transgenic pigs and mice by linker based sperm-mediated gene transfer.

    Directory of Open Access Journals (Sweden)

    Shih Ping Yao

    2002-04-01

    Full Text Available Abstract Background Transgenic animals have become valuable tools for both research and applied purposes. The current method of gene transfer, microinjection, which is widely used in transgenic mouse production, has only had limited success in producing transgenic animals of larger or higher species. Here, we report a linker based sperm-mediated gene transfer method (LB-SMGT that greatly improves the production efficiency of large transgenic animals. Results The linker protein, a monoclonal antibody (mAb C, is reactive to a surface antigen on sperm of all tested species including pig, mouse, chicken, cow, goat, sheep, and human. mAb C is a basic protein that binds to DNA through ionic interaction allowing exogenous DNA to be linked specifically to sperm. After fertilization of the egg, the DNA is shown to be successfully integrated into the genome of viable pig and mouse offspring with germ-line transfer to the F1 generation at a highly efficient rate: 37.5% of pigs and 33% of mice. The integration is demonstrated again by FISH analysis and F2 transmission in pigs. Furthermore, expression of the transgene is demonstrated in 61% (35/57 of transgenic pigs (F0 generation. Conclusions Our data suggests that LB-SMGT could be used to generate transgenic animals efficiently in many different species.

  11. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    International Nuclear Information System (INIS)

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  12. G-CSF receptor-binding cyclic peptides designed with artificial amino-acid linkers

    International Nuclear Information System (INIS)

    Shibata, Kenji; Maruyama-Takahashi, Kumiko; Yamasaki, Motoo; Hirayama, Noriaki

    2006-01-01

    Designing small molecules that mimic the receptor-binding local surface structure of large proteins such as cytokines or growth factors is fascinating and challenging. In this study, we designed cyclic peptides that reproduce the receptor-binding loop structures of G-CSF. We found it is important to select a suitable linker to join two or more discontinuous sequences and both termini of the peptide corresponding to the receptor-binding loop. Structural simulations based on the crystallographic structure of KW-2228, a stable and potent analog of human G-CSF, led us to choose 4-aminobenzoic acid (Abz) as a part of the linker. A combination of 4-Abz with β-alanine or glycine, and disulfide bridges between cysteins or homocysteins, gave a structure suitable for receptor binding. In this structure, the side-chains of several amino acids important for the interactions with the receptor are protruding from one side of the peptide ring. This artificial peptide showed G-CSF antagonistic activity in a cell proliferation assay

  13. A Switchable Linker-Based Immunoassay for Ultrasensitive Visible Detection of Salmonella in Tomatoes.

    Science.gov (United States)

    Hahn, Jungwoo; Kim, Eunghee; You, Young Sang; Gunasekaran, Sundaram; Lim, Seokwon; Choi, Young Jin

    2017-10-01

    On-site detection for sensitive identification of foodborne pathogens on fresh produce with minimal use of specialized instrumentation is crucial to the food industry. A switchable linker (SL)-based immunoassay was designed for ultrasensitive on-site detection of Salmonella in tomato samples. The assay is based on large-scale aggregation of gold nanoparticles (GNPs), induced by a quantitative relationship among the biotinylated Salmonella polyclonal antibody (b-Ab) used as the SL, the functionalized GNPs, and Salmonella. Important factors such as the concentration of SLs, time required for large-scale aggregation, and selectivity of b-Ab were optimized to minimize the detection time (within 45 min with gentle agitation) and achieve the lowest limit of detection (LOD; 10 CFU/g in tomato samples) possible. This SL-based immunoassay with its relatively low LOD and short detection time may meet the need for rapid, simple, on-site analysis of pathogens in fresh produce. The novel switchable linker-based immunoassay is a rapid, specific, and sensitive method that has potential applications for routine diagnostics of Salmonella in tomato products. These advantages make it a practical approach for general use in the processing industry to detect Salmonella rapidly and to implement appropriate regulatory procedures. Furthermore, it could be applied to other fresh products including cantaloupe, strawberry, and cucumbers. © 2017 Institute of Food Technologists®.

  14. The First MS-Cleavable, Photo-Thiol-Reactive Cross-Linker for Protein Structural Studies

    Science.gov (United States)

    Iacobucci, Claudio; Piotrowski, Christine; Rehkamp, Anne; Ihling, Christian H.; Sinz, Andrea

    2018-04-01

    Cleavable cross-linkers are gaining increasing importance for chemical cross-linking/mass spectrometry (MS) as they permit a reliable and automated data analysis in structural studies of proteins and protein assemblies. Here, we introduce 1,3-diallylurea (DAU) as the first CID-MS/MS-cleavable, photo-thiol-reactive cross-linker. DAU is a commercially available, inexpensive reagent that efficiently undergoes an anti-Markovnikov hydrothiolation with cysteine residues in the presence of a radical initiator upon UV-A irradiation. Radical cysteine cross-linking proceeds via an orthogonal "click reaction" and yields stable alkyl sulfide products. DAU reacts at physiological pH and cross-linking reactions with peptides, and proteins can be performed at temperatures as low as 4 °C. The central urea bond is efficiently cleaved upon collisional activation during tandem MS experiments generating characteristic product ions. This improves the reliability of automated cross-link identification. Different radical initiators have been screened for the cross-linking reaction of DAU using the thiol-containing compounds cysteine and glutathione. Our concept has also been exemplified for the biologically relevant proteins bMunc13-2 and retinal guanylyl cyclase-activating protein-2. [Figure not available: see fulltext.

  15. Structural basis for activation of ZAP-70 by phosphorylation of the SH2-kinase linker.

    Science.gov (United States)

    Yan, Qingrong; Barros, Tiago; Visperas, Patrick R; Deindl, Sebastian; Kadlecek, Theresa A; Weiss, Arthur; Kuriyan, John

    2013-06-01

    Serial activation of the tyrosine kinases Lck and ZAP-70 initiates signaling downstream of the T cell receptor. We previously reported the structure of an autoinhibited ZAP-70 variant in which two regulatory tyrosine residues (315 and 319) in the SH2-kinase linker were replaced by phenylalanine. We now present a crystal structure of ZAP-70 in which Tyr 315 and Tyr 319 are not mutated, leading to the recognition of a five-residue sequence register error in the SH2-kinase linker of the original crystallographic model. The revised model identifies distinct roles for these two tyrosines. As seen in a recently reported structure of the related tyrosine kinase Syk, Tyr 315 of ZAP-70 is part of a hydrophobic interface between the regulatory apparatus and the kinase domain, and the integrity of this interface would be lost upon engagement of doubly phosphorylated peptides by the SH2 domains. Tyr 319 is not necessarily dislodged by SH2 engagement, which activates ZAP-70 only ∼5-fold in vitro. In contrast, phosphorylation by Lck activates ZAP-70 ∼100-fold. This difference is due to the ability of Tyr 319 to suppress ZAP-70 activity even when the SH2 domains are dislodged from the kinase domain, providing stringent control of ZAP-70 activity downstream of Lck.

  16. Iminodiacetic acid as bifunctional linker for dimerization of cyclic RGD peptides

    International Nuclear Information System (INIS)

    Xu, Dong; Zhao, Zuo-Quan; Chen, Shu-Ting; Yang, Yong; Fang, Wei; Liu, Shuang

    2017-01-01

    Introduction: In this study, I2P-RGD 2 was used as the example to illustrate a novel approach for dimerization of cyclic RGD peptides. The main objective of this study was to explore the impact of bifunctional linkers (glutamic acid vs. iminodiacetic acid) on tumor-targeting capability and excretion kinetics of the 99m Tc-labeled dimeric cyclic RGD peptides. Methods: HYNIC-I2P-RGD 2 was prepared by reacting I2P-RGD 2 with HYNIC-OSu in the presence of diisopropylethylamine, and was evaluated for its α v β 3 binding affinity against 125 I-echistatin bound to U87MG glioma cells. 99m Tc-I2P-RGD 2 was prepared with high specific activity (~185 GBq/μmol). The athymic nude mice bearing U87MG glioma xenografts were used to evaluate its biodistribution properties and image quality in comparison with those of 99m Tc-3P-RGD 2 . Results: The IC 50 value for HYNIC-I2P-RGD 2 was determined to be 39 ± 6 nM, which was very close to that (IC 50 = 33 ± 5 nM) of HYNIC-3P-RGD 2 . Replacing glutamic acid with iminodiacetic acid had little impact on α v β 3 binding affinity of cyclic RGD peptides. 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 shared similar tumor uptake values over the 2 h period, and its α v β 3 -specificity was demonstrated by a blocking experiment. The uptake of 99m Tc-I2P-RGD 2 was significantly lower than 99m Tc-3P-RGD 2 in the liver and kidneys. The U87MG glioma tumors were visualized by SPECT with excellent contrast using both 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 . Conclusion: Iminodiacetic acid is an excellent bifunctional linker for dimerization of cyclic RGD peptides. Bifunctional linkers have significant impact on the excretion kinetics of 99m Tc radiotracers. Because of its lower liver uptake and better tumor/liver ratios, 99m Tc-I2P-RGD 2 may have advantages over 99m Tc-3P-RGD 2 for diagnosis of tumors in chest region. -- Graphical abstract: This report presents novel approach for dimerization of cyclic RGD peptides using iminodiacetic acid as a

  17. Synthesis, DNA Binding, and Anticancer Properties of Bis-Naphthalimide Derivatives with Lysine-Modified Polyamine Linkers

    Directory of Open Access Journals (Sweden)

    Yu Huang

    2018-01-01

    Full Text Available A series of bis-naphthalimide derivatives with different diamine linkers were designed and synthesized. All of the synthesized bis-naphthalimide derivatives were characterized by NMR and HRMS spectra. The binding ability between the compounds and CT DNA was evaluated by using UV–Vis titration experiments. The bis-naphthalimide compound with an ethylenediamine linker showed the largest binding constant with CT DNA. Hence, it was used as the model compound to study the DNA binding selectivity by UV–Vis titration aiming at different DNA duplexes. As a result, this compound showed binding preference to AT-rich duplexes. The DNA binding modes of the compounds were also measured by viscosity titration. The cytotoxicity of the compounds was evaluated by MTT assay. Compounds with 1,6-diaminohexane or 1,4-phenylenedimethanamine linkers showed higher cytotoxicity compared with other bis-naphthalimide derivatives.

  18. Mutations in Biosynthetic Enzymes for the Protein Linker Region of Chondroitin/Dermatan/Heparan Sulfate Cause Skeletal and Skin Dysplasias

    Directory of Open Access Journals (Sweden)

    Shuji Mizumoto

    2015-01-01

    Full Text Available Glycosaminoglycans, including chondroitin, dermatan, and heparan sulfate, have various roles in a wide range of biological events such as cell signaling, cell proliferation, tissue morphogenesis, and interactions with various growth factors. Their polysaccharides covalently attach to the serine residues on specific core proteins through the common linker region tetrasaccharide, -xylose-galactose-galactose-glucuronic acid, which is produced through the stepwise addition of respective monosaccharides by four distinct glycosyltransferases. Mutations in the human genes encoding the glycosyltransferases responsible for the biosynthesis of the linker region tetrasaccharide cause a number of genetic disorders, called glycosaminoglycan linkeropathies, including Desbuquois dysplasia type 2, spondyloepimetaphyseal dysplasia, Ehlers-Danlos syndrome, and Larsen syndrome. This review focused on recent studies on genetic diseases caused by defects in the biosynthesis of the common linker region tetrasaccharide.

  19. Linker length dependent binding of a focal adhesion kinase derived peptide to the Src SH3-SH2 domains.

    Science.gov (United States)

    Lindfors, Hanna E; Venkata, Bharat Somireddy; Drijfhout, Jan W; Ubbink, Marcellus

    2011-02-18

    The interaction between a peptide encompassing the SH3 and SH2 binding motifs of focal adhesion kinase (FAK) and the Src SH3-SH2 domains has been investigated with NMR spectroscopy and calorimetry. The binding to both motifs is anti-cooperative. Reduction of the long linker connecting the motifs does not lead to cooperativity. Short linkers that do not allow simultaneous intramolecular binding of the peptide to both motifs cause peptide-mediated dimerisation, even with a linker of only three amino acids. The role of the SH3 binding motif is discussed in view of the independent nature of the SH interactions. Copyright © 2011 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  20. The S4-S5 linker acts as a signal integrator for HERG K+ channel activation and deactivation gating.

    Directory of Open Access Journals (Sweden)

    Chai Ann Ng

    Full Text Available Human ether-à-go-go-related gene (hERG K(+ channels have unusual gating kinetics. Characterised by slow activation/deactivation but rapid inactivation/recovery from inactivation, the unique gating kinetics underlie the central role hERG channels play in cardiac repolarisation. The slow activation and deactivation kinetics are regulated in part by the S4-S5 linker, which couples movement of the voltage sensor domain to opening of the activation gate at the distal end of the inner helix of the pore domain. It has also been suggested that cytosolic domains may interact with the S4-S5 linker to regulate activation and deactivation kinetics. Here, we show that the solution structure of a peptide corresponding to the S4-S5 linker of hERG contains an amphipathic helix. The effects of mutations at the majority of residues in the S4-S5 linker of hERG were consistent with the previously identified role in coupling voltage sensor movement to the activation gate. However, mutations to Ser543, Tyr545, Gly546 and Ala548 had more complex phenotypes indicating that these residues are involved in additional interactions. We propose a model in which the S4-S5 linker, in addition to coupling VSD movement to the activation gate, also contributes to interactions that stabilise the closed state and a separate set of interactions that stabilise the open state. The S4-S5 linker therefore acts as a signal integrator and plays a crucial role in the slow deactivation kinetics of the channel.

  1. Preparation of value-added metal-organic frameworks (MOFs) using waste PET bottles as source of acid linker

    CSIR Research Space (South Africa)

    Dyosiba, Xoliswa

    2016-12-01

    Full Text Available of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker Xoliswa Dyosiba, Jianwei Ren, Nicholas M. Musyoka, Henrietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango PII: S2214-9937(16)30053-7 DOI: doi:10.1016/j..., Hen- rietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango, Preparation of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker, Sustainable Materials and Technologies (2016), doi:10.1016/j.susmat.2016...

  2. A Linker for the Solid-Phase Synthesis of Hydroxamic Acids and Identification of HDAC6 Inhibitors

    DEFF Research Database (Denmark)

    Bang, Claus Gunnar; Jensen, Jakob Feldthusen; Cohrt, Anders Emil O'Hanlon

    2017-01-01

    We herein present broadly useful, readily available and nonintegral hydroxylamine linkers for the routine solid-phase synthesis of hydroxamic acids. The developed protocols enable the efficient synthesis and release of a wide range of hydroxamic acids from various resins, relying on high control...... and flexibility with respect to reagents and synthetic processes. A trityl-based hydroxylamine linker was used to synthesize a library of peptide hydroxamic acids. The inhibitory effects of the compounds were examined for seven HDAC enzyme subtypes using a chemiluminescence-based assay....

  3. Novel cross-linkers for PDMS networks for controlled and well distributed grafting of functionalities by click chemistry

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Dimitrov, Ivaylo; Daugaard, Anders Egede

    2013-01-01

    by 35%. The contact angle of PDMS films was increased from 108° to 116° by the introduction of a small poly(pentafluorostyrene) chain. Finally, 17α-ethynyl-1,3,5(10)-estratriene-3,17β-diol and 1-ethynyl-3,5- bis(trifluoromethyl)benzene were incorporated as examples of other functional groups. © 2013......-linkers have been utilized to prepare novel polydimethylsiloxane (PDMS) networks. All functional cross-linkers were successfully incorporated into the networks and were demonstrated to be well distributed within the PDMS films. This was substantiated by fluorescence microscopy of a film prepared with the 4...

  4. Click polymerization for the synthesis of reduction-responsive polymeric prodrug

    Science.gov (United States)

    Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

    2018-05-01

    Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

  5. SCATTERING FROM RAMIFIED POLYMERIC SYSTEMS

    Directory of Open Access Journals (Sweden)

    M.Benhamou

    2004-01-01

    Full Text Available Here, of great interest to us is a quantitative study of the scattering properties from ramified polymeric systems of arbitrary topology. We consider three types of systems, namely ramified polymers in solution, ramified polymer blends, or ternary mixtures made of two ramified polymers of different chemical nature immersed in a good solvent. To achieve the goal of the study, use is made of the Random Phase Approximation. First we determine the exact expression of the form factor of an ideal ramified polymer of any topology, from which we extract the exact expression of its gyration radius. Using the classical Zimm's formulae and the exact form factor, we determine all scattering properties of these three types of ramified polymeric systems. The main conclusion is that ramification of the chains induces drastic changes of the scattering properties.

  6. Polymeric nanoparticles for optical sensing.

    Science.gov (United States)

    Canfarotta, Francesco; Whitcombe, Michael J; Piletsky, Sergey A

    2013-12-01

    Nanotechnology is a powerful tool for use in diagnostic applications. For these purposes a variety of functional nanoparticles containing fluorescent labels, gold and quantum dots at their cores have been produced, with the aim of enhanced sensitivity and multiplexing capabilities. This work will review progress in the application of polymeric nanoparticles in optical diagnostics, both for in vitro and in vivo detection, together with a discussion of their biodistribution and biocompatibility. © 2013.

  7. Polymeric Coatings for Combating Biocorrosion

    Science.gov (United States)

    Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

    2018-03-01

    Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

  8. Non-equilibrium supramolecular polymerization.

    Science.gov (United States)

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  9. Supramolecular polymeric materials via cyclodextrin-guest interactions.

    Science.gov (United States)

    Harada, Akira; Takashima, Yoshinori; Nakahata, Masaki

    2014-07-15

    CONSPECTUS: Cyclodextrins (CDs) have many attractive functions, including molecular recognition, hydrolysis, catalysis, and polymerization. One of the most important uses of CDs is for the molecular recognition of hydrophobic organic guest molecules in aqueous solutions. CDs are desirable host molecules because they are environmentally benign and offer diverse functions. This Account demonstrates some of the great advances in the development of supramolecular materials through host-guest interactions within the last 10 years. In 1990, we developed topological supramolecular complexes with CDs, polyrotaxane, and CD tubes, and these preparation methods take advantage of self-organization between the CDs and the polymers. The combination of polyrotaxane with αCD forms a hydrogel through the interaction of αCDs with the OH groups on poly(ethylene glycol). We categorized these polyrotaxane chemistries within main chain type complexes. At the same time, we studied the interactions of side chain type supramolecular complexes with CDs. In these systems the guest molecules modified the polymers and selectively formed inclusion complexes with CDs. The systems that used low molecular weight compounds did not show such selectivity with CDs. The multivalency available within the complex cooperatively enhances the selective binding of CD with guest molecules via the polymer side chains, a phenomenon that is analogous to binding patterns observed in antigen-antibody complexes. To incorporate the molecular recognition properties of CDs within the polymer side chains, we first prepared stimuli-responsive sol-gel switching materials through host-guest interactions. We chose azobenzene derivatives for their response to light and ferrocene derivatives for their response to redox conditions. The supramolecular materials were both redox-responsive and self-healing, and these properties resulted from host-guest interactions. These sol-gels with built in switches gave us insight for

  10. Preferential 5-Methylcytosine Oxidation in the Linker Region of Reconstituted Positioned Nucleosomes by Tet1 Protein.

    Science.gov (United States)

    Kizaki, Seiichiro; Zou, Tingting; Li, Yue; Han, Yong-Woon; Suzuki, Yuki; Harada, Yoshie; Sugiyama, Hiroshi

    2016-11-07

    Tet (ten-eleven translocation) family proteins oxidize 5-methylcytosine (mC) to 5-hydroxymethylcytosine (hmC), 5-formylcytosine (fC), and 5-carboxycytosine (caC), and are suggested to be involved in the active DNA demethylation pathway. In this study, we reconstituted positioned mononucleosomes using CpG-methylated 382 bp DNA containing the Widom 601 sequence and recombinant histone octamer, and subjected the nucleosome to treatment with Tet1 protein. The sites of oxidized methylcytosine were identified by bisulfite sequencing. We found that, for the oxidation reaction, Tet1 protein prefers mCs located in the linker region of the nucleosome compared with those located in the core region. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Efficient loading of primary alcohols onto a solid phase using a trityl bromide linker

    DEFF Research Database (Denmark)

    Crestey, François; Ottesen, Lars Korsgaard; Jaroszewski, Jerzy Witold

    2008-01-01

    The Letter describes an improved, rapid and mild strategy for the loading of primary alcohols onto a polystyrene trityl resin via a highly reactive trityl bromide linker. This protocol facilitates an efficient resin loading even of acid-sensitive or heat-labile alcohols, which otherwise require...... expensive or non-commercial resin types. Secondary alcohols were only attached in moderate to low yields, while attempts to load a tertiary alcohol expectedly failed. Importantly, selective attachment of diols via a primary alcohol group in the presence of more hindered alcohol groups proved possible....... The effects of activation time and reagent excess as well as alcohol structure were investigated. This improved method provides a convenient access to O-linked resin-bound N-Fmoc-protected amino alcohols that may be employed in SPS of peptides with C-terminal alcohol functionalities. In the case...

  12. Temperature-triggered release of a liquid cross-linker micro-encapsulated in a glassy polymer for low temperature curing

    NARCIS (Netherlands)

    Senatore, D.; Cate, ten A.T.; Laven, J.; Benthem, van R.A.T.M.; With, de G.

    2013-01-01

    In order to prevent a liquid epoxy cross-linker from premature, Arrhenius-law predicted, reaction with an acid-functional polyester resin, the liquid cross-linker has been physically separated from the resin by encapsulation while release is only possible by a temperature-controlled trigger. The

  13. Synthesis of Selective Butyrylcholinesterase Inhibitors Coupled between α-Lipoic Acid and Polyphenols by Using 2-(Piperazin-1-yl)ethanol Linker

    Energy Technology Data Exchange (ETDEWEB)

    Yeun, Go Heun; Lee, Seung Hwan; LIm, Yong Bae; Lee, Hye Sook; Lee, Bong Ho; Park, Jeong Ho [Hanbat National Univ., Daejeon (Korea, Republic of); Won, Mooho [Kangwon National Univ., Chuncheon (Korea, Republic of)

    2013-04-15

    In the previous paper (Bull. Korean Chem. Soc., 2011, 32, 2997), the hybrid molecules between α-lipoic acid (ALA) and polyphenols (PPs) connected with neutral 2-(2-aminoethoxy)ethanol linker (linker-1) showed new biological activity such as butyrylcholinesterase (BuChE) inhibition. In order to increase the binding affinity of the hybrid compounds to cholinesterase (ChE), the neutral 2-(2-aminoethoxy)ethanol (linker 1) was switched to the cationic 2-(piperazin-1-yl)ethanol linker (linker 2). The IC{sub 50} values of the linker-2 hybrid molecules for BuChE inhibition were lower than those of linker-1 hybrid molecules (except 9-2) and they also had the same great selectivity for BuChE over AChE (> 800 fold) as linker-1 hybrid molecules. ALA-acetyl caffeic acid (10-2, ALA-AcCA) was shown as an effective inhibitor of BuChE (IC{sub 50} = 0.44 ± 0.24 μM). A kinetic study using 7-2 showed that it is the same mixed type inhibition as 7-1. Its inhibition constant (Ki) to BuChE is 4.3 ± 0.09 μM.

  14. Synthesis of Selective Butyrylcholinesterase Inhibitors Coupled between α-Lipoic Acid and Polyphenols by Using 2-(Piperazin-1-yl)ethanol Linker

    International Nuclear Information System (INIS)

    Yeun, Go Heun; Lee, Seung Hwan; LIm, Yong Bae; Lee, Hye Sook; Lee, Bong Ho; Park, Jeong Ho; Won, Mooho

    2013-01-01

    In the previous paper (Bull. Korean Chem. Soc., 2011, 32, 2997), the hybrid molecules between α-lipoic acid (ALA) and polyphenols (PPs) connected with neutral 2-(2-aminoethoxy)ethanol linker (linker-1) showed new biological activity such as butyrylcholinesterase (BuChE) inhibition. In order to increase the binding affinity of the hybrid compounds to cholinesterase (ChE), the neutral 2-(2-aminoethoxy)ethanol (linker 1) was switched to the cationic 2-(piperazin-1-yl)ethanol linker (linker 2). The IC 50 values of the linker-2 hybrid molecules for BuChE inhibition were lower than those of linker-1 hybrid molecules (except 9-2) and they also had the same great selectivity for BuChE over AChE (> 800 fold) as linker-1 hybrid molecules. ALA-acetyl caffeic acid (10-2, ALA-AcCA) was shown as an effective inhibitor of BuChE (IC 50 = 0.44 ± 0.24 μM). A kinetic study using 7-2 showed that it is the same mixed type inhibition as 7-1. Its inhibition constant (Ki) to BuChE is 4.3 ± 0.09 μM

  15. Modulations of DNA Contacts by Linker Histones and Post-translational Modifications Determine the Mobility and Modifiability of Nucleosomal H3 Tails.

    Science.gov (United States)

    Stützer, Alexandra; Liokatis, Stamatios; Kiesel, Anja; Schwarzer, Dirk; Sprangers, Remco; Söding, Johannes; Selenko, Philipp; Fischle, Wolfgang

    2016-01-21

    Post-translational histone modifications and linker histone incorporation regulate chromatin structure and genome activity. How these systems interface on a molecular level is unclear. Using biochemistry and NMR spectroscopy, we deduced mechanistic insights into the modification behavior of N-terminal histone H3 tails in different nucleosomal contexts. We find that linker histones generally inhibit modifications of different H3 sites and reduce H3 tail dynamics in nucleosomes. These effects are caused by modulations of electrostatic interactions of H3 tails with linker DNA and largely depend on the C-terminal domains of linker histones. In agreement, linker histone occupancy and H3 tail modifications segregate on a genome-wide level. Charge-modulating modifications such as phosphorylation and acetylation weaken transient H3 tail-linker DNA interactions, increase H3 tail dynamics, and, concomitantly, enhance general modifiability. We propose that alterations of H3 tail-linker DNA interactions by linker histones and charge-modulating modifications execute basal control mechanisms of chromatin function. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Eviction of linker histone H1 by NAP-family histone chaperones enhances activated transcription.

    Science.gov (United States)

    Zhang, Qian; Giebler, Holli A; Isaacson, Marisa K; Nyborg, Jennifer K

    2015-01-01

    In the Metazoan nucleus, core histones assemble the genomic DNA to form nucleosome arrays, which are further compacted into dense chromatin structures by the linker histone H1. The extraordinary density of chromatin creates an obstacle for accessing the genetic information. Regulation of chromatin dynamics is therefore critical to cellular homeostasis, and histone chaperones serve as prominent players in these processes. In the current study, we examined the role of specific histone chaperones in negotiating the inherently repressive chromatin structure during transcriptional activation. Using a model promoter, we demonstrate that the human nucleosome assembly protein family members hNap1 and SET/Taf1β stimulate transcription in vitro during pre-initiation complex formation, prior to elongation. This stimulatory effect is dependent upon the presence of activators, p300, and Acetyl-CoA. We show that transcription from our chromatin template is strongly repressed by H1, and that both histone chaperones enhance RNA synthesis by overcoming H1-induced repression. Importantly, both hNap1 and SET/Taf1β directly bind H1, and function to enhance transcription by evicting the linker histone from chromatin reconstituted with H1. In vivo studies demonstrate that SET/Taf1β, but not hNap1, strongly stimulates activated transcription from the chromosomally-integrated model promoter, consistent with the observation that SET/Taf1β is nuclear, whereas hNap1 is primarily cytoplasmic. Together, these observations indicate that SET/Taf1β may serve as a critical regulator of H1 dynamics and gene activation in vivo. These studies uncover a novel function for SET that mechanistically couples transcriptional derepression with H1 dynamics. Furthermore, they underscore the significance of chaperone-dependent H1 displacement as an essential early step in the transition of a promoter from a dense chromatin state into one that is permissive to transcription factor binding and robust

  17. Cytoskeletal Linker Protein Dystonin Is Not Critical to Terminal Oligodendrocyte Differentiation or CNS Myelination.

    Directory of Open Access Journals (Sweden)

    Samantha F Kornfeld

    Full Text Available Oligodendrocyte differentiation and central nervous system myelination require massive reorganization of the oligodendrocyte cytoskeleton. Loss of specific actin- and tubulin-organizing factors can lead to impaired morphological and/or molecular differentiation of oligodendrocytes, resulting in a subsequent loss of myelination. Dystonin is a cytoskeletal linker protein with both actin- and tubulin-binding domains. Loss of function of this protein results in a sensory neuropathy called Hereditary Sensory Autonomic Neuropathy VI in humans and dystonia musculorum in mice. This disease presents with severe ataxia, dystonic muscle and is ultimately fatal early in life. While loss of the neuronal isoforms of dystonin primarily leads to sensory neuron degeneration, it has also been shown that peripheral myelination is compromised due to intrinsic Schwann cell differentiation abnormalities. The role of this cytoskeletal linker in oligodendrocytes, however, remains unclear. We sought to determine the effects of the loss of neuronal dystonin on oligodendrocyte differentiation and central myelination. To address this, primary oligodendrocytes were isolated from a severe model of dystonia musculorum, Dstdt-27J, and assessed for morphological and molecular differentiation capacity. No defects could be discerned in the differentiation of Dstdt-27J oligodendrocytes relative to oligodendrocytes from wild-type littermates. Survival was also compared between Dstdt-27J and wild-type oligodendrocytes, revealing no significant difference. Using a recently developed migration assay, we further analysed the ability of primary oligodendrocyte progenitor cell motility, and found that Dstdt-27J oligodendrocyte progenitor cells were able to migrate normally. Finally, in vivo analysis of oligodendrocyte myelination was done in phenotype-stage optic nerve, cerebral cortex and spinal cord. The density of myelinated axons and g-ratios of Dstdt-27J optic nerves was normal, as

  18. Synthesis of two new alkyne-bearing linkers used for the preparation of siRNA for labeling by click chemistry with fluorine-18

    International Nuclear Information System (INIS)

    Flagothier, Jessica; Kaisin, Geoffroy; Mercier, Frederic; Thonon, David; Teller, Nathalie; Wouters, Johan; Luxen, André

    2012-01-01

    Oligonucleotides (ONs) and more particularly siRNAs are promising drugs but their pharmacokinetics and biodistribution are widely unknown. Positron Emission Tomography (PET) using fluorine-18 is a suitable technique to quantify these biological processes. Click chemistry (Huisgen cycloaddition) is the current method for labeling siRNA. In order to study the influence of a linker bearing by [ 18 F] labeled ONs, on the in vivo pharmacokinetic and metabolism, we have developed two modified ONs by two new linkers. Here we report the synthesis of two alkyne-bearing linkers, the incorporation onto a ONs and the conjugation by click chemistry with a [ 18 F] prosthetic group. - Highlights: ► Synthesis of two new alkyne linkers. ► Functionalization at the 3′-end siRNA by alkyne linker derived of proline. ► Click chemistry between alkyne modified siRNA and [ 18 F] prosthetic group.

  19. One-pot preparation of mRNA/cDNA display by a novel and versatile puromycin-linker DNA.

    Science.gov (United States)

    Mochizuki, Yuki; Biyani, Manish; Tsuji-Ueno, Sachika; Suzuki, Miho; Nishigaki, Koichi; Husimi, Yuzuru; Nemoto, Naoto

    2011-09-12

    A rapid, easy, and robust preparation method for mRNA/cDNA display using a newly designed puromycin-linker DNA is presented. The new linker is structurally simple, easy to synthesize, and cost-effective for use in "in vitro peptide and protein selection". An introduction of RNase T1 nuclease site to the new linker facilitates the easy recovery of mRNA/cDNA displayed protein by an improvement of the efficiency of ligating the linker to mRNAs and efficient release of mRNA/cDNA displayed protein from the solid-phase (magnetic bead). For application demonstration, affinity selections were successfully performed. Furthermore, we introduced a "one-pot" preparation protocol to perform mRNA display easy. Unlike conventional approaches that require tedious and downstream multistep process including purification, this protocol will make the mRNA/cDNA display methods more practical and convenient and also facilitate the development of next-generation, high-throughput mRNA/cDNA display systems amenable to automation.

  20. Mechanistic Evaluation of Motion in Redox-Driven Rotaxanes Reveals Longer Linkers Hasten Forward Escape's and Hinder Backward Translations

    DEFF Research Database (Denmark)

    Andersen, S. S.; Share, A. I.; Poulsen, B. L.

    2014-01-01

    temperatures to provide activation enthalpies (Delta H-double dagger) and entropies (Delta S-double dagger). Longer glycol linkers led to modest increases in the forward escape (t(1/2) = 60 to 69 s); though not because of a diffusive walk. The reduced rate of motion backward depended on folded structures...

  1. The interdomain flexible linker of the polypeptide GalNAc transferases dictates their long-range glycosylation preferences

    DEFF Research Database (Denmark)

    Rivas, Matilde De Las; Lira-Navarrete, Erandi; Daniel, Earnest James Paul

    2017-01-01

    The polypeptide GalNAc-transferases (GalNAc-Ts), that initiate mucin-type O-glycosylation, consist of a catalytic and a lectin domain connected by a flexible linker. In addition to recognizing polypeptide sequence, the GalNAc-Ts exhibit unique long-range N- A nd/or C-terminal prior glycosylation ...

  2. Synthesis and catalytic evaluation in the Heck reaction of deposited palladium catalysts immobilized via amide linkers and their molecular analogues

    Czech Academy of Sciences Publication Activity Database

    Semler, M.; Čejka, Jiří; Štěpnička, P.

    2014-01-01

    Roč. 227, MAY 2014 (2014), s. 207-214 ISSN 0920-5861 R&D Projects: GA ČR GA104/09/0561; GA ČR(CZ) GA13-08944S Institutional support: RVO:61388955 Keywords : deposited catalysts * palladium * amide linkers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.893, year: 2014

  3. Differential solvation of intrinsically disordered linkers drives the formation of spatially organized droplets in ternary systems of linear multivalent proteins

    Science.gov (United States)

    Harmon, Tyler S.; Holehouse, Alex S.; Pappu, Rohit V.

    2018-04-01

    Intracellular biomolecular condensates are membraneless organelles that encompass large numbers of multivalent protein and nucleic acid molecules. The bodies assemble via a combination of liquid–liquid phase separation and gelation. A majority of condensates included multiple components and show multilayered organization as opposed to being well-mixed unitary liquids. Here, we put forward a simple thermodynamic framework to describe the emergence of spatially organized droplets in multicomponent systems comprising of linear multivalent polymers also known as associative polymers. These polymers, which mimic proteins and/or RNA have the architecture of domains or motifs known as stickers that are interspersed by flexible spacers known as linkers. Using a minimalist numerical model for a four-component system, we have identified features of linear multivalent molecules that are necessary and sufficient for generating spatially organized droplets. We show that differences in sequence-specific effective solvation volumes of disordered linkers between interaction domains enable the formation of spatially organized droplets. Molecules with linkers that are preferentially solvated are driven to the interface with the bulk solvent, whereas molecules that have linkers with negligible effective solvation volumes form cores in the core–shell architectures that emerge in the minimalist four-component systems. Our modeling has relevance for understanding the physical determinants of spatially organized membraneless organelles.

  4. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

    Science.gov (United States)

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-01-01

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246

  5. High-resolution two-dimensional liquid chromatography analysis of key linker drug intermediate used in antibody drug conjugates.

    Science.gov (United States)

    Venkatramani, C J; Huang, Shu Rong; Al-Sayah, Mohammad; Patel, Ila; Wigman, Larry

    2017-10-27

    In this manuscript, the application of high-resolution sampling (HRS) two-dimensional liquid chromatography (2D-LC) in the detailed analysis of key linker drug intermediate is presented. Using HRS, selected regions of the primary column eluent were transferred to a secondary column with fidelity enabling qualitative and quantitative analysis of linker drugs. The primary column purity of linker drug intermediate ranged from 88.9% to 94.5% and the secondary column purity ranged from 99.6% to 99.9%, showing lot-to-lot variability, significant differences between the three lots, and substantiating the synthetic and analytical challenges of ADCs. Over 15 impurities co-eluting with the linker drug intermediate in the primary dimension were resolved in the secondary dimension. The concentrations of most of these impurities were over three orders of magnitude lower than the linker drug. Effective peak focusing and high-speed secondary column analysis resulted in sharp peaks in the secondary dimension, improving the signal-to-noise ratios. The sensitivity of 2D-LC separation was over five fold better than conventional HPLC separation. The limit of quantitation (LOQ) was less than 0.01%. Many peaks originating from primary dimension were resolved into multiple components in the complementary secondary dimension, demonstrating the complexity of these samples. The 2D-LC was highly reproducible, showing good precision between runs with%RSD of peak areas less than 0.1 for the main component. The absolute difference in the peak areas of impurities less than 0.1% were within ±0.01% and for impurities in the range of 0.1%-0.3%, the absolute difference were ±0.02%, which are comparable to 1D-LC. The overall purity of the linker drug intermediate was determined from the product of primary and secondary column purity (HPLC Purity=%peak area of main component in the primary dimension×%peak area of main component in the secondary dimension). Additionally, the 2D-LC separation enables

  6. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu

    2012-05-02

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  7. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu; Hsiao, Vincent; Zheng, Yue Bing; Huang, Tony Jun

    2012-01-01

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  8. Volumetric polymerization shrinkage of contemporary composite resins

    OpenAIRE

    Nagem Filho, Halim; Nagem, Haline Drumond; Francisconi, Paulo Afonso Silveira; Franco, Eduardo Batista; Mondelli, Rafael Francisco Lia; Coutinho, Kennedy Queiroz

    2007-01-01

    The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill ...

  9. Pivotal role of extended linker 2 in the activation of Gα by G protein-coupled receptor.

    Science.gov (United States)

    Huang, Jianyun; Sun, Yutong; Zhang, J Jillian; Huang, Xin-Yun

    2015-01-02

    G protein-coupled receptors (GPCRs) relay extracellular signals mainly to heterotrimeric G-proteins (Gαβγ) and they are the most successful drug targets. The mechanisms of G-protein activation by GPCRs are not well understood. Previous studies have revealed a signal relay route from a GPCR via the C-terminal α5-helix of Gα to the guanine nucleotide-binding pocket. Recent structural and biophysical studies uncover a role for the opening or rotating of the α-helical domain of Gα during the activation of Gα by a GPCR. Here we show that β-adrenergic receptors activate eight Gαs mutant proteins (from a screen of 66 Gαs mutants) that are unable to bind Gβγ subunits in cells. Five of these eight mutants are in the αF/Linker 2/β2 hinge region (extended Linker 2) that connects the Ras-like GTPase domain and the α-helical domain of Gαs. This extended Linker 2 is the target site of a natural product inhibitor of Gq. Our data show that the extended Linker 2 is critical for Gα activation by GPCRs. We propose that a GPCR via its intracellular loop 2 directly interacts with the β2/β3 loop of Gα to communicate to Linker 2, resulting in the opening and closing of the α-helical domain and the release of GDP during G-protein activation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  10. Evaluation of ¹¹¹in-labelled exendin-4 derivatives containing different meprin β-specific cleavable linkers.

    Directory of Open Access Journals (Sweden)

    Andreas Jodal

    Full Text Available Cleavable linkers, which are specifically cleaved by defined conditions or enzymes, are powerful tools that can be used for various purposes. Amongst other things, they have been successfully used to deliver toxic payloads as prodrugs into target tissues. In this work novel linker sequences targeting meprin β, a metalloprotease expressed in the kidney brush-border membrane, were designed and included in the sequence of three radiolabelled exendin-4 derivatives. As radiolabelled exendin-4 derivatives strongly accumulate in the kidneys, we hypothesised that specific cleavage of the radiolabelled moiety at the kidney brush-border membrane would allow easier excretion of the activity into the urine and therefore improve the pharmacological properties of the peptide.The insertion of a cleavable linker did not negatively influence the in vitro properties of the peptides. They showed a good affinity to the GLP-1 receptor expressed in CHL cells, a high internalisation and sufficiently high stability in fresh human blood plasma. In vitro digestion with recombinant meprin β rapidly metabolised the corresponding linker sequences. After 60 min the majority of the corresponding peptides were digested and at the same time the anticipated fragments were formed. The peptides were also quickly metabolised in CD1 nu/nu mouse kidney homogenates. Immunofluorescence staining of meprin β in kidney sections confirmed the expression of the protease in the kidney brush-border membrane. Biodistribution in GLP-1 receptor positive tumour-xenograft bearing mice revealed high specific uptake of the 111In-labelled tracers in receptor positive tissue. Accumulation in the kidneys, however, was still high and comparable to the lead compound 111In-Ex4NOD40.In conclusion, we show that the concept of cleavable linkers specific for meprin β is feasible, as the peptides are rapidly cleaved by the enzyme while retaining their biological properties.

  11. Prescreening of Nicotine Hapten Linkers in Vitro To Select Hapten-Conjugate Vaccine Candidates for Pharmacokinetic Evaluation in Vivo.

    Science.gov (United States)

    Arutla, Viswanath; Leal, Joseph; Liu, Xiaowei; Sokalingam, Sriram; Raleigh, Michael; Adaralegbe, Adejimi; Liu, Li; Pentel, Paul R; Hecht, Sidney M; Chang, Yung

    2017-05-08

    Since the demonstration of nicotine vaccines as a possible therapeutic intervention for the effects of tobacco smoke, extensive effort has been made to enhance nicotine specific immunity. Linker modifications of nicotine haptens have been a focal point for improving the immunogenicity of nicotine, in which the evaluation of these modifications usually relies on in vivo animal models, such as mice, rats or nonhuman primates. Here, we present two in vitro screening strategies to estimate and predict the immunogenic potential of our newly designed nicotine haptens. One utilizes a competition enzyme-linked immunoabsorbent assay (ELISA) to profile the interactions of nicotine haptens or hapten-protein conjugates with nicotine specific antibodies, both polyclonal and monoclonal. Another relies on computational modeling of the interactions between haptens and amino acid residues near the conjugation site of the carrier protein to infer linker-carrier protein conjugation effect on antinicotine antibody response. Using these two in vitro methods, we ranked the haptens with different linkers for their potential as viable vaccine candidates. The ELISA-based hapten ranking was in an agreement with the results obtained by in vivo nicotine pharmacokinetic analysis. A correlation was found between the average binding affinity (IC 50 ) of the haptens to an anti-Nic monoclonal antibody and the average brain nicotine concentration in the immunized mice. The computational modeling of hapten and carrier protein interactions helps exclude conjugates with strong linker-carrier conjugation effects and low in vivo efficacy. The simplicity of these in vitro screening strategies should facilitate the selection and development of more effective nicotine conjugate vaccines. In addition, these data highlight a previously under-appreciated contribution of linkers and hapten-protein conjugations to conjugate vaccine immunogenicity by virtue of their inclusion in the epitope that binds and

  12. Polymeric membrane materials for artificial organs.

    Science.gov (United States)

    Kawakami, Hiroyoshi

    2008-01-01

    Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

  13. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  14. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.

    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  15. Active Ester Containing Surfmer for One-Stage Polymer Nanoparticle Surface Functionalization in Mini-Emulsion Polymerization

    Directory of Open Access Journals (Sweden)

    Vanessa L. Albernaz

    2018-04-01

    Full Text Available Functional surface active monomers (surfmers are molecules that combine the functionalities of surface activity, polymerizability, and reactive groups. This study presents an improved pathway for the synthesis of the active ester containing surfmer p-(11-acrylamidoundecanoyloxyphenyl dimethylsulfonium methyl sulfate (AUPDS. Further, the preparation of poly(methyl methacrylate and polystyrene nanoparticles (NPs by mini-emulsion polymerization using AUPDS is investigated, leading to NPs with active ester groups on their surface. By systematically varying reaction parameters and reagent concentrations, it was found that AUPDS feed concentrations between 2–4 mol% yielded narrowly distributed and stable spherical particles with average sizes between 83 and 134 nm for non-cross-linked NPs, and up to 163 nm for cross-linked NPs. By basic hydrolysis of the active ester groups in aqueous dispersion, the positive ζ-potential (ZP was converted into a negative ZP and charge quantities determined by polyelectrolyte titrations before and after hydrolysis were in the same range, indicating that the active ester groups were indeed accessible in aqueous suspension. Increasing cross-linker amounts over 10 mol% also led to a decrease of ZP of NPs, probably due to internalization of the AUPDS during polymerization. In conclusion, by using optimized reaction conditions, it is possible to prepare active ester functionalized NPs in one stage using AUPDS as a surfmer in mini-emulsion polymerization.

  16. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  17. Investigation of Optimum Polymerization Conditions for Synthesis of Cross-Linked Polyacrylamide-Amphoteric Surfmer Nanocomposites for Polymer Flooding in Sandstone Reservoirs

    Directory of Open Access Journals (Sweden)

    A. N. El-hoshoudy

    2015-01-01

    Full Text Available Currently enhanced oil recovery (EOR technology is getting more attention by many countries since energy crises are getting worse and frightening. Polymer flooding by hydrophobically associated polyacrylamides (HAPAM and its modified silica nanocomposite are a widely implemented technique through enhanced oil recovery (EOR technology. This polymers class can be synthesized by copolymerization of acrylamide (AM, reactive surfmer, functionalized silica nanoparticles, and a hydrophobic cross-linker moiety in the presence of water soluble initiator via heterogeneous emulsion polymerization technique, to form latexes that can be applied during polymer flooding. Chemical structure of the prepared copolymers was proven through different techniques such as Fourier transform infrared spectroscopy (FTIR, and nuclear magnetic spectroscopy (1H&13C-NMR, and molecular weight was measured by gel permeation chromatography. Study of the effects of monomer, surfmer, cross-linker, silica, and initiator concentrations as well as reaction temperature was investigated to determine optimum polymerization conditions through single factor and orthogonal experiments. Evaluation of the prepared copolymers for enhancing recovered oil amount was evaluated by carrying out flooding experiments on one-dimensional sandstone model to determine recovery factor.

  18. Modification of Titanium Substrates with Chimeric Peptides Comprising Antimicrobial and Titanium-Binding Motifs Connected by Linkers To Inhibit Biofilm Formation.

    Science.gov (United States)

    Liu, Zihao; Ma, Shiqing; Duan, Shun; Xuliang, Deng; Sun, Yingchun; Zhang, Xi; Xu, Xinhua; Guan, Binbin; Wang, Chao; Hu, Meilin; Qi, Xingying; Zhang, Xu; Gao, Ping

    2016-03-02

    Bacterial adhesion and biofilm formation are the primary causes of implant-associated infection, which is difficult to eliminate and may induce failure in dental implants. Chimeric peptides with both binding and antimicrobial motifs may provide a promising alternative to inhibit biofilm formation on titanium surfaces. In this study, chimeric peptides were designed by connecting an antimicrobial motif (JH8194: KRLFRRWQWRMKKY) with a binding motif (minTBP-1: RKLPDA) directly or via flexible/rigid linkers to modify Ti surfaces. We evaluated the binding behavior of peptides using quartz crystal microbalance (QCM) and atomic force microscopy (AFM) techniques and investigated the effect of the modification of titanium surfaces with these peptides on the bioactivity of Streptococcus gordonii (S. gordonii) and Streptococcus sanguis (S. sanguis). Compared with the flexible linker (GGGGS), the rigid linker (PAPAP) significantly increased the adsorption of the chimeric peptide on titanium surfaces (p chimeric peptide with the rigid linker exhibited more effective antimicrobial ability than the peptide with the flexible linker. This finding was ascribed to the ability of the rigid linker to separate functional domains and reduce their interference to the maximum extent. Consequently, the performance of chimeric peptides with specific titanium-binding motifs and antimicrobial motifs against bacteria can be optimized by the proper selection of linkers. This rational design of chimeric peptides provides a promising alternative to inhibit the formation of biofilms on titanium surfaces with the potential to prevent peri-implantitis and peri-implant mucositis.

  19. Multivalent cyclic RGD ligands: influence of linker lengths on receptor binding

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, Holger; Schaefer, Martin; Bauder-Wuest, Ulrike; Eder, Matthias; Oltmanns, Doerte [Department of Radiopharmaceutical Chemistry, German Cancer Research Center, Im Neuenheimer Feld 280, 69120 Heidelberg (Germany); Haberkorn, Uwe; Mier, Walter [Department of Nuclear Medicine, University Hospital Heidelberg, Im Neuenheimer Feld 400, 69120 Heidelberg (Germany); Eisenhut, Michael, E-mail: m.eisenhut@dkfz.d [Department of Radiopharmaceutical Chemistry, German Cancer Research Center, Im Neuenheimer Feld 280, 69120 Heidelberg (Germany)

    2010-11-15

    Peptides involving the RGD motive (arginine-glycine-aspartic acid) recognize members of the integrin receptor family. Since the receptors are located mainly on the surface of endothelial cells, structural modifications including multimers of c(RGDfE) were recently found to improve the binding avidity for {alpha}{sub v{beta}3} integrin significantly. The multivalent RGD peptides exhibited rather loose linkages partly including oligo(ethylene glycol) spacers (EG{sub n}) with different chain lengths. Therefore, the dependence of multivalent RGD systems with and without EG{sub n} linkers were investigated on their binding properties to cultured {alpha}{sub v{beta}3} integrin-expressing U87MG cells. Methods: We synthesized a series of di-, tri- and tetravalent rigid scaffolds (terephthalic acid, trimesic acid and adamantane-1,3,5,7-tetracarboxylic acid) conjugated to c(RGDyK) ligands, which were linked contiguously or separated by the oligo(ethylene glycol) spacers. The inhibition constants of these c(RGDyK) derivatives were determined by competition assays with {sup 125}I-labeled echistatin. Results: While c(RGDyK) function is a relative weak competitor against [{sup 125}I]echistatin (K{sub i}, 329{+-}18 nM) for {alpha}{sub v{beta}3} integrin-expressing U87MG cells, RGD dimers improved the competition potency considerably (K{sub i}, 64{+-}23 nM). This effect was even more pronounced with the RGD trimers (K{sub i}, 40{+-}7 nM) and tetramers (K{sub i}, 26{+-}9 nM). The introduction of EG{sub n} spacers and the increase of linker lengths proved to be detrimental since more competitors were needed to compete with [{sup 125}I]echistatin. The EG{sub 6} group, for example, reduced the inhibition constants by 29% (dimer), 57% (trimer) and 97% (tetramer). Conclusion: The binding experiments performed with the three forms of multivalent RGD ligands indicate the weakening of competitive potency against [{sup 125}I]echistatin with the introduction of EG{sub n} spacers. This effect

  20. Polymeric implant of methylprednisolone for spinal injury ...

    African Journals Online (AJOL)

    Polymeric implant of methylprednisolone for spinal injury: preparation and characterization. Bo Yin, Jian-Jun Ji, Ming Yang. Abstract. Purpose: To improve the effectiveness and reduce the systemic side effects of methylprednisolone in traumatic spinal injuries, its polymeric implants were prepared using chitosan and sodium ...

  1. Nanoparticles from a controlled polymerization process

    International Nuclear Information System (INIS)

    Tirumala, V.R.; Caneba, G.T.; Dar, Y.; Wang, H.-H.; Mancini, D.C.

    2003-01-01

    Free-radical retrograde precipitation polymerization process in the past has shown excellent control characteristics over reaction rate, molecular weight, and in the entrapment of live radicals for the generation of block copolymers. The same principle has now been extended to study the reaction confinement to a nanoscale region. Nanosized polymer particles have been reported to form from block copolymers, conventional precipitation polymerization methods, or through emulsion polymerization approaches. In this work, we present a new method of generating nanosized polymer particles by polymerizing the monomer in an environment that precipitates the polymer above the lower critical solution temperature. The nanoparticles have been characterized by both tapping-mode atomic force microscopy observations and in situ synchrotron time-resolved small-angle X-ray scattering analysis. The results from both the techniques showed the formation of nanoparticles in the size range of 15-30 nm, directly from the polymerization process.

  2. Fluid Effects in Polymers and Polymeric Composites

    CERN Document Server

    Weitsman, Y Jack

    2012-01-01

    Fluid Effects in Polymers and Polymeric Composites, written by the late Dr. Y. Jack Weitsman, addresses the wide range of parameters that affect the interaction of fluids with polymers and polymeric composites. The book aims at broadening the scope of available data, mostly limited up to this time to weight-gain recordings of fluid ingress into polymers and composites, to the practical circumstances of fluctuating exposure. Various forms of experimental data are given, in conjunction with theoretical models derived from basic scientific principles, and correlated with severity of exposure conditions and interpreted by means of rationally based theoretical models. The practical implications of the effects of fluids are discussed. The issue of fluid effects on polymers and polymeric composites is of concern to engineers and scientists active in aerospace and naval structures, as an increasing portion of these structures are made of polymeric composites and employ polymeric adhesives as a joining device. While...

  3. ROMP-Derived cyclooctene-based monolithic polymeric materials reinforced with inorganic nanoparticles for applications in tissue engineering

    Directory of Open Access Journals (Sweden)

    Franziska Weichelt

    2010-12-01

    Full Text Available Porous monolithic inorganic/polymeric hybrid materials have been prepared via ring-opening metathesis copolymerization starting from a highly polar monomer, i.e., cis-5-cyclooctene-trans-1,2-diol and a 7-oxanorborn-2-ene-derived cross-linker in the presence of porogenic solvents and two types of inorganic nanoparticles (i.e., CaCO3 and calcium hydroxyapatite, respectively using the third-generation Grubbs initiator RuCl2(Py2(IMesH2(CHPh. The physico-chemical properties of the monolithic materials, such as pore size distribution and microhardness were studied with regard to the nanoparticle type and content. Moreover, the reinforced monoliths were tested for the possible use as scaffold materials in tissue engineering, by carrying out cell cultivation experiments with human adipose tissue-derived stromal cells.

  4. Inverse Effects on Gating and Modulation Caused by a Mutation in the M2-M3 Linker of the GABAA Receptor γ SubunitS⃞

    OpenAIRE

    O'Shea, Sean M.; Williams, Carrie A.; Jenkins, Andrew

    2009-01-01

    M2-M3 linkers are receptor subunit domains known to be critical for the normal function of cysteine-loop ligand-gated ion channels. Previous studies of α and β subunits of type “A” GABA receptors suggest that these linkers couple extracellular elements involved in GABA binding to the transmembrane segments that control the opening of the ion channel. To study the importance of the γ subunit M2-M3 linker, we examined the macroscopic and single-channel effects of an engi...

  5. A Class of Rigid Linker-bearing Glucosides for Membrane Protein Structural Study.

    Science.gov (United States)

    Sadaf, Aiman; Mortensen, Jonas S; Capaldi, Stefano; Tikhonova, Elena; Hariharan, Parameswaran; de Castro Ribeiro, Orquidea; Loland, Claus J; Guan, Lan; Byrne, Bernadette; Chae, Pil Seok

    2016-03-01

    Membrane proteins are amphipathic bio-macromolecules incompatible with the polar environments of aqueous media. Conventional detergents encapsulate the hydrophobic surfaces of membrane proteins allowing them to exist in aqueous solution. Membrane proteins stabilized by detergent micelles are used for structural and functional analysis. Despite the availability of a large number of detergents, only a few agents are sufficiently effective at maintaining the integrity of membrane proteins to allow successful crystallization. In the present study, we describe a novel class of synthetic amphiphiles with a branched tail group and a triglucoside head group. These head and tail groups were connected via an amide or ether linkage by using a tris(hydroxylmethyl)aminomethane (TRIS) or neopentyl glycol (NPG) linker to produce TRIS-derived triglucosides (TDTs) and NPG-derived triglucosides (NDTs), respectively. Members of this class conferred enhanced stability on target membrane proteins compared to conventional detergents. Because of straightforward synthesis of the novel agents and their favourable effects on a range of membrane proteins, these agents should be of wide applicability to membrane protein science.

  6. Gold nanoparticles deposited on linker-free silicon substrate and embedded in aluminum Schottky contact.

    Science.gov (United States)

    Gorji, Mohammad Saleh; Razak, Khairunisak Abdul; Cheong, Kuan Yew

    2013-10-15

    Given the enormous importance of Au nanoparticles (NPs) deposition on Si substrates as the precursor for various applications, we present an alternative approach to deposit Au NPs on linker-free n- and p-type Si substrates. It is demonstrated that, all conditions being similar, there is a significant difference between densities of the deposited NPs on both substrates. The Zeta-potential and polarity of charges surrounding the hydroxylamine reduced seeded growth Au NPs, are determined by a Zetasizer. To investigate the surface properties of Si substrates, contact angle measurement is performed. Field-emission scanning electron microscope is then utilized to distinguish the NPs density on the substrates. Finally, Al/Si Schottky barrier diodes with embedded Au NPs are fabricated, and their structural and electrical characteristics are further evaluated using an energy-filtered transmission electron microscope and current-voltage measurements, respectively. The results reveal that the density of NPs is significantly higher on n-type Si substrate and consequently has more pronounced effects on the electrical characteristics of the diode. It is concluded that protonation of Si-OH group on Si surface in low pH is responsible for the immobilization of Au NPs, which eventually contributes to the lowering of barrier height and enhances the electrical characteristics. Copyright © 2013 Elsevier Inc. All rights reserved.

  7. Preparation and in vivo evaluation of novel linkers for 211At labeling of proteins

    International Nuclear Information System (INIS)

    Talanov, Vladimir S.; Yordanov, Alexander T.; Garmestani, Kayhan; Milenic, Diane E.; Arora, Hans C.; Plascjak, Paul S.; Eckelman, William C.; Waldmann, Thomas A.; Brechbiel, Martin W.

    2004-01-01

    The syntheses, radiolabeling, antibody conjugation and in vivo evaluation of new linkers for 211 At labeling of monoclonal antibodies are described. Syntheses of the N-succinimidyl esters and labeling with 211 At to form succinimidyl 4-methoxymethyl-3-[ 211 At]astatobenzoate (9) and succinimidyl 4-methylthiomethyl-3-[ 211 At]astatobenzoate (11) from the corresponding bromo-aryl esters is reported. Previously reported succinimidyl N-{4-[ 211 At]astatophenethyl}succinamate (SAPS) is employed as a standard of in vivo stability. Each agent is conjugated with Herceptin in parallel with their respective 125 I analogue, succinimidyl 4-methoxymethyl-3-[ 125 I]iodobenzoate (10), succinimidyl 4-methylthiomethyl-3-[ 125 I]iodobenzoate (12) and succinimidyl N-{4-[ 125 I]iodophenethyl}succinamate (SIPS), respectively, for comparative assessment in LS-174T xenograft-bearing mice. With 9 and 11, inclusion of an electron pair donor in the ortho position does not appear to provide in vivo stability comparable to SAPS. Variables in radiolabeling chemistry of these three agents with 211 At are notable. Sequential elimination of acetic acid and oxidizing agent, N-chlorosuccinimide (NCS), from the 211 At radiolabeling protocol for forming SAPS improves yield, product purity and consistency. NCS appears to be critical for the radiolabeling of 6 with 211 At. Formation of 11, however, is found to require the absence of NCS. Elimination of acetic acid is found to have no effect on radiolabeling efficiency or yield for either of these reactions

  8. Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers

    International Nuclear Information System (INIS)

    Yang, Li; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

    2016-01-01

    The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

  9. Missing Linker Defects in a Homochiral Metal-Organic Framework: Tuning the Chiral Separation Capacity.

    Science.gov (United States)

    Slater, Benjamin; Wang, Zeru; Jiang, Shanxue; Hill, Matthew R; Ladewig, Bradley P

    2017-12-20

    Efficient chiral separation remains a very challenging task due to the identical physical and chemical properties of the enantiomers of a molecule. Enantiomers only behave differently from each other in the presence of other chiral species. Homochiral metal-organic frameworks (MOFs) have received much attention for their promising enantioseparation properties. However, there are still challenges to overcome in this field such as high enantiomeric separation. Structural defects play an important role in the properties of MOFs and can significantly change the pore architecture. In this work, we introduced missing linker defects into a homochiral metal-organic framework [Zn 2 (bdc)(l-lac)(dmf)] (ZnBLD; bdc = 1,4-benzenedicarboxylic acid, l-lac = l-lactic acid, dmf = N,N'-dimethylformamide) and observed an increase in enantiomeric excess for 1-phenylethanol of 35% with the defective frameworks. We adjusted the concentration of monocarboxylic acid ligand l-lactic acid by varying the ratio of Zn 2+ to ligand from 0.5 to 0.85 mmol. Additionally, a defective framework was synthesized with propanoic acid as modulator. In order to elucidate the correlation between defects and enantiomeric excess, five characterization techniques (FTIR, TGA, 1 H NMR, ICP, and PXRD) were employed. Full width at half-maximum analysis (fwhm) was performed on the powder X-ray diffraction traces and showed that the higher concentration of monocarboxylic acid MOFs were isostructural but suffered from increased fwhm values.

  10. Enhanced Charge Separation Efficiency in Pyridine-Anchored Phthalocyanine-Sensitized Solar Cells by Linker Elongation.

    Science.gov (United States)

    Ikeuchi, Takuro; Agrawal, Saurabh; Ezoe, Masayuki; Mori, Shogo; Kimura, Mutsumi

    2015-11-01

    A series of zinc phthalocyanine sensitizers (PcS22-24) having a pyridine anchoring group are designed and synthesized to investigate the structural dependence on performance in dye-sensitized solar cells. The pyridine-anchor zinc phthalocyanine sensitizer PcS23 shows 79 % incident-photon to current-conversion efficiency (IPCE) and 6.1 % energy conversion efficiency, which are comparable with similar phthalocyanine dyes having a carboxylic acid anchoring group. Based on DFT calculations, the high IPCE is attributed with the mixture of an excited-state molecular orbital of the sensitizer and the orbitals of TiO2 . Between pyridine and carboxylic acid anchor dyes, opposite trends are observed in the linker-length dependence of the IPCE. The red-absorbing PcS23 is applied for co-sensitization with a carboxyl-anchor organic dye D131 that has a complementary spectral response. The site-selective adsorption of PcS23 and D131 on the TiO2 surface results in a panchromatic photocurrent response for the whole visible-light region of sun light. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    Science.gov (United States)

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-06-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

  12. Nucleosome–nucleosome interactions via histone tails and linker DNA regulate nuclear rigidity

    Science.gov (United States)

    Shimamoto, Yuta; Tamura, Sachiko; Masumoto, Hiroshi; Maeshima, Kazuhiro

    2017-01-01

    Cells, as well as the nuclei inside them, experience significant mechanical stress in diverse biological processes, including contraction, migration, and adhesion. The structural stability of nuclei must therefore be maintained in order to protect genome integrity. Despite extensive knowledge on nuclear architecture and components, however, the underlying physical and molecular mechanisms remain largely unknown. We address this by subjecting isolated human cell nuclei to microneedle-based quantitative micromanipulation with a series of biochemical perturbations of the chromatin. We find that the mechanical rigidity of nuclei depends on the continuity of the nucleosomal fiber and interactions between nucleosomes. Disrupting these chromatin features by varying cation concentration, acetylating histone tails, or digesting linker DNA results in loss of nuclear rigidity. In contrast, the levels of key chromatin assembly factors, including cohesin, condensin II, and CTCF, and a major nuclear envelope protein, lamin, are unaffected. Together with in situ evidence using living cells and a simple mechanical model, our findings reveal a chromatin-based regulation of the nuclear mechanical response and provide insight into the significance of local and global chromatin structures, such as those associated with interdigitated or melted nucleosomal fibers. PMID:28428255

  13. Role of H1 linker histones in mammalian development and stem cell differentiation.

    Science.gov (United States)

    Pan, Chenyi; Fan, Yuhong

    2016-03-01

    H1 linker histones are key chromatin architectural proteins facilitating the formation of higher order chromatin structures. The H1 family constitutes the most heterogeneous group of histone proteins, with eleven non-allelic H1 variants in mammals. H1 variants differ in their biochemical properties and exhibit significant sequence divergence from one another, yet most of them are highly conserved during evolution from mouse to human. H1 variants are differentially regulated during development and their cellular compositions undergo dramatic changes in embryogenesis, gametogenesis, tissue maturation and cellular differentiation. As a group, H1 histones are essential for mouse development and proper stem cell differentiation. Here we summarize our current knowledge on the expression and functions of H1 variants in mammalian development and stem cell differentiation. Their diversity, sequence conservation, complex expression and distinct functions suggest that H1s mediate chromatin reprogramming and contribute to the large variations and complexity of chromatin structure and gene expression in the mammalian genome. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Modeling liquid crystal polymeric devices

    Science.gov (United States)

    Gimenez Pinto, Vianney Karina

    The main focus of this work is the theoretical and numerical study of materials that combine liquid crystal and polymer. Liquid crystal elastomers are polymeric materials that exhibit both the ordered properties of the liquid crystals and the elastic properties of rubbers. Changing the order of the liquid crystal molecules within the polymer network can induce shape change. These materials are very valuable for applications such as actuators, sensors, artificial muscles, haptic displays, etc. In this work we apply finite element elastodynamics simulations to study the temperature induced shape deformation in nematic elastomers with complex director microstructure. In another topic, we propose a novel numerical method to model the director dynamics and microstructural evolution of three dimensional nematic and cholesteric liquid crystals. Numerical studies presented in this work are in agreement with experimental observations and provide insight into the design of application devices.

  15. Polymerization of lanthanide acrylonitrile complexes.

    Science.gov (United States)

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A

    2002-01-01

    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  16. Polymeric materials from renewable resources

    Energy Technology Data Exchange (ETDEWEB)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; Silva, Cristina G. da; Castro, Daniele O.; Ramires, Elaine C.; Oliveira, Fernando de; Santos, Rachel P. O. [Macromolecular Materials and Lignocellulosic Fibers Group, Center for Research on Science and Technology of BioResources, Institute of Chemistry of São Carlos, University of São Paulo, CP 780, 13560-970 São Carlos, São Paulo (Brazil)

    2016-05-18

    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called “biopolyethylene” (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  17. Polymeric materials from renewable resources

    Science.gov (United States)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; da Silva, Cristina G.; Castro, Daniele O.; Ramires, Elaine C.; de Oliveira, Fernando; Santos, Rachel P. O.

    2016-05-01

    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called "biopolyethylene" (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  18. Dual-purpose linker for alpha helix stabilization and imaging agent conjugation to glucagon-like peptide-1 receptor ligands.

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Liao, Jianshan; Thurber, Greg M

    2015-02-18

    Peptides display many characteristics of efficient imaging agents such as rapid targeting, fast background clearance, and low non-specific cellular uptake. However, poor stability, low affinity, and loss of binding after labeling often preclude their use in vivo. Using glucagon-like peptide-1 receptor (GLP-1R) ligands exendin and GLP-1 as a model system, we designed a novel α-helix-stabilizing linker to simultaneously address these limitations. The stabilized and labeled peptides showed an increase in helicity, improved protease resistance, negligible loss or an improvement in binding affinity, and excellent in vivo targeting. The ease of incorporating azidohomoalanine in peptides and efficient reaction with the dialkyne linker enable this technique to potentially be used as a general method for labeling α helices. This strategy should be useful for imaging beta cells in diabetes research and in developing and testing other peptide targeting agents.

  19. Optimizing the relaxivity of GdIII complexes appended to InP/ZnS quantum dots by linker tuning.

    Science.gov (United States)

    Stasiuk, Graeme J; Tamang, Sudarsan; Imbert, Daniel; Gateau, Christelle; Reiss, Peter; Fries, Pascal; Mazzanti, Marinella

    2013-06-21

    Three bimodal MRI/optical nanosized contrast agents with high per-nanoparticle relaxivity (up to 2523 mM(-1) s(-1) at 35 MHz and 932 mM(-1) s(-1) at 200 MHz) have been prepared connecting up to 115 tris-aqua Gd(III) complexes to fluorescent non-toxic InP/ZnS quantum dots. The structure of the linker has an important effect on the relaxivity of the final multimeric contrast agent.

  20. A Small Number of Residues Can Determine if Linker Histones Are Bound On or Off Dyad in the Chromatosome.

    Science.gov (United States)

    Zhou, Bing-Rui; Feng, Hanqiao; Ghirlando, Rodolfo; Li, Shipeng; Schwieters, Charles D; Bai, Yawen

    2016-10-09

    Linker histones bind to the nucleosome and regulate the structure and function of chromatin. We have previously shown that the globular domains of chicken H5 and Drosophila H1 linker histones bind to the nucleosome with on- or off-dyad modes, respectively. To explore the determinant for the distinct binding modes, we investigated the binding of a mutant globular domain of H5 to the nucleosome. This mutant, termed GH5_pMut, includes substitutions of five globular domain residues of H5 with the corresponding residues in the globular domain of Drosophila H1. The residues at these five positions play important roles in nucleosome binding by either H5 or Drosophila H1. NMR and spin-labeling experiments showed that GH5_pMut bound to the nucleosome off the dyad. We further found that the nucleosome array condensed by either the GH5_pMut or the globular domain of Drosophila H1 displayed a similar sedimentation coefficient, whereas the same nucleosome array condensed by the wild-type globular domain of H5 showed a much larger sedimentation coefficient. Moreover, NMR and spin-labeling results from the study of the nucleosome in complex with the full-length human linker histone H1.0, whose globular domain shares high sequence conservation with the corresponding globular domain of H5, are consistent with an on-dyad binding mode. Taken together, our results suggest that a small number of residues in the globular domain of a linker histone can control its binding location on the nucleosome and higher-order chromatin structure. Copyright © 2016. Published by Elsevier Ltd.

  1. Wrinkling of solidifying polymeric coatings

    Science.gov (United States)

    Basu, Soumendra Kumar

    2005-07-01

    In coatings, wrinkles are viewed as defects or as desired features for low gloss, and texture. In either case, discovering the origin of wrinkles and the conditions that lead to their formation is important. This research examines what wrinkling requires and proposes a mechanism to explain the observations. All curing wrinkling coatings contain multi-functional reactants. Upon curing, all develop a depth-wise gradient in solidification that result in a cross-linked elastic skin atop a viscous bottom layer. It is hypothesized that compressive stress develops in the skin when liquid below diffuses up into the skin. High enough compressive stress buckles the skin to produce wrinkles. The hypothesis is substantiated by experimental and theoretical evidences. Effects of various application and compositional parameters on wrinkle size in a liquid-applied acrylic coating and a powder-applied epoxy coating were examined. All three components, namely resin, cross-linker and catalyst blocked with at least equimolar volatile blocker, proved to be required for wrinkling. The wrinkling phenomenon was modeled with a theory that accounts for gradient generation, cross-linking reaction and skinning; predictions compared well with observations. Two-layer non-curing coatings that have a stiff elastic layer atop a complaint elastic bottom layer wrinkled when the top layer is compressed. The top layer was compressed by either moisture absorption or differential thermal expansion. Experimental observations compared well with predictions from a theory based on force balance in multilayer systems subjected to differential contraction or expansion. A model based on the Flory-Rehner free energy of a constrained cross-linked gel was constructed that predicts the compressive stress generated in a coating when it absorbs solvent. Linear stability analysis predicts that when a compressed elastic layer is attached atop a viscous layer, it is always unstable to buckles whose wavelength exceeds a

  2. Design of Tail-Clamp Peptide Nucleic Acid Tethered with Azobenzene Linker for Sequence-Specific Detection of Homopurine DNA

    Directory of Open Access Journals (Sweden)

    Shinjiro Sawada

    2017-10-01

    Full Text Available DNA carries genetic information in its sequence of bases. Synthetic oligonucleotides that can sequence-specifically recognize a target gene sequence are a useful tool for regulating gene expression or detecting target genes. Among the many synthetic oligonucleotides, tail-clamp peptide nucleic acid (TC-PNA offers advantages since it has two homopyrimidine PNA strands connected via a flexible ethylene glycol-type linker that can recognize complementary homopurine sequences via Watson-Crick and Hoogsteen base pairings and form thermally-stable PNA/PNA/DNA triplex structures. Here, we synthesized a series of TC-PNAs that can possess different lengths of azobenzene-containing linkers and studied their binding behaviours to homopurine single-stranded DNA. Introduction of azobenzene at the N-terminus amine of PNA increased the thermal stability of PNA-DNA duplexes. Further extension of the homopyrimidine PNA strand at the N-terminus of PNA-AZO further increased the binding stability of the PNA/DNA/PNA triplex to the target homopurine sequence; however, it induced TC-PNA/DNA/TC-PNA complex formation. Among these TC-PNAs, 9W5H-C4-AZO consisting of nine Watson-Crick bases and five Hoogsteen bases tethered with a beta-alanine conjugated azobenzene linker gave a stable 1:1 TC-PNA/ssDNA complex and exhibited good mismatch recognition. Our design for TC-PNA-AZO can be utilized for detecting homopurine sequences in various genes.

  3. Identification of Epithelial-Mesenchymal Transition-related Target Genes Induced by the Mutation of Smad3 Linker Phosphorylation

    Science.gov (United States)

    Park, Sujin; Yang, Kyung-Min; Park, Yuna; Hong, Eunji; Hong, Chang Pyo; Park, Jinah; Pang, Kyoungwha; Lee, Jihee; Park, Bora; Lee, Siyoung; An, Haein; Kwak, Mi-Kyung; Kim, Junil; Kang, Jin Muk; Kim, Pyunggang; Xiao, Yang; Nie, Guangjun; Ooshima, Akira

    2018-01-01

    Background Smad3 linker phosphorylation plays essential roles in tumor progression and metastasis. We have previously reported that the mutation of Smad3 linker phosphorylation sites (Smad3-Erk/Pro-directed kinase site mutant constructs [EPSM]) markedly reduced the tumor progression while increasing the lung metastasis in breast cancer. Methods We performed high-throughput RNA-Sequencing of the human prostate cancer cell lines infected with adenoviral Smad3-EPSM to identify the genes regulated by Smad3-EPSM. Results In this study, we identified genes which are differentially regulated in the presence of Smad3-EPSM. We first confirmed that Smad3-EPSM strongly enhanced a capability of cell motility and invasiveness as well as the expression of epithelial-mesenchymal transition marker genes, CDH2, SNAI1, and ZEB1 in response to TGF-β1 in human pancreatic and prostate cancer cell lines. We identified GADD45B, CTGF, and JUNB genes in the expression profiles associated with cell motility and invasiveness induced by the Smad3-EPSM. Conclusions These results suggested that inhibition of Smad3 linker phosphorylation may enhance cell motility and invasiveness by inducing expression of GADD45B, CTGF, and JUNB genes in various cancers. PMID:29629343

  4. Butane-1,2,3,4-tetraol-based amphiphilic stereoisomers for membrane protein study: importance of chirality in the linker region

    DEFF Research Database (Denmark)

    Das, Manabendra; Du, Yang; Mortensen, Jonas S.

    2017-01-01

    of the targeted membrane proteins depending on the chirality of the linker region. These findings indicate an important role for detergent stereochemistry in membrane protein stabilization. In addition, we generally observed enhanced detergent efficacy with increasing alkyl chain length, reinforcing...

  5. Method for forming polymerized microfluidic devices

    Science.gov (United States)

    Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

    2013-03-12

    Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

  6. AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

    Institute of Scientific and Technical Information of China (English)

    Hong-kun Li; Jing-zhi Sun; An-jun Qin; Ben Zhong Tang

    2012-01-01

    The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field.This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles (PTAs) with linear and hyperbranched structures.The Cu(Ⅰ)-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.

  7. Mutations in B3GALT6, which Encodes a Glycosaminoglycan Linker Region Enzyme, Cause a Spectrum of Skeletal and Connective Tissue Disorders

    OpenAIRE

    Nakajima, Masahiro; Mizumoto, Shuji; Miyake, Noriko; Kogawa, Ryo; Iida, Aritoshi; Ito, Hironori; Kitoh, Hiroshi; Hirayama, Aya; Mitsubuchi, Hiroshi; Miyazaki, Osamu; Kosaki, Rika; Horikawa, Reiko; Lai, Angeline; Mendoza-Londono, Roberto; Dupuis, Lucie

    2013-01-01

    Proteoglycans (PGs) are a major component of the extracellular matrix in many tissues and function as structural and regulatory molecules. PGs are composed of core proteins and glycosaminoglycan (GAG) side chains. The biosynthesis of GAGs starts with the linker region that consists of four sugar residues and is followed by repeating disaccharide units. By exome sequencing, we found that B3GALT6 encoding an enzyme involved in the biosynthesis of the GAG linker region is responsible for a sever...

  8. Engineering of a novel Ca2+-regulated kinesin molecular motor using a calmodulin dimer linker

    International Nuclear Information System (INIS)

    Shishido, Hideki; Maruta, Shinsaku

    2012-01-01

    Highlights: ► Engineered kinesin–M13 and calmodulin involving single cysteine were prepared. ► CaM mutant was cross-linked to dimer by bifunctional thiol reactive reagent. ► Kinesin–M13 was dimerized via CaM dimer in the presence of calcium. ► Function of the engineered kinesin was regulated by a Ca 2+ -calmodulin dimer linker. -- Abstract: The kinesin–microtubule system holds great promise as a molecular shuttle device within biochips. However, one current barrier is that such shuttles do not have “on–off” control of their movement. Here we report the development of a novel molecular motor powered by an accelerator and brake system, using a kinesin monomer and a calmodulin (CaM) dimer. The kinesin monomer, K355, was fused with a CaM target peptide (M13 peptide) at the C-terminal part of the neck region (K355–M13). We also prepared CaM dimers using CaM mutants (Q3C), (R86C), or (A147C) and crosslinkers that react with cysteine residues. Following induction of K355–M13 dimerization with CaM dimers, we measured K355–M13 motility and found that it can be reversibly regulated in a Ca 2+ -dependent manner. We also found that velocities of K355–M13 varied depending on the type and crosslink position of the CaM dimer used; crosslink length also had a moderate effect on motility. These results suggest Ca 2+ -dependent dimerization of K355–M13 could be used as a novel molecular shuttle, equipped with an accelerator and brake system, for biochip applications.

  9. Preparation and in vivo evaluation of a novel stabilized linker for 211At labeling of protein

    International Nuclear Information System (INIS)

    Talanov, Vladimir S.; Garmestani, Kayhan; Regino, Celeste A.S.; Milenic, Diane E.; Plascjak, Paul S.; Waldmann, Thomas A.; Brechbiel, Martin W.

    2006-01-01

    Significant improvement of in vivo stability of 211 At-labeled radioimmunoconjugates achieved upon employment of a recently reported new linker, succinimidyl N-2-(4-[ 211 At]astatophenethyl)succinamate (SAPS), prompted additional studies of its chemistry. The 211 At radiolabeling of succinimidyl N-2-(4-tributylstannylphenethyl)succinamate (1) was noted to decline after storage at -15 o C for greater than 6 months. Compound 1 was found to degrade via a ring closure reaction with the formation of N-2-(4-tributylstannylphenethyl)succinimide (3), and a modified procedure for the preparation of 1 was developed. The N-methyl structural analog of 1, succinimidyl N-2-(4-tributylstannylphenethyl)-N-methyl succinamate (SPEMS), was synthesized to investigate the possibility of improving the stability of reagent-protein linkage chemistry. Radiolabeling of SPEMS with 211 At generates succinimidyl N-2-(4-[ 211 At]astatophenethyl)-N-methyl succinamate (Methyl-SAPS), with yields being consistent for greater than 1 year. Radiolabelings of 1 and SPEMS with 125 I generated succinimidyl N-2-(4-[ 125 I]iodophenethyl)succinamate (SIPS) and succinimidyl N-2-(4-[ 125 I]iodophenethyl)-N-methyl succinamate (Methyl-SIPS), respectively, and showed no decline in yields. Methyl-SAPS, SAPS, Methyl-SIPS and SIPS were conjugated to Herceptin for a comparative assessment in LS-174T xenograft-bearing mice. The conjugates of Herceptin with Methyl-SAPS or Methyl-SIPS demonstrated immunoreactivity equivalent to if not superior to the SAPS and SIPS paired analogs. The in vivo studies also revealed that the N-methyl modification resulted in a superior statinated product

  10. X-ray-enhanced cancer cell migration requires the linker of nucleoskeleton and cytoskeleton complex.

    Science.gov (United States)

    Imaizumi, Hiromasa; Sato, Katsutoshi; Nishihara, Asuka; Minami, Kazumasa; Koizumi, Masahiko; Matsuura, Nariaki; Hieda, Miki

    2018-04-01

    The linker of nucleoskeleton and cytoskeleton (LINC) complex is a multifunctional protein complex that is involved in various processes at the nuclear envelope, including nuclear migration, mechanotransduction, chromatin tethering and DNA damage response. We recently showed that a nuclear envelope protein, Sad1 and UNC84 domain protein 1 (SUN1), a component of the LINC complex, has a critical function in cell migration. Although ionizing radiation activates cell migration and invasion in vivo and in vitro, the underlying molecular mechanism remains unknown. Here, we examined the involvement of the LINC complex in radiation-enhanced cell migration and invasion. A sublethal dose of X-ray radiation promoted human breast cancer MDA-MB-231 cell migration and invasion, whereas carbon ion beam radiation suppressed these processes in a dose-dependent manner. Depletion of SUN1 and SUN2 significantly suppressed X-ray-enhanced cell migration and invasion. Moreover, depletion or overexpression of each SUN1 splicing variant revealed that SUN1_888 containing 888 amino acids of SUN1 but not SUN1_916 was required for X-ray-enhanced migration and invasion. In addition, the results suggested that X-ray irradiation affected the expression level of SUN1 splicing variants and a SUN protein binding partner, nesprins. Taken together, our findings supported that the LINC complex contributed to photon-enhanced cell migration and invasion. © 2018 The Authors. Cancer Science published by John Wiley & Sons Australia, Ltd on behalf of Japanese Cancer Association.

  11. Distribution of linker histone variants during plant cell differentiation in the developmental zones of the maize root, dedifferentiation in callus culture after auxin treatment

    Directory of Open Access Journals (Sweden)

    ANASTASIOS ALATZAS

    2008-01-01

    Full Text Available Although several linker histone variants have been studied in both animal and plant organisms, little is known about their distribution during processes that involve alterations in chromatin function, such as differentiation, dedifferentiation and hormone treatment. In this study, we identified linker histone variants by using specific anti-histone Hl antibodies. Each variant's ratio to total Hl in the three developmental zones of maize (Zea mays L. root and in callus cultures derived from them was estimated in order to define possible alterations either during plant cell differentiation or during their dedifferentiation. We also evaluated linker histone variants' ratios in the developmental zones of maize roots treated with auxin in order to examine the effects of exogenous applied auxin to linker histone variant distribution. Finally, immunohistochemical detection was used to identify the root tissues containing each variant and correlate them with the physiological status of the plant cells. According to the results presented in this study, linker histone variants' ratios are altered in the developmental zones of maize root, while they are similar to the meristematic zone in samples from callus cultures and to the differentiation zone in samples from roots treated with auxin. We propose that the alterations in linker histone variants' ratios are correlated with plant cell differentiation and dedifferentiation.

  12. Synthesis and polymerization of vinyl triazolium ionic liquids

    Science.gov (United States)

    Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian

    2018-05-15

    Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.

  13. Better flocculants by radiation induced polymerization

    International Nuclear Information System (INIS)

    Laizier, J.; Gaussens, G.

    1978-01-01

    The use of radiation induced polymerization should theoritically allow to prepare better flocculants. The testings of several products prepared by such a process shows that better properties are indeed obtained: better efficiencies, lower amounts needed, better overall properties [fr

  14. Compression Behavior of High Performance Polymeric Fibers

    National Research Council Canada - National Science Library

    Kumar, Satish

    2003-01-01

    Hydrogen bonding has proven to be effective in improving the compressive strength of rigid-rod polymeric fibers without resulting in a decrease in tensile strength while covalent crosslinking results in brittle fibers...

  15. Silicon dioxide obtained by Polymeric Precursor Method

    International Nuclear Information System (INIS)

    Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A.

    2011-01-01

    The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO 2 oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

  16. Thermal polymerization of Moringa oleifera oil

    International Nuclear Information System (INIS)

    Melo, Tania M.S.; Novack, Katia M.; Leandro, Cristiano

    2011-01-01

    It is increasingly clear both for society and the scientific community, that is necessary to find alternatives to reduce the use of polymeric materials because of their damage to the environment. One way to minimize the environmental problems related to the use of polymers is try to make them quickly degradable. In this study it was obtained a material with polymeric appearance derived from heating of the vegetable oil extracted from seeds of Moringa oleifera. The resulting product is an interesting alternative to obtain polymeric materials that may have biodegradable characteristics, coming from a renewable source and low cost. Moringa oil can be used since it has a high content of unsaturated fatty acids, and its main constituent oleic acid. All samples were characterized by FTIR, NMR and GPC. It was obtained a polymeric material, malleable, high viscosity, with some elasticity, low crystallinity and no unpleasant odor. (author)

  17. Deformation and flow of polymeric materials

    CERN Document Server

    Münstedt, Helmut

    2014-01-01

    This book describes the properties of single polymer molecules and polymeric materials and the methods how to characterize them. Molar masses, molar mass distributions and branching structure are discussed in detail. These properties are decisive for a deeper understanding of structure/properties relationships of polymeric materials. This book therefore describes and discusses them in detail. The mechanical behavior as a function of time and temperature is a key subject of the book. The authors present it on the basis of many original results they have obtained in their long research careers. They present the temperature dependence of mechanical properties of various polymeric materials in a wide temperature range: from cryogenic temperatures to the melt. Besides an extensive data collection on the transitions of various different polymeric materials, they also carefully present the physical explanations of the observed phenomena. Glass transition and melting temperatures are discussed, particularly, with the...

  18. Polymerization of sodium methacrylate induced by irradiation

    International Nuclear Information System (INIS)

    Galvan S, A.

    1998-01-01

    This work has two objectives, first: it is pretended to localize the lines of carbon links in its IR spectra, and second: following the polymerization of sodium methacrylate according to that it is irradiated with gamma rays. (Author)

  19. Reverse-osmosis membranes by plasma polymerization

    Science.gov (United States)

    Hollahan, J. R.; Wydeven, T.

    1972-01-01

    Thin allyl amine polymer films were developed using plasma polymerization. Resulting dry composite membranes effectively reject sodium chloride during reverse osmosis. Films are 98% sodium chloride rejective, and 46% urea rejective.

  20. Bioadhesive polymeric platforms for transmucosal drug delivery ...

    African Journals Online (AJOL)

    Bioadhesive polymeric platforms for transmucosal drug delivery systems – a review. ... administration of certain classes of drugs, especially peptides and proteins. ... characteristics of desired bioadhesive polymers, this article then proceeds to ...

  1. Transformation kinetics of mixed polymeric substrates under ...

    African Journals Online (AJOL)

    bglucosidase and a-mannosidase were abundantly secreted in the growth medium. This research is the first report on mixed polymeric substrate biodegradation under sewer condition by A. niger, and could be considered as an open window on ...

  2. Post polymerization cure shape memory polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

    2017-01-10

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  3. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

    Science.gov (United States)

    Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  4. Polymeric Nanogels Obtained by Radiation Technique

    Energy Technology Data Exchange (ETDEWEB)

    Ulanski, P.; Kadłubowski, A. K.; Olejnik,; Rokita, B.; Wach, R.; Rosiak, J. M. [Institute of Applied Radiation Chemistry, Technical University of Lodz, Lodz (Poland)

    2009-07-01

    Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials.

  5. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

    Science.gov (United States)

    Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  6. Volumetric polymerization shrinkage of contemporary composite resins

    Directory of Open Access Journals (Sweden)

    Halim Nagem Filho

    2007-10-01

    Full Text Available The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill Magic, Alert, and Solitaire to determine whether there are differences among these materials. The tests were conducted with precision of 0.1 mg. The volumetric shrinkage was measured by hydrostatic weighing before and after polymerization and calculated by known mathematical equations. One-way ANOVA (a or = 0.05 was used to determine statistically significant differences in volumetric shrinkage among the tested composite resins. Suprafill (1.87±0.01 and Definite (1.89±0.01 shrank significantly less than the other composite resins. SureFil (2.01±0.06, Filtek Z250 (1.99±0.03, and Fill Magic (2.02±0.02 presented intermediate levels of polymerization shrinkage. Alert and Solitaire presented the highest degree of polymerization shrinkage. Knowing the polymerization shrinkage rates of the commercially available composite resins, the dentist would be able to choose between using composite resins with lower polymerization shrinkage rates or adopting technical or operational procedures to minimize the adverse effects deriving from resin contraction during light-activation.

  7. Post polymerization cure shape memory polymers

    Science.gov (United States)

    Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

    2014-11-11

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  8. Polymeric Nanogels Obtained by Radiation Technique

    International Nuclear Information System (INIS)

    Ulanski, P.; Kadłubowski, A.K.; Olejnik; Rokita, B.; Wach, R.; Rosiak, J.M.

    2009-01-01

    Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials

  9. Stimuli-Responsive Polymeric Nanoparticles.

    Science.gov (United States)

    Liu, Xiaolin; Yang, Ying; Urban, Marek W

    2017-07-01

    There is increasing evidence that stimuli-responsive nanomaterials have become significantly critical components of modern materials design and technological developments. Recent advances in synthesis and fabrication of stimuli-responsive polymeric nanoparticles with built-in stimuli-responsive components (Part A) and surface modifications of functional nanoparticles that facilitate responsiveness (Part B) are outlined here. The synthesis and construction of stimuli-responsive spherical, core-shell, concentric, hollow, Janus, gibbous/inverse gibbous, and cocklebur morphologies are discussed in Part A, with the focus on shape, color, or size changes resulting from external stimuli. Although inorganic/metallic nanoparticles exhibit many useful properties, including thermal or electrical conductivity, catalytic activity, or magnetic properties, their assemblies and formation of higher order constructs are often enhanced by surface modifications. Section B focuses on selected surface reactions that lead to responsiveness achieved by decorating nanoparticles with stimuli-responsive polymers. Although grafting-to and grafting-from dominate these synthetic efforts, there are opportunities for developing novel synthetic approaches facilitating controllable recognition, signaling, or sequential responses. Many nanotechnologies utilize a combination of organic and inorganic phases to produce ceramic or metallic nanoparticles. One can envision the development of new properties by combining inorganic (metals, metal oxides) and organic (polymer) phases into one nanoparticle designated as "ceramers" (inorganics) and "metamers" (metallic). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Nonperturbative Renormalization Group Approach to Polymerized Membranes

    Science.gov (United States)

    Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

    2014-03-01

    Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

  11. The tempered polymerization of human neuroserpin.

    Directory of Open Access Journals (Sweden)

    Rosina Noto

    Full Text Available Neuroserpin, a member of the serpin protein superfamily, is an inhibitor of proteolytic activity that is involved in pathologies such as ischemia, Alzheimer's disease, and Familial Encephalopathy with Neuroserpin Inclusion Bodies (FENIB. The latter belongs to a class of conformational diseases, known as serpinopathies, which are related to the aberrant polymerization of serpin mutants. Neuroserpin is known to polymerize, even in its wild type form, under thermal stress. Here, we study the mechanism of neuroserpin polymerization over a wide range of temperatures by different techniques. Our experiments show how the onset of polymerization is dependent on the formation of an intermediate monomeric conformer, which then associates with a native monomer to yield a dimeric species. After the formation of small polymers, the aggregation proceeds via monomer addition as well as polymer-polymer association. No further secondary mechanism takes place up to very high temperatures, thus resulting in the formation of neuroserpin linear polymeric chains. Most interesting, the overall aggregation is tuned by the co-occurrence of monomer inactivation (i.e. the formation of latent neuroserpin and by a mechanism of fragmentation. The polymerization kinetics exhibit a unique modulation of the average mass and size of polymers, which might suggest synchronization among the different processes involved. Thus, fragmentation would control and temper the aggregation process, instead of enhancing it, as typically observed (e.g. for amyloid fibrillation.

  12. Characterization behavior of some polymeric composite ion exchangers

    International Nuclear Information System (INIS)

    El-Zahhar, A.A; Ahdel-Aziz, H.M.; Siyam, T.

    2005-01-01

    Polymeric composite resins were prepared by template polymerization process in aqueous solution. Thermogravimetric analysis (TGA), differential thermal analysis (DTA) and The X-ray diffraction patterns (XRD) were performed to evaluate the physico chemical properties of the different polymeric composite resins. The TGA and DTA clarify high thermal stability of prepared polymeric composite resins. XRD of prepared polymeric composite shows that there is crystalline structure of some resins while other are amorphous one

  13. Substitution of the Lys linker with the β-Ala linker dramatically decreased the renal uptake of 99mTc-labeled Arg-X-Asp-conjugated and X-Ala-Asp-conjugated α-melanocyte stimulating hormone peptides.

    Science.gov (United States)

    Flook, Adam M; Yang, Jianquan; Miao, Yubin

    2014-11-13

    The purpose of this study was to examine whether the substitution of the Lys linker with the β-Ala could reduce the renal uptake of (99m)Tc-labeled Arg-X-Asp-conjugated and X-Ala-Asp-conjugated α-melanocyte stimulating hormone (α-MSH) peptides. RSD-β-Ala-(Arg(11))CCMSH (1) {c[Arg-Ser-Asp-dTyr-Asp]-β-Ala-Cys-Cys-Glu-His-dPhe-Arg-Trp-Cys-Arg-Pro-Val-NH2}, RTD-β-Ala-(Arg(11))CCMSH (2), RVD-β-Ala-(Arg(11))CCMSH (3), RAD-β-Ala-(Arg(11))CCMSH (4), NAD-β-Ala-(Arg(11))CCMSH (5), and EAD-β-Ala-(Arg(11))CCMSH (6) peptides were synthesized and evaluated for their melanocortin 1 (MC1) receptor binding affinities in B16/F1 melanoma cells. The biodistribution of their (99m)Tc-conjugates were determined in B16/F1 melanoma-bearing C57 mice. The substitution of the Lys linker with β-Ala linker dramatically reduced the renal uptake of all six (99m)Tc-peptides. (99m)Tc-4 exhibited the highest melanoma uptake (15.66 ± 6.19% ID/g) and the lowest kidney uptake (20.18 ± 3.86% ID/g) among these (99m)Tc-peptides at 2 h postinjection. The B16/F1 melanoma lesions could be clearly visualized by single photon emission computed tomography (SPECT)/CT using (99m)Tc-4 as an imaging probe.

  14. Nanoparticle-Supported Molecular Polymerization Catalysts

    OpenAIRE

    Amgoune, Abderramane; Krumova, Marina; Mecking, Stefan

    2008-01-01

    Homogeneous molecular catalysts are immobilzed in a well-defined fashion on individual silica nanoparticles with a narrow particle size distribution by covalent attachment. This synthetic methodology is demonstrated with modified salicylaldiminato-substituted titanium(IV) complexes incorporating a trimethoxysilane-terminated linker: dichloro-bis[κ2-N,O-6-(3-(trimethoxysilyl)propoxyphenylimino)-2-tert-butyl-phenolato]titanium(IV) (3) and dichlorobis[κ2-N,O-6-(4-(trimethoxysilyl)propoxy-2,3,5,6...

  15. Fabrication of electrospun HPGL scaffolds via glycidyl methacrylate cross-linker: Morphology, mechanical and biological properties

    Energy Technology Data Exchange (ETDEWEB)

    Baratéla, Fernando José Costa; Zazuco Higa, Olga [Biotechnology Center, Institute of Energy and Nuclear Research (IPEN), Av. Professor Lineu Prestes 2242, 05508-000 São Paulo, SP (Brazil); Duarte dos Passos, Esdras [PostGraduate Program in Materials for Engineering, Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil); Alencar de Queiroz, Alvaro Antonio, E-mail: alencar@unifei.edu.br [Physics and Chemistry Institute (IFQ), Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil); High Voltage Laboratory (LAT-EFEI), Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil)

    2017-04-01

    Electrospinning is a suitable method to produce scaffolds composed of nanoscale to microscale fibers, which are comparable to the extracellular matrix (ECM). Hyperbranched polyglycerol (HPGL) is a highly biocompatible polyether polyol potentially useful for the design of fibrous scaffolds mimicking the ECM architecture. However, scaffolds developed from HPGL have poor mechanical properties and morphological stability in the aqueous environments required for tissue engineering applications. This work reports the production of stable electrospun HPGL scaffolds (EHPGLS) using glycidyl methacrylate (GMA) as cross-linker to enhance the water stability and mechanical property of electrospun HPGL. The diameter and morphology of the produced EHPGLS were analyzed by scanning electron microscopy (SEM). It was observed that electrical fields in the range of 0.2 kV·cm{sup −1} to 1.0 kV·cm{sup −1} decrease the average fiber diameter of EHPGLS. The increase in porosity of EHPGLS with GMA concentration indicates the in situ formation of a heterogeneous structure resultant from the phase separation during crosslinking of HPGL by GMA. EHPGLS containing 20% (w/w) GMA concentration possessed highest tensile strength (295.4 ± 11.32 kPa), which is approximately 58 times higher than that of non-crosslinked EHPGLS (5.1 ± 2.12 kPa). The MTS cell viability results showed that the EHPGLS have no significant cytotoxicity effect on Chinese hamster ovary (CHO-K1) cells. Scanning electron microscopy (SEM) indicates that the cultured BALB/3T3 fibroblasts cells were able to keep contact each other's, thus forming a homogeneous monolayer on the internal surface of the EHPGLS. - Highlights: • A hyperbranched polyglycerol (HPGL) scaffold with elastic modulus of 295.4 ± 11.32 kPa was developed for soft tissue repair. • HPGL scaffold was prepared by electrospinning method. • The porosity of HPGL scaffolds can be tuned by selecting the degree of GMA in HPGL. • Electrospun HPGL

  16. Integrity of the Linker of Nucleoskeleton and Cytoskeleton Is Required for Efficient Herpesvirus Nuclear Egress.

    Science.gov (United States)

    Klupp, Barbara G; Hellberg, Teresa; Granzow, Harald; Franzke, Kati; Dominguez Gonzalez, Beatriz; Goodchild, Rose E; Mettenleiter, Thomas C

    2017-10-01

    Herpesvirus capsids assemble in the nucleus, while final virion maturation proceeds in the cytoplasm. This requires that newly formed nucleocapsids cross the nuclear envelope (NE), which occurs by budding at the inner nuclear membrane (INM), release of the primary enveloped virion into the perinuclear space (PNS), and subsequent rapid fusion with the outer nuclear membrane (ONM). During this process, the NE remains intact, even at late stages of infection. In addition, the spacing between the INM and ONM is maintained, as is that between the primary virion envelope and nuclear membranes. The linker of nucleoskeleton and cytoskeleton (LINC) complex consists of INM proteins with a luminal SUN (Sad1/UNC-84 homology) domain connected to ONM proteins with a KASH (Klarsicht, ANC-1, SYNE homology) domain and is thought to be responsible for spacing the nuclear membranes. To investigate the role of the LINC complex during herpesvirus infection, we generated cell lines constitutively expressing dominant negative (dn) forms of SUN1 and SUN2. Ultrastructural analyses revealed a significant expansion of the PNS and the contiguous intracytoplasmic lumen, most likely representing endoplasmic reticulum (ER), especially in cells expressing dn-SUN2. After infection, primary virions accumulated in these expanded luminal regions, also very distant from the nucleus. The importance of the LINC complex was also confirmed by reduced progeny virus titers in cells expressing dn-SUN2. These data show that the intact LINC complex is required for efficient nuclear egress of herpesviruses, likely acting to promote fusion of primary enveloped virions with the ONM. IMPORTANCE While the viral factors for primary envelopment of nucleocapsids at the inner nuclear membrane are known to the point of high-resolution structures, the roles of cellular components and regulators remain enigmatic. Furthermore, the machinery responsible for fusion with the outer nuclear membrane is unsolved. We show here

  17. Genotoxic evaluation of polymeric nanoparticles

    Directory of Open Access Journals (Sweden)

    Tamara Iglesias Alonso

    2015-06-01

    Full Text Available An important strategy for optimizing the therapeutic efficacy of many conventional drugs is the development of polymeric nanoparticles (NPs, as it may expand their activities, reduce their toxicity, increase their bioactivity and improve biodistribution. The main objective of this study was to evaluate the genotoxicity of 8 different poly (anhydride NPs designed for the oral administration of therapeutic compounds by using the comet assay in combination with the enzyme formamidopypiridine DNA-glycosylase (FPG. Furthermore, the mitogen capacity of the NPs was evaluated by the proliferation assay. All NPs were tested at four concentrations (0, 0.5, 1 and 2 mg/mL in Caco-2 cells after 3 hours of treatment while selected NPs were also tested after 24 h. The comet assay was performed immediately after the treatment and cell proliferation was assessed by counting the treated cells after their incubation at 37 °C for 48h. Cells treated with 1 µM of the photosensitizer Ro 19-8022 plus 5 min of light, as well as cells treated with 100 µM H2O2 were included as positive controls in all the experiments. All NPs studied did not result in any increase in the frequency of strand breaks or alkali-labile sites in Caco-2 cells but they induced a slight concentration-dependent increase in net FPG sensitive sites (oxidized and/or alkylated bases. Furthermore, treated cells did not show changes in levels of proliferation in comparison with the negative control.

  18. Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

  19. Preparation of Thermo-Responsive and Cross-Linked Fluorinated Nanoparticles via RAFT-Mediated Aqueous Polymerization in Nanoreactors.

    Science.gov (United States)

    Ma, Jiachen; Zhang, Luqing; Geng, Bing; Azhar, Umair; Xu, Anhou; Zhang, Shuxiang

    2017-01-25

    In this work, a thermo-responsive and cross-linked fluoropolymer poly(2,2,2-Trifluoroethyl) methacrylate (PTFEMA) was successfully prepared by reversible addition-fragmentation chain transfer (RAFT) mediated aqueous polymerization with a thermo-responsive diblock poly(dimethylacrylamide- b - N -isopropylacrylamide) (PDMA- b -PNIPAM) that performed a dual function as both a nanoreactor and macro-RAFT agent. The cross-linked polymer particles proved to be in a spherical-like structure of about 50 nm in diameter and with a relatively narrow particle size distribution. ¹H-NMR and 19 F-NMR spectra showed that thermo-responsive diblock P(DMA- b -NIPAM) and cross-linked PTFEMA particles were successfully synthesized. Influence of the amount of ammonium persulfate (APS), the molar ratio of monomers to RAFT agent, influence of the amount of cross-linker on aqueous polymerization and thermo-responsive characterization of the particles are investigated. Monomer conversion increased from 44% to 94% with increasing the molar ratio of APS and P(DMA- b -NIPAM) from 1:9 to1:3. As the reaction proceeded, the particle size increased from 29 to 49 nm due to the consumption of TFEMA monomer. The size of cross-linked nanoparticles sharply decreased from 50.3 to 40.5 nm over the temperature range 14-44 °C, suggesting good temperature sensitivity for these nanoparticles.

  20. Structural Polymorphism of the Actin-Espin System: A Prototypical System of Filaments and Linkers in Stereocilia

    International Nuclear Information System (INIS)

    Purdy, Kirstin R.; Wong, Gerard C. L.; Bartles, James R.

    2007-01-01

    We examine the interaction between cytoskeletal F-actin and espin 3A, a prototypical actin bundling protein found in sensory cell microvilli, including ear cell stereocilia. Espin induces twist distortions in F-actin as well as facilitates bundle formation. Mutations in one of the two F-actin binding sites of espin, which have been implicated in deafness, can tune espin-actin interactions and radically transform the system's phase behavior. These results are compared to recent theoretical work on the general phase behavior linker-rod systems

  1. The First Extracellular Linker Is Important for Several Aspects of the Gating Mechanism of Human TRPA1 Channel

    Czech Academy of Sciences Publication Activity Database

    Maršáková, Lenka; Barvík, I.; Zíma, V.; Zímová, Lucie; Vlachová, Viktorie

    2017-01-01

    Roč. 10, Jan 31 (2017), č. článku 16. ISSN 1662-5099 R&D Projects: GA ČR(CZ) GA15-15839S; GA ČR(CZ) GBP304/12/G069; GA MŠk(CZ) EE2.3.30.0025 Institutional support: RVO:67985823 Keywords : TRP channel * S1-S2 linker * allyl isothiocynate * sensor module Subject RIV: FH - Neurology OBOR OECD: Neuroscience s (including psychophysiology Impact factor: 5.076, year: 2016

  2. Micropatterning of biomolecules on a glass substrate in fused silica microchannels by using photolabile linker-based surface activation

    International Nuclear Information System (INIS)

    Jang, K.; Mawatari, K.; Kitamori, T.; Xu, Y.; Sato, K.; Tanaka, Y.

    2012-01-01

    We report on a straightforward method for creating micropatterns of multiple biomolecules. The anti-fouling agent 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer and a photolabile linker (PL) were covalently linked to an amino-terminated silane surface. Patterns were generated by selective removal of the MPC polymer via UV irradiation. Multiple micropatterns of fluorescein isothiocyanate (FITC)-labeled bovine serum albumin (BSA) and rhodamine-labeled goat fragment antigen-binding fragments (FAB) were deposited on a same glass substrate. We also employed micropatterning of multiple biomolecules in that Texas red-labeled BSA and FITC-labeled rabbit anti-mouse IgG were placed inside a microchannel. (author)

  3. Polymerization of N-(fluoro phenyl) maleimides

    International Nuclear Information System (INIS)

    Barrales-Rienda, J.M.; Ramos, J.G.; Chaves, M.S.

    1979-01-01

    Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by azobisisobutyronitrile in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. 6 figures, 8 tables

  4. Characterization of A Am/MBA hydrogels prepared by radiation induced polymerization

    International Nuclear Information System (INIS)

    Mahmudi, N.; Rendevski, S.

    2012-01-01

    In this research the network structure of polyacrylamide hydrogels prepared by gamma radiation-induced polymerization has been investigated. The average molecular weight between cross-link junctions ‾M c and effective cross-link density of hydrogels were calculated from swelling data as well as shear modulus data. The mechanical tests showed that by increasing the amount of the cross linker methylenebisacrylamide (MBA) into hydrogels, the value of shear modulus G and cross-link density ν e increased, but the average molecular weight between cross-link junctions ‾M c , decreased. The ‾M c and the effective cross-link density ν e obtained from the mechanical characterization were significantly different than the values obtained from swelling experiments. These differences were attributed to the uncertainty on the value of the χ parameter used in the Flory-Rehner equations. The results have shown that simple compression analyses can be used for the determination of ν e without any need of polymer-solvent interaction parameter for its calculations from the swelling analysis. (Author)

  5. DNA-nanoparticle assemblies go organic: Macroscopic polymeric materials with nanosized features

    Directory of Open Access Journals (Sweden)

    Mentovich Elad D

    2012-05-01

    Full Text Available Abstract Background One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Method Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. Results and conclusions One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC, which creates an all-organic engineered network.

  6. DNA-nanoparticle assemblies go organic: macroscopic polymeric materials with nanosized features.

    Science.gov (United States)

    Mentovich, Elad D; Livanov, Konstantin; Prusty, Deepak K; Sowwan, Mukules; Richter, Shachar

    2012-05-30

    One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network.

  7. Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

    Directory of Open Access Journals (Sweden)

    Christian Dollendorf

    2013-08-01

    Full Text Available A redox-responsive polycationic system was synthesized via copolymerization of N,N-diethylacrylamide (DEAAm and 2-(dimethylaminoethyl methacrylate (DMAEMA. N,N’-bis(4-chlorobutanoylcystamine was used as disulfide-containing cross-linker to form networks by the quaternization of tertiary amine groups. The insoluble cationic hydrogels become soluble by reduction of disulfide to mercaptanes by use of dithiothreitol (DTT, tris(2-carboxyethylphosphine (TCEP or cysteamine, respectively. The soluble polymeric system can be cross-linked again by using oxygen or hydrogen peroxide under basic conditions. The redox-responsive polymer networks can be used for molecular inclusion and controlled release. As an example, phenolphthalein, methylene blue and reactive orange 16 were included into the network. After treatment with DTT a release of the dye could be recognized. Physical properties of the cross-linked materials, e.g., glass transition temperature (Tg, swelling behavior and cloud points (Tc were investigated. Redox-responsive behavior was further analyzed by rheological measurements.

  8. Polymeric micelles with ionic cores containing biodegradable cross-links for delivery of chemotherapeutic agents.

    Science.gov (United States)

    Kim, Jong Oh; Sahay, Gaurav; Kabanov, Alexander V; Bronich, Tatiana K

    2010-04-12

    Novel functional polymeric nanocarriers with ionic cores containing biodegradable cross-links were developed for delivery of chemotherapeutic agents. Block ionomer complexes (BIC) of poly(ethylene oxide)-b-poly(methacylic acid) (PEO-b-PMA) and divalent metal cations (Ca(2+)) were utilized as templates. Disulfide bonds were introduced into the ionic cores by using cystamine as a biodegradable cross-linker. The resulting cross-linked micelles with disulfide bonds represented soft, hydrogel-like nanospheres and demonstrated a time-dependent degradation in the conditions mimicking the intracellular reducing environment. The ionic character of the cores allowed to achieve a very high level of doxorubicin (DOX) loading (50% w/w) into the cross-linked micelles. DOX-loaded degradable cross-linked micelles exhibited more potent cytotoxicity against human A2780 ovarian carcinoma cells as compared to micellar formulations without disulfide linkages. These novel biodegradable cross-linked micelles are expected to be attractive candidates for delivery of anticancer drugs.

  9. Fabrication of Reductive-Responsive Prodrug Nanoparticles with Superior Structural Stability by Polymerization-Induced Self-Assembly and Functional Nanoscopic Platform for Drug Delivery.

    Science.gov (United States)

    Zhang, Wen-Jian; Hong, Chun-Yan; Pan, Cai-Yuan

    2016-09-12

    A highly efficient strategy, polymerization-induced self-assembly (PISA) for fabrication of the polymeric drug delivery systems in cancer chemotherapy is reported. Diblock prodrug copolymer, PEG-b-P(MEO2MA-co-CPTM) was used as the macro-RAFT agent to fabricate prodrug nanoparticles through PISA. The advantages of fabricating intelligent drug delivery system via this approach are as following: (1) Simultaneous fulfillment of polymerization, self-assembly, and drug encapsulation in one-pot at relatively high concentration (100 mg/mL); (2) Almost complete monomer conversion allows direct application of the resultant prodrug nanoparticles without further purification; (3) Robust structures of the resultant prodrug nanoparticles, because the cross-linker was used as the comonomer, resulted in core-cross-linking simultaneously with the formation of the prodrug nanoparticles; (4) The drug content in the resultant prodrug nanoparticles can be accurately modulated just via adjusting the feed molar ratio of MEO2MA/CPTM in the synthesis of PEG-b-P(MEO2MA-co-CPTM). The prodrug nanoparticles with similar diameters but various drug contents were obtained using different prodrug macro-CTA. In consideration of the long-term biological toxicity, the prodrug nanoparticles with higher drug content exhibit more excellent anticancer efficiency due to that lower dosage of them are enough for effectively killing HeLa cells.

  10. Impact of cathepsin B-sensitive triggers and hydrophilic linkers on in vitro efficacy of novel site-specific antibody-drug conjugates.

    Science.gov (United States)

    Bryden, Francesca; Martin, Camille; Letast, Stéphanie; Lles, Eva; Viéitez-Villemin, Inmaculada; Rousseau, Anaïs; Colas, Cyril; Brachet-Botineau, Marie; Allard-Vannier, Emilie; Larbouret, Christel; Viaud-Massuard, Marie-Claude; Joubert, Nicolas

    2018-03-14

    Herein we describe the synthesis and evaluation of four novel HER2-targeting, cathepsin B-sensitive antibody-drug conjugates bearing a monomethylauristatin E (MMAE) cytotoxic payload, constructed via the conjugation of cleavable linkers to trastuzumab using a site-specific bioconjugation methodology. These linkers vary by both cleavable trigger motif and hydrophilicity, containing one of two cathepsin B sensitive dipeptides (Val-Cit and Val-Ala), and engendered with either hydrophilic or hydrophobic character via application of a PEG 12 spacer. Through evaluation of physical properties, in vitro cytotoxicity, and receptor affinity of the resulting antibody-drug conjugates (ADCs), we have demonstrated that while both dipeptide triggers are effective, the increased hydrophobicity of the Val-Ala pair limits its utility within this type of linker. In addition, while PEGylation augments linker hydrophilicity, this change does not translate to more favourable ADC hydrophilicity or potency. While all described structures demonstrated excellent and similar in vitro cytotoxicity, the ADC with the ValCitPABMMAE linker shows the most promising combination of in vitro potency, structural homogeneity, and hydrophilicity, warranting further evaluation into its therapeutic potential.

  11. Mechanically Strong Aerogels Formed by Templated Growth of Polymer Cross- Linkers on Inorganic Nanoparticles

    Science.gov (United States)

    Leventis, Nicholas; Fabrizio, Eve F.; Johnston, Chris; Meador, Maryann

    2004-01-01

    In the search for materials with better mechanical, thermal, and electrical properties, it is becoming evident that oftentimes dispersing ceramic nanoparticles in plastics improves performance. Along these lines, chemical bonding (both covalent and noncovalent) between a filler and a polymer improves their compatibility, and thus enhances certain properties of the polymeric matrix above and beyond what is accomplished by simple doping with the filler. When a similarly sized dopant and matrix are used, elementary building blocks may also have certain distinct advantages (e.g., in catalysis). In this context, researchers at the NASA Glenn Research Center reasoned that in the extreme case, where the dopant and the matrix (e.g., a filler and a polymer) are not only sized similarly, but their relative amounts are comparable, the relative roles of the dopant and matrix can be reversed. Then, if the "filler," or a certain form thereof, possesses desirable properties of its own, such properties could be magnified by cross-linking with a polymer. We at Glenn have identified silica as such a filler in its lowest-density form, namely the silica aerogel.

  12. Electrospun polymeric nanofibers for transdermal drug delivery

    Directory of Open Access Journals (Sweden)

    Mahya Rahmani

    2017-04-01

    Full Text Available Conventional transdermal drug delivery systems (TDDS have been designed for drug delivery through the skin. These systems use the permeability property of stratum corneum, the outermost surface layer of the skin. Applying polymeric micro and nanofibers in drug delivery has recently attracted great attention and the electrospinning technique is the preferred method for polymeric micro-nanofibers fabrication with a great potential for drug delivery. More studies in the field of nanofibers containing drug are divided two categories: first, preparation and characterization of nanofibers containing drug and second, investigation of their therapeutic applications. Drugs used in electrospun nanofibers can be categorized into three main groups, including antibiotics and antimicrobial agents, anti-inflammatory agents and vitamins with therapeutic applications. In this paper, we review the application of electrospun polymeric scaffolds in TDDS and also introduce several pharmaceutical and therapeutic agents which have been used in polymer nanofibrous patches.

  13. Cross-linking of polymeric materials

    International Nuclear Information System (INIS)

    Bloom, L.I.; Du Plessis, T.A.; Meij, G.O.

    1991-01-01

    The invention provides a method of producing a cured polymeric artifact from a polymeric thermoplastic starting material, the material of the artifact having reduced thermoplasticity relative to the starting material and exhibiting an enhanced degree of cross-linking relative to the starting material. The method includes subjecting a polymeric thermoplastic starting material, which is capable of being cross-linked by irradiation, to sufficient irradiation partially to cross-linked the starting material to produce a thermoplastic partially cross-linked intermediate material. The thermoplasticity of the intermediate material is then reduced by heating it to raise its melting point. The invention also provides a method of making a partially cross-linked feedstocks and a master batch for use in making such artifacts

  14. Laser microstructuring for fabricating superhydrophobic polymeric surfaces

    Science.gov (United States)

    Cardoso, M. R.; Tribuzi, V.; Balogh, D. T.; Misoguti, L.; Mendonça, C. R.

    2011-02-01

    In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157°. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces.

  15. Preparation, structural analysis and bioactivity of ribonuclease A-albumin conjugate: tetra-conjugation or PEG as the linker.

    Science.gov (United States)

    Li, Chunju; Lin, Qixun; Wang, Jun; Shen, Lijuan; Ma, Guanghui; Su, Zhiguo; Hu, Tao

    2012-12-31

    Ribonuclease A (RNase A) is a therapeutic enzyme with cytotoxic action against tumor cells. Its clinical application is limited by the short half-life and insufficient stability. Conjugation of albumin can overcome the limitation, whereas dramatically decrease the enzymatic activity of RNase A. Here, three strategies were proposed to prepare the RNase A-bovine serum albumin (BSA) conjugates. R-SMCC-B (a conjugate of four RNase A attached with one BSA) and R-PEG-B (a mono-conjugate) were prepared using Sulfo-SMCC (a short bifunctional linker) and mal-PEG-NHS (a bifunctional PEG), respectively. Mal-PEG-NHS and hexadecylamine (HDA) were used to prepare the mono-conjugate, R-HDA-B, where HDA was adopted to bind BSA. The PEG linker can elongate the proximity between RNase A and BSA. In contrast, four RNase A were closely located on BSA in R-SMCC-B. R-SMCC-B showed the lowest K(m) and the highest relative enzymatic activity and k(cat)/K(m) in the three conjugates. Presumably, the tetravalent interaction of RNase A in R-SMCC-B can increase the binding affinity to its substrate. In addition, the slow release of BSA from R-HDA-B may increase the enzymatic activity of R-HDA-B. Our study is expected to provide strategies to develop protein-albumin conjugate with high therapeutic potential. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Wall to membrane linkers, stretch activated channels, and the detection of tension, voltage, temperature, auxin, and pH

    Science.gov (United States)

    Pickard, B. G.

    1992-01-01

    Introduction. The higher plant is a heterogeneous, mechanically prestressed structure continually subject to shifting forces. When a cell grows in a plant at gravitropic equilibrium, it must create localized maxima of shear in walls of neighboring cells. Such mechanical stress and strain are likely detected in a variety of ways. However, tension-sensitive ion channels are of particular interest because it appears that they are elaborately evolved for sensory function. We hypothesize that 1) the patchy patterns of high shear are focused via wall-to-membrane linkers onto the plasma membrane, where 2) they are translated by mechanosensory cation channels into corresponding patterns of high cytosolic Ca2+, which 3) initiate local enhancement of wall expansion. Further, we hypothesize that the local promotion of enhancement is achieved at least in part by local intensification of auxin transport across the plasma membrane. By implication, when an organ is asymmetrically pressed, rubbed, or bent or when it is displaced in the gravitational field, the net asymmetry of shear stress occurring across the organ would lead to asymmetric redistribution of auxin and corrective asymmetric growth. We shall describe a representative mechanosensitive Ca(2+) -selective cation channel (MCaC) with susceptibilities to xenobiotics implicating it as a force transducer in thigmo- and gravitropism. Then, we shall consider whether a putative wall-to-membrane linker (WML) could be a key feature of the molecular architecture permitting the stress distributed in the wall system to be focused on the channels.

  17. Probing the Influence of Linker Length and Flexibility in the Design and Synthesis of New Trehalase Inhibitors

    Directory of Open Access Journals (Sweden)

    Giampiero D’Adamio

    2018-02-01

    Full Text Available This work aims to synthesize new trehalase inhibitors selective towards the insect trehalase versus the porcine trehalase, in view of their application as potentially non-toxic insecticides and fungicides. The synthesis of a new pseudodisaccharide mimetic 8, by means of a stereoselective α-glucosylation of the key pyrrolizidine intermediate 13, was accomplished. The activity of compound 8 as trehalase inhibitor towards C. riparius trehalase was evaluated and the results showed that 8 was active in the μM range and showed a good selectivity towards the insect trehalase. To reduce the overall number of synthetic steps, simpler and more flexible disaccharide mimetics 9–11 bearing a pyrrolidine nucleus instead of the pyrrolizidine core were synthesized. The biological data showed the key role of the linker chain’s length in inducing inhibitory properties, since only compounds 9 (α,β-mixture, bearing a two-carbon atom linker chain, maintained activity as trehalase inhibitors. A proper change in the glucosyl donor-protecting groups allowed the stereoselective synthesis of the β-glucoside 9β, which was active in the low micromolar range (IC50 = 0.78 μM and 12-fold more potent (and more selective than 9α towards the insect trehalase.

  18. Parsing the roles of neck-linker docking and tethered head diffusion in the stepping dynamics of kinesin.

    Science.gov (United States)

    Zhang, Zhechun; Goldtzvik, Yonathan; Thirumalai, D

    2017-11-14

    Kinesin walks processively on microtubules (MTs) in an asymmetric hand-over-hand manner consuming one ATP molecule per 16-nm step. The individual contributions due to docking of the approximately 13-residue neck linker to the leading head (deemed to be the power stroke) and diffusion of the trailing head (TH) that contributes in propelling the motor by 16 nm have not been quantified. We use molecular simulations by creating a coarse-grained model of the MT-kinesin complex, which reproduces the measured stall force as well as the force required to dislodge the motor head from the MT, to show that nearly three-quarters of the step occurs by bidirectional stochastic motion of the TH. However, docking of the neck linker to the leading head constrains the extent of diffusion and minimizes the probability that kinesin takes side steps, implying that both the events are necessary in the motility of kinesin and for the maintenance of processivity. Surprisingly, we find that during a single step, the TH stochastically hops multiple times between the geometrically accessible neighboring sites on the MT before forming a stable interaction with the target binding site with correct orientation between the motor head and the [Formula: see text] tubulin dimer.

  19. Improving the performance of DomainDiscovery of protein domain boundary assignment using inter-domain linker index

    Directory of Open Access Journals (Sweden)

    Zomaya Albert Y

    2006-12-01

    Full Text Available Abstract Background Knowledge of protein domain boundaries is critical for the characterisation and understanding of protein function. The ability to identify domains without the knowledge of the structure – by using sequence information only – is an essential step in many types of protein analyses. In this present study, we demonstrate that the performance of DomainDiscovery is improved significantly by including the inter-domain linker index value for domain identification from sequence-based information. Improved DomainDiscovery uses a Support Vector Machine (SVM approach and a unique training dataset built on the principle of consensus among experts in defining domains in protein structure. The SVM was trained using a PSSM (Position Specific Scoring Matrix, secondary structure, solvent accessibility information and inter-domain linker index to detect possible domain boundaries for a target sequence. Results Improved DomainDiscovery is compared with other methods by benchmarking against a structurally non-redundant dataset and also CASP5 targets. Improved DomainDiscovery achieves 70% accuracy for domain boundary identification in multi-domains proteins. Conclusion Improved DomainDiscovery compares favourably to the performance of other methods and excels in the identification of domain boundaries for multi-domain proteins as a result of introducing support vector machine with benchmark_2 dataset.

  20. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Neergaard, Jesper; Hassager, Ole

    1999-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane. The polymeric materialis described by an arbitrary combination of a viscoelastic and a purely viscous component to the stress. Some viscoelastic materials described by a Mooney......-Rivlin model show a monotone increasingpressure during inflation of a spherical membrane. These materials develop a homogeneous membrane thickness in agreement with the Considere-Pearson condition. Molecularly based models such as the neo-Hookean, Doi-Edwards or Tom-Pom model show a pressure maximum when...... inflated. Membranesdescribed by these models develop a local thinning of the membrane which may lead to bursting in finite time....

  1. Polymeric materials obtained by electron beam irradiation

    International Nuclear Information System (INIS)

    Dragusin, M.; Moraru, R.; Martin, D.; Radoiu, M.; Marghitu, S.; Oproiu, C.

    1995-01-01

    Research activities in the field of electron beam irradiation of monomer aqueous solution to produce polymeric materials used for waste waters treatment, agriculture and medicine are presented. The technologies and special features of these polymeric materials are also described. The influence of the chemical composition of the solution to ba irradiated, absorbed dose level and absorbed dose rate level are discussed. Two kinds of polyelectrolytes, PA and PV types and three kinds of hydrogels, pAAm, pAAmNa and pNaAc types, the production of which was first developed with IETI-10000 Co-60 source and then adapted to the linacs built in Accelerator Laboratory, are described. (author)

  2. Mechanism and kinetics of addition polymerizations

    CERN Document Server

    Kucera, M

    1991-01-01

    This volume presents an up-to-date survey of knowledge concerning addition type polymerizations. It contains nine chapters, each of which covers a particular basic term. Whenever necessary, the phenomena are discussed from the viewpoint of both stationary and non-stationary state of radical, ionic (i.e. anionic and cationic) and coordination polymerization. Special attention has been paid to the propagation process. It provides not only a general overview but also information on important special cases (theoretical conditions of propagation, influence of external factors, controlled propagatio

  3. Polymeric matrix materials for infrared metamaterials

    Science.gov (United States)

    Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

    2014-04-22

    A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

  4. Immobilization of biocatalysts for enzymatic polymerizations : Possibilities, advantages, applications

    NARCIS (Netherlands)

    Miletic, Nemanja; Nastasovic, Aleksandra; Loos, Katja; Miletić, Nemanja; Nastasović, Aleksandra

    Biotechnology also holds tremendous opportunities for realizing functional polymeric materials. Biocatalytic pathways to polymeric materials are an emerging research area with not only enormous scientific and technological promise, but also a tremendous impact on environmental issues. Many of the

  5. Polymerization Initiated at the Sidewalls of Carbon Nanotubes

    Science.gov (United States)

    Tour, James M.; Hudson, Jared L.

    2011-01-01

    A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

  6. Interfacial Polymerization of Polyaniline Nanofibers Grafted to Au Surfaces

    National Research Council Canada - National Science Library

    Sawall, D

    2004-01-01

    .... The in-situ polymerization technique of these PANI nanofibers in the presence of sulfonated polystyrene allowed for the growth of PANI 2-D nanostructures embedded in the polymerized sulfonated host...

  7. Crystallization and preliminary X-ray analysis of Acetivibrio cellulolyticus cellulosomal type II cohesin module: two versions having different linker lengths

    International Nuclear Information System (INIS)

    Noach, Ilit; Alber, Orly; Bayer, Edward A.; Lamed, Raphael; Levy-Assaraf, Maly; Shimon, Linda J. W.; Frolow, Felix

    2007-01-01

    The cloning, expression, purification, crystallization and preliminary X-ray characterization of two protein constructs of the second type II cohesin module from A. cellulolyticus ScaB are described. Both constructs contain the native N-terminal linker, but only one of them contains the full-length 45-residue C-terminal linker; the other contains a five-residue segment of this linker. The second type II cohesin module of the cellulosomal scaffoldin polypeptide ScaB from Acetivibrio cellulolyticus (CohB2) was cloned into two constructs: one containing a short (five-residue) C-terminal linker (CohB2-S) and the second incorporating the full native 45-residue linker (CohB2-L). Both constructs encode proteins that also include the full native six-residue N-terminal linker. The CohB2-S and CohB2-L proteins were expressed, purified and crystallized in the orthorhombic crystal system, but with different unit cells and symmetries: space group P2 1 2 1 2 1 with unit-cell parameters a = 90.36, b = 68.65, c = 111.29 Å for CohB2-S and space group P2 1 2 1 2 with unit-cell parameters a = 68.76, b = 159.22, c = 44.21 Å for CohB2-L. The crystals diffracted to 2.0 and 2.9 Å resolution, respectively. The asymmetric unit of CohB2-S contains three cohesin molecules, while that of CohB2-L contains two molecules

  8. The linker domain of poly(rC) binding protein 2 is a major determinant in poliovirus cap-independent translation.

    Science.gov (United States)

    Sean, Polen; Nguyen, Joseph H C; Semler, Bert L

    2008-09-01

    Poliovirus, a member of the enterovirus genus in the family Picornaviridae, is the causative agent of poliomyelitis. Translation of the viral genome is mediated through an internal ribosomal entry site (IRES) encoded within the 5' noncoding region (5' NCR). IRES elements are highly structured RNA sequences that facilitate the recruitment of ribosomes for translation. Previous studies have shown that binding of a cellular protein, poly(rC) binding protein 2 (PCBP2), to a major stem-loop structure in the genomic 5' NCR is necessary for the translation of picornaviruses containing type I IRES elements, including poliovirus, coxsackievirus, and human rhinovirus. PCBP1, an isoform that shares approximately 90% amino acid identity to PCBP2, cannot efficiently stimulate poliovirus IRES-mediated translation, most likely due to its reduced binding affinity to stem-loop IV within the poliovirus IRES. The primary differences between PCBP1 and PCBP2 are found in the so-called linker domain between the second and third K-homology (KH) domains of these proteins. We hypothesize that the linker region of PCBP2 augments binding to poliovirus stem-loop IV RNA. To test this hypothesis, we generated six PCBP1/PCBP2 chimeric proteins. The recombinant PCBP1/PCBP2 chimeric proteins were able to interact with poliovirus stem-loop I RNA and participate in protein-protein interactions. We demonstrated that the PCBP1/PCBP2 chimeric proteins with the PCBP2 linker, but not with the PCBP1 linker, were able to interact with poliovirus stem-loop IV RNA, and could subsequently stimulate poliovirus IRES-mediated translation. In addition, using a monoclonal anti-PCBP2 antibody (directed against the PCBP2 linker domain) in mobility shift assays, we showed that the PCBP2 linker domain modulates binding to poliovirus stem-loop IV RNA via a mechanism that is not inhibited by the antibody.

  9. Substitutions in conserved regions preceding and within the linker affect activity and flexibility of tRNase ZL, the long form of tRNase Z.

    Directory of Open Access Journals (Sweden)

    Makenzie Saoura

    Full Text Available The enzyme tRNase Z, a member of the metallo-β-lactamase family, endonucleolytically removes 3' trailers from precursor tRNAs, preparing them for CCA addition and aminoacylation. The short form of tRNase Z, tRNase ZS, functions as a homodimer and is found in all prokaryotes and some eukaryotes. The long form, tRNase ZL, related to tRNase ZS through tandem duplication and found only in eukaryotes, possesses ~2,000-fold greater catalytic efficiency than tRNase ZS. tRNase ZL consists of related but diverged amino and carboxy domains connected by a flexible linker (also referred to as a flexible tether and functions as a monomer. The amino domain retains the flexible arm responsible for substrate recognition and binding while the carboxy domain retains the active site. The linker region was explored by Ala-scanning through two conserved regions of D. melanogaster tRNase Z: NdomTprox, located at the carboxy end of the amino domain proximal to the linker, and Tflex, a flexible site in the linker. Periodic substitutions in a hydrophobic patch (F329 and L332 at the carboxy end of NdomTprox show 2,700 and 670-fold impairment relative to wild type, respectively, accompanied by reduced linker flexibility at N-T inside the Ndom- linker boundary. The Ala substitution for N378 in the Tflex region has 10-fold higher catalytic efficiency than wild type and locally decreased flexibility, while the Ala substitution at R382 reduces catalytic efficiency ~50-fold. These changes in pre-tRNA processing kinetics and protein flexibility are interpreted in light of a recent crystal structure for S. cerevisiae tRNase Z, suggesting transmission of local changes in hydrophobicity into the skeleton of the amino domain.

  10. Synthesis, recognition and evaluation of molecularly imprinted polymer nanoparticle using miniemulsion polymerization for controlled release and analysis of risperidone in human plasma samples

    International Nuclear Information System (INIS)

    Asadi, Ebadullah; Azodi-Deilami, Saman; Abdouss, Majid; Kordestani, Davood; Rahimi, Alireza; Asadi, Somayeh

    2014-01-01

    We prepared high selective imprinted nanoparticle polymers by a miniemulsion polymerization technique, using risperidone as the template, MAA as the functional monomers, and TRIM as the cross-linker in acetonitrile as solvent. The morphology of the nanoparticles determined by scanning electron microscopy (SEM) images and drug release, binding properties and dynamic light scattering (DLS) of molecularly imprinted polymers (MIPs) were studied. Controlled release of risperidone from nanoparticles was investigated through in 1% wt sodium dodecyl sulfate aqueous solution and by measuring the absorbance by HPLC-UV. The results showed that the imprinted nanoparticles exhibited a higher binding level and slower release rate than non-imprinted nanoparticles, which contributed to interaction of risperidone with imprinted cavities within nanoparticles. Furthermore, the results from HPLC showed good precision (5% for 50.0 µg L -1 ) and recoveries (between 86-91) using MIP from human plasma samples

  11. Novel, one-step synthesis of zwitterionic polymer nanoparticles via distillation-precipitation polymerization and its application for dye removal membrane.

    Science.gov (United States)

    Ibrahim, G P Syed; Isloor, Arun M; Inamuddin; Asiri, Abdullah M; Ismail, Norafiqah; Ismail, Ahmed Fauzi; Ashraf, Ghulam Md

    2017-11-21

    In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As  far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m 2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.

  12. Yeast linker histone Hho1p is required for efficient RNA polymerase I processivity and transcriptional silencing at the ribosomal DNA

    OpenAIRE

    Levy, Anat; Eyal, Miri; Hershkovits, Gitit; Salmon-Divon, Mali; Klutstein, Michael; Katcoff, Don Jay

    2008-01-01

    Nucleosome core particles in eukaryotes are linked by a stretch of DNA that is usually associated with a linker histone. Here, we show in yeast, that the presence of yeast linker histone Hho1p represses expression of a pol II transcribed gene (MET15) embedded in the rDNA. In vivo deletions of Hho1p sequences showed that the second globular domain is sufficient for that repression, whereas the presence of the N terminus is required for its derepression. In contrast, a run-on assay confirmed by...

  13. Vibrating polymeric microsieves: Antifouling strategies for microfiltration

    NARCIS (Netherlands)

    Girones nogue, Miriam; Akbarsyah, Imam J.; Bolhuis-Versteeg, Lydia A.M.; Lammertink, Rob G.H.; Wessling, Matthias

    2006-01-01

    Constant flux performance in time is achieved with polyethersulfone (PES) polymeric microsieves when filtering protein solutions, skimmed milk and white beer in combination with backpulsing. Such microsieves are fabricated by phase separation micromolding (PSμM) and possess pores around 2 μm. The

  14. Inflation and Failure of Polymeric Membranes

    DEFF Research Database (Denmark)

    Hassager, Ole; Neergaard, Jesper

    2000-01-01

    We consider the inflation of an axisymmetric polymeric membrane.Some membranes composed of viscoelastic materialsdescribed by a Mooney-Rivlin model show a monotone increasingpressure during inflation. These materialsdevelop a homogeneous membrane thickness in agreement with the Considere...... is found to stabilize the inflated polymer membrane....

  15. Gamma Radiation-Induced Template Polymerization Technique

    International Nuclear Information System (INIS)

    Siyam, T.

    2005-01-01

    Gamma radiation induced copolymerization of acrylamide sodiumacrylate (AM-AANa) in the presence and absence of the polymer additive was studied at low monomer concentration(1.4M/l). The results showed that the exponents of the dose rate for the polymerization rate was found to be 1.3 and 1.4 in the absence and in the presence of the polymer additive respectively. The molecular weight of the formed polymer increased by addition of the polymer to the system. In the presence of the polymer the comonomers polymerize on the added polymer. In the absence of the added polymer the comonomers polymerize according to the copolymerization process at the initial stage of the copolymerization. While at high conversion the residual comonomers polymerize on the formed macromolecular chains of the produced polymer. These studies showed that the copolymerization in the presence of added polymer is completely template copolymerization while in the absence of the polymer the copolymerization process is only template process with a high conversion

  16. Polymerization of epoxidized triglycerides with fluorosulfonic acid

    Science.gov (United States)

    The use of triglycerides as agri-based renewable raw materials for the development of new products is highly desirable in view of uncertain future petroleum prices. A new method of polymerizing epoxidized soybean oil has been devised with the use of fluorosulfonic acid. Depending on the reaction con...

  17. On viscoelastic instability in polymeric filaments

    DEFF Research Database (Denmark)

    Rasmussen, Henrik Koblitz; Hassager, Ole

    1999-01-01

    The 3D Lagrangian Integral Method is used to simulate the effects of surface tension on the viscoelastic end-plate instability, occuring in the rapid extension of some polymeric filaments between parallel plates. It is shovn that the surface tension delays the onset of the instability. Furthermore...

  18. Polymeric additive performance in closed whitewater systems

    Science.gov (United States)

    T. H. Wegner

    1984-01-01

    “With more stringent requirements on discharge water quality and with escalating water treatment costs, water recycling within the paper mill is of growing importance. A serious problem resulting from more white-water recycling is reduced drainage and fiber or fines retention because of diminished polymeric additive performance. To provide better insight for overcoming...

  19. Latent tracks in polymeric etched track detectors

    International Nuclear Information System (INIS)

    Yamauchi, Tomoya

    2013-01-01

    Track registration properties in polymeric track detectors, including Poly(allyl diglycol carbonate), Bispenol A polycarbonate, Poly(ethylen terephtarate), and Polyimide, have been investigated by means of Fourie transform Infararede FT-IR spectrometry. Chemical criterion on the track formation threshold has been proposes, in stead of the conventional physical track registration models. (author)

  20. Bioactive Polymeric Materials for Tissue Repair

    Directory of Open Access Journals (Sweden)

    Diane R. Bienek

    2017-01-01

    Full Text Available Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field.

  1. Hyaluronan polymeric micelles for topical drug delivery

    Czech Academy of Sciences Publication Activity Database

    Šmejkalová, D.; Muthný, T.; Nešporová, K.; Hermannová, M.; Achbergerová, E.; Huerta-Angelesa, G.; Marek Svoboda, M.; Čepa, M.; Machalová, V.; Luptáková, Dominika; Velebný, V.

    2017-01-01

    Roč. 156, JAN 20 (2017), s. 86-96 ISSN 0144-8617 Institutional support: RVO:61388971 Keywords : Skin penetration * Polymeric micelle * Hyaluronan Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 4.811, year: 2016

  2. The Morphology of Emulsion Polymerized Latex Particles

    Science.gov (United States)

    Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

    1987-11-01

    Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

  3. Pressure-induced polymerization of phenoxyethyl acrylate

    Energy Technology Data Exchange (ETDEWEB)

    Kaminski, K; Wrzalik, R; Paluch, M; Ziolo, J [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland); Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States)

    2008-06-18

    Polymerization of phenoxyethyl acrylate was induced without catalyst or initiators by the application of hydrostatic pressure at elevated temperature. Broadband dielectric and infrared spectroscopy were employed to follow the course of the reaction, which reached a degree of conversion of 60%. The structure of the obtained polymer was determined from density functional theory calculations.

  4. Immobilization of Trichoderma reesei by radiation polymerization

    International Nuclear Information System (INIS)

    Zhou Ruimin; Ma Zueteh; Kaetus, Isao; Kumakura, Minoro

    1993-01-01

    Immobilization of Trichoderma reesei was carried out by radiation polymerization. It was found that the activity of fixed cells increased with increasing surface area of the carrier and was affected by the concentration of monomer tetraethylenglycol dimethacrylate and the shape of the substrate composition and structure of cotton textile fabrics. (author)

  5. Polymerization of different lignins by laccase

    NARCIS (Netherlands)

    Mattinen, M.L.; Suortti, T.; Gosselink, R.J.A.; Argyropoulos, D.S.; Evtuguin, D.; Suurnäkki, A.; Jong, de E.; Tamminen, T.

    2008-01-01

    In this study the oxidative polymerization of different lignins, i.e. Flax Soda lignin, Spruce EMAL, and Eucalyptus Dioxane lignin by Trametes hirsuta laccase was compared. Initially the structures of the different lignins were compared by Fourier transform infrared spectroscopy. The reactivity of

  6. Interaction of acetamiprid with extracellular polymeric substances ...

    African Journals Online (AJOL)

    Extracellular polymeric substances (EPS) are important components of activated sludge and it plays an important role in removing pollutants. The interaction between EPS and organic pollutants is still little known. In the present study, the interaction of soluble/bound EPS with acetamiprid, a neonicotinoid insecticide, was ...

  7. Radiation sterilization of polymeric implant materials

    International Nuclear Information System (INIS)

    Bruck, S.D.; Mueller, E.P.

    1988-01-01

    High-energy irradiation sterilization of medical devices and implants composed of polymeric biomaterials that are in contact with tissue and/or blood, may adversely affect their long-term mechanical and/or biological performance (tissue and/or blood compatibility). Since many polymeric implants may contain trace quantities of catalysts and/or other additives, the effect of high-energy radiation on these additives, and possible synergistic effects with the polymer chains under the influence of high-energy radiation, must be considered. It is essential to indicate whether polymeric implants are used in short-term (acute) or long-term (chronic) applications. Relatively small changes in their physicochemical, mechanical, and biological properties may be tolerable in the short term, whereas similar changes may lead to catastrophic failures in long-term applications. Therefore, polymeric implants which are to be sterilized by high-energy irradiation should be carefully evaluated for long-term property changes which may be induced by the radiation

  8. Ion induced polymerization in benzene frozen films

    Energy Technology Data Exchange (ETDEWEB)

    Calcagno, G [Catania Univ. (Italy). Ist. di Fisica; Strazzulla, G [Catania Univ. (Italy). Osservatorio Astrofisico; Fichera, M; Foti, G [Catania Univ. (Italy). Ist. di Radiologia

    1983-07-01

    The cross section of the polymerization process induced by energetic protons colliding with frozen benzene layers has been measured. The results have been described by a simple theory and they show that the process is a volume one occurring along the ion track and interesting all of the crossed layers.

  9. Vinyl acetate polymerization by ionizing radiation

    International Nuclear Information System (INIS)

    Mesquita, Andrea Cercan

    2002-01-01

    The aim of this work is the synthesis and characterization of the poly(vinyl acetate) using the ionizing radiation. Six polymerizations of vinyl acetate were carried out using three techniques of polymerization: in bulk, emulsion and solution. In the technique of solution polymerization were used two solvents, the alcohol ethyl and the methylethylketone, in two proportions 1:0.5 and 1:1 related to the monomer. The solutions were irradiated with gamma rays from a 60 Co source, with dose rate between 5.25 kGy/h and 6.26 kGy/h. The polymers obtained were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The glass transition temperature (Tg) was investigated by Differential Scanning Calorimeter (DSC). The molecular weight was analyzed by the technique of Gel Permeation Chromatography (GPC). Tests of density, hardness and Vicat softening temperature were carried out. The infrared spectroscopy and others results confirmed that the polymers obtained by polymerization of vinyl acetate in bulk, emulsion and solution, using ionizing radiation, really correspond at poly(vinyl acetate). (author)

  10. Microfluidic production of polymeric micro- and nanoparticles

    NARCIS (Netherlands)

    Serra, C.; Kahn, I.U.; Cortese, B.; Croon, de M.H.J.M.; Hessel, V.; Ono, T.; Anton, N.; Vandamme, Th.

    2013-01-01

    Polymeric micro- and nanoparticles have attracted a wide attention of researchers in various areas such as drug delivery, sensing, imaging, cosmetics, diagnostics, and biotechnology. However, processes with conventional equipment do not always allow a precise control of their morphology, size, size

  11. Characteristic emission in glutaraldehyde polymerized hemoglobin

    International Nuclear Information System (INIS)

    Ma Li; Wang Xiaojun

    2011-01-01

    Hemoglobin with different modifications has been investigated using spectroscopic techniques. A new emission at around 371 nm has been observed under excitation of 305 nm from glutaraldehyde polymerized human hemoglobin. Intensity and peak position of the emission are dependent on both oxidation state and ligand environment and the emission has been identified from the hemoglobin oligomer.

  12. Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

    Directory of Open Access Journals (Sweden)

    Jianbo Tan

    2017-12-01

    Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

  13. SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

    Institute of Scientific and Technical Information of China (English)

    Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

    2000-01-01

    Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

  14. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  15. Experimental study of living free radical polymerization using trifunctional initiator and polymerization mediated by nitroxide

    International Nuclear Information System (INIS)

    Galhardo, Eduardo; Lona, Liliane M.F.

    2009-01-01

    Controlled free radical polymerization or living free radical polymerization has received increasing attention as a technique for the production of polymers with microstructure highly controlled. In particular, narrow molecular weight distributions are obtained with polydispersity very close to one. In this research it was investigate the controlled polymerization mediated by nitroxide, using a cyclic trifunctional peroxide. As long as we know, there are only publications in literature dealing with NMRP using mono- and bi-functional initiators. It was believed that the trifunctional peroxide can increase the rate of polymerization, since more free radicals are generated, if compared with initiators with lower functionality. Furthermore, the fact of the initiator be cyclic means that branches are not generated in the chains, which theoretically prevents an increase in polydispersity of the polymer. The effect of the dissociation constant of the trifunctional initiator in the velocity of the reaction was analyzed. (author)

  16. 21 CFR 870.3650 - Pacemaker polymeric mesh bag.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

  17. FtsZ Polymerization Assays : Simple Protocols and Considerations

    NARCIS (Netherlands)

    Król, Ewa; Scheffers, Dirk-Jan

    2013-01-01

    During bacterial cell division, the essential protein FtsZ assembles in the middle of the cell to form the so-called Z-ring. FtsZ polymerizes into long filaments in the presence of GTP in vitro, and polymerization is regulated by several accessory proteins. FtsZ polymerization has been extensively

  18. Effects of linker variation on the in vitro and in vivo characteristics of an 111In-labeled RGD peptide

    International Nuclear Information System (INIS)

    Dijkgraaf, Ingrid; Liu, Shuang; Kruijtzer, John A.W.; Soede, Annemieke C.; Oyen, Wim J.G.; Liskamp, Rob M.J.; Corstens, Frans H.M.; Boerman, Otto C.

    2007-01-01

    Introduction: Due to the selective expression of the α v β 3 integrin in tumors, radiolabeled arginine-glycine-aspartic acid (RGD) peptides are attractive candidates for tumor targeting. Minor modifications of these peptides could have a major impact on in vivo characteristics. In this study, we systematically investigated the effects of linker modification between two cyclic RGD sequences and DOTA (1,4,7,10-tetraazadodecane-N,N',N ' ,N'''-tetraacetic acid) on the in vitro and in vivo characteristics of the tracer. Methods: A dimeric RGD peptide was synthesized and conjugated either directly with DOTA or via different linkers: PEG 4 (polyethylene glycol), glutamic acid or lysine. The RGD peptides were radiolabeled with 111 In, and their in vitro and in vivo α v β 3 -binding characteristics were determined. Results: LogP values varied between -2.82±0.06 and -3.95±0.33. The IC 50 values for DOTA-E-[c(RGDfK)] 2 , DOTA-PEG 4 -E-[c(RGDfK)] 2 , DOTA-E-E-[c(RGDfK)] 2 and DOTA-K-E-[c(RGDfK)] 2 were comparable. Two hours after injection, the tumor uptakes of the 111 In-labeled compounds were not significantly different. The kidney accumulation of [ 111 In]-DOTA-K-E-[c(RGDfK)] 2 [4.05±0.20% of the injected dose per gram (ID/g)] was significantly higher as compared with that of [ 111 In]-DOTA-E-[c(RGDfK)] 2 (2.63±0.19% ID/g; P 111 In]-DOTA-E-E-[c(RGDfK)] 2 (2.16±0.21% ID/g; P 111 In]-DOTA-E-E-[c(RGDfK)] 2 (2.12±0.09% ID/g) was significantly higher as compared with that of [ 111 In]-DOTA-E-[c(RGDfK)] 2 (1.64±0.1% ID/g; P 111 In]-DOTA-K-E-[c(RGDfK)] 2 (1.52±0.04% ID/g; P v β 3 and tumor uptake. Insertion of lysine caused enhanced kidney retention; that of glutamic acid also resulted in enhanced retention in the kidneys. PEG 4 appeared to be the most suitable linker as compared with glutamic acid and lysine because it has the highest tumor-to-blood ratio and the lowest uptake in the kidney and liver

  19. THE EFFECTS OF N-2-HYDROXYETHYL-N-METHYL-P-TOLUIDINE ON METHYL METHACRYLATE RADICAL POLYMERIZATION AND ACRYLONITRILE PHOTOINDUCED POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; ZHANG Zhanghua; FENG Xinde

    1992-01-01

    The effects of N-2-hydroxyethyl-N-methyl-p-toluidine (HMT) on MMA polymerization using organic peroxide as an initiator and on AN photoinduced polymerization have been investigated respectively. The kinetics of polymerization and the overall activation energy of polymerization were determined. Based on kinetics study and the end group analysis of the polymer obtained by UV spectrum method, the initiation mechanism is proposed.

  20. A theory for fracture of polymeric gels

    Science.gov (United States)

    Mao, Yunwei; Anand, Lallit

    2018-06-01

    A polymeric gel is a cross-linked polymer network swollen with a solvent. If the concentration of the solvent or the deformation is increased to substantial levels, especially in the presence of flaws, then the gel may rupture. Although various theoretical aspects of coupling of fluid permeation with large deformation of polymeric gels are reasonably well-understood and modeled in the literature, the understanding and modeling of the effects of fluid diffusion on the damage and fracture of polymeric gels is still in its infancy. In this paper we formulate a thermodynamically-consistent theory for fracture of polymeric gels - a theory which accounts for the coupled effects of fluid diffusion, large deformations, damage, and also the gradient effects of damage. The particular constitutive equations for fracture of a gel proposed in our paper, contain two essential new ingredients: (i) Our constitutive equation for the change in free energy of a polymer network accounts for not only changes in the entropy, but also changes in the internal energy due the stretching of the Kuhn segments of the polymer chains in the network. (ii) The damage and failure of the polymer network is taken to occur by chain-scission, a process which is driven by the changes in the internal energy of the stretched polymer chains in the network, and not directly by changes in the configurational entropy of the polymer chains. The theory developed in this paper is numerically implemented in an open-source finite element code MOOSE, by writing our own application. Using this simulation capability we report on our study of the fracture of a polymeric gel, and some interesting phenomena which show the importance of the diffusion of the fluid on fracture response of the gel are highlighted.

  1. NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

    CERN Document Server

    1998-01-01

    The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

  2. CD6 and Linker of Activated T Cells are Potential Interaction Partners for T Cell-Specific Adaptor Protein.

    Science.gov (United States)

    Hem, C D; Ekornhol, M; Granum, S; Sundvold-Gjerstad, V; Spurkland, A

    2017-02-01

    The T cell-specific adaptor protein (TSAd) contains several protein interaction domains, and is merging as a modulator of T cell activation. Several interaction partners for the TSAd proline-rich region and phosphotyrosines have been identified, including the Src and Tec family kinases lymphocyte-specific protein tyrosine kinase and interleukin 2-inducible T cell kinase. Via its Src homology 2 (SH2) domain, TSAd may thus function as a link between these enzymes and other signalling molecules. However, few binding partners to the TSAd SH2 domain in T cells are hitherto known. Through the use of in silico ligand prediction, peptide spot arrays, pull-down and immunoprecipitation experiments, we here report novel interactions between the TSAd SH2 domain and CD6 phosphotyrosine (pTyr) 629 and linker of activated T cells (LAT) pTyr 171 , pTyr 191 and pTyr 226 . © 2016 The Foundation for the Scandinavian Journal of Immunology.

  3. Self-organization of Au–CdSe hybrid nanoflowers at different length scales via bi-functional diamine linkers

    Energy Technology Data Exchange (ETDEWEB)

    AbouZeid, Khaled Mohamed [Virginia Commonwealth University, Department of Chemistry (United States); Mohamed, Mona Bakr [Cairo University, National Institute of Laser Enhanced Science (NILES) (Egypt); El-Shall, M. Samy, E-mail: mselshal@vcu.edu [Virginia Commonwealth University, Department of Chemistry (United States)

    2016-01-15

    This work introduces a series of molecular bridging bi-functional linkers to produce laterally self-assembled nanostructures of the Au–CdSe nanoflowers on different length scales ranging from 10 nm to 100 microns. Assembly of Au nanocrystals within amorphous CdSe rods is found in the early stages of the growth of the Au–CdSe nanoflowers. The Au–CdSe nanoflowers are formed through a one-pot low temperature (150 °C) process where CdSe clusters are adsorbed on the surface of the Au cores, and they then start to form multiple arms and branches resulting in flower-shaped hybrid nanostructures. More complex assembly at a micron length scale can be achieved by means of bi-functional capping agents with appropriate alkyl chain lengths, such as 1,12-diaminododecane.

  4. Ag2S Quantum Dot-Sensitized Solar Cells by First Principles: The Effect of Capping Ligands and Linkers.

    Science.gov (United States)

    Amaya Suárez, Javier; Plata, Jose J; Márquez, Antonio M; Fernández Sanz, Javier

    2017-09-28

    Quantum dots solar cells, QDSCs, are one of the candidates for being a reliable alternative to fossil fuels. However, the well-studied CdSe and CdTe-based QDSCs present a variety of issues for their use in consumer-goods applications. Silver sulfide, Ag 2 S, is a promising material, but poor efficiency has been reported for QDSCs based on this compound. The potential influence of each component of QDSCs is critical and key for the development of more efficient devices based on Ag 2 S. In this work, density functional theory calculations were performed to study the nature of the optoelectronic properties for an anatase-TiO 2 (101) surface sensitized with different silver sulfide nanoclusters. We demonstrated how it is possible to deeply tune of its electronic properties by modifying the capping ligands and linkers to the surface. Finally, an analysis of the electron injection mechanism for this system is presented.

  5. Antibiotic polymeric nanoparticles for biofilm-associated infection therapy.

    Science.gov (United States)

    Cheow, Wean Sin; Hadinoto, Kunn

    2014-01-01

    Polymeric nanoparticles are highly attractive as drug delivery vehicles due to their high structural integrity, stability during storage, ease of preparation and functionalization, and controlled release capability. Similarly, lipid-polymer hybrid nanoparticles, which retain the benefits of polymeric nanoparticles plus the enhanced biocompatibility and prolonged circulation time owed to the lipids, have recently emerged as a superior alternative to polymeric nanoparticles. Drug nanoparticle complex prepared by electrostatic interaction of oppositely charged drug and polyelectrolytes represents another type of polymeric nanoparticle. This chapter details the preparation, characterization, and antibiofilm efficacy testing of antibiotic-loaded polymeric and hybrid nanoparticles and antibiotic nanoparticle complex.

  6. Studies on Rate Enhancement of Polymerization in NMRP

    Institute of Scientific and Technical Information of China (English)

    HUANG Jian-ying; XU Miao-qing; YAN Ming-fa; CHEN Yi-hong; CHU Jia-yan; ZHUANG Jia-ming; DAI Li-zong; ZOU You-si

    2005-01-01

    In NMRP, the polymerization of MMA, the polymerization of St and the copolymerization of MMA with St were distinctly accelerated by the addition of a small amount of MN. The polymerization proceeds in a living fashion as indicated by the increase in molecular weight with the increase of time and conversion and a relatively low polydispersity. It has been found that the addition of MN results in a nearly one hundred times higher rate of the polymerization of MMA, a nearly twenty times higher rate of the polymerization of St and a nearly fifteen times higher rate of the copolymerization of St and MMA.

  7. Regulating repression: roles for the sir4 N-terminus in linker DNA protection and stabilization of epigenetic states.

    Directory of Open Access Journals (Sweden)

    Stephanie Kueng

    Full Text Available Silent information regulator proteins Sir2, Sir3, and Sir4 form a heterotrimeric complex that represses transcription at subtelomeric regions and homothallic mating type (HM loci in budding yeast. We have performed a detailed biochemical and genetic analysis of the largest Sir protein, Sir4. The N-terminal half of Sir4 is dispensable for SIR-mediated repression of HM loci in vivo, except in strains that lack Yku70 or have weak silencer elements. For HM silencing in these cells, the C-terminal domain (Sir4C, residues 747-1,358 must be complemented with an N-terminal domain (Sir4N; residues 1-270, expressed either independently or as a fusion with Sir4C. Nonetheless, recombinant Sir4C can form a complex with Sir2 and Sir3 in vitro, is catalytically active, and has sedimentation properties similar to a full-length Sir4-containing SIR complex. Sir4C-containing SIR complexes bind nucleosomal arrays and protect linker DNA from nucleolytic digestion, but less effectively than wild-type SIR complexes. Consistently, full-length Sir4 is required for the complete repression of subtelomeric genes. Supporting the notion that the Sir4 N-terminus is a regulatory domain, we find it extensively phosphorylated on cyclin-dependent kinase consensus sites, some being hyperphosphorylated during mitosis. Mutation of two major phosphoacceptor sites (S63 and S84 derepresses natural subtelomeric genes when combined with a serendipitous mutation (P2A, which alone can enhance the stability of either the repressed or active state. The triple mutation confers resistance to rapamycin-induced stress and a loss of subtelomeric repression. We conclude that the Sir4 N-terminus plays two roles in SIR-mediated silencing: it contributes to epigenetic repression by stabilizing the SIR-mediated protection of linker DNA; and, as a target of phosphorylation, it can destabilize silencing in a regulated manner.

  8. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  9. Microencapsulation of Epoxidized Linseed Oil Liquid Cross-Linker in Poly(N-vinyl-pyrrolidone): Optimization by a Design-of-Experiments Approach

    NARCIS (Netherlands)

    Senatore, D.; Laven, J.; Benthem, van R.A.T.M.; La Camera, D.; With, de G.

    2010-01-01

    A liquid cross-linker, epoxidized linseed oil (ELO), was encapsulated in a plastic with a high glass transition temperature (poly(N-vinyl-2-pyrrolidone); PVP). The process parameters of the spray-drying employed were optimized by a Design-of-Experiments (DoE) approach. Three factors concerning both

  10. Modulation of procaspase-7 self-activation by PEST amino acid residues of the N-terminal prodomain and intersubunit linker.

    Science.gov (United States)

    Alves, Juliano; Garay-Malpartida, Miguel; Occhiucci, João M; Belizário, José E

    2017-12-01

    Procaspase-7 zymogen polypeptide is composed of a short prodomain, a large subunit (p20), and a small subunit (p10) connected to an intersubunit linker. Caspase-7 is activated by an initiator caspase-8 and -9, or by autocatalysis after specific cleavage at IQAD 198 ↓S located at the intersubunit linker. Previously, we identified that PEST regions made of amino acid residues Pro (P), Glu (E), Asp (D), Ser (S), Thr (T), Asn (N), and Gln (Q) are conserved flanking amino acid residues in the cleavage sites within a prodomain and intersubunit linker of all caspase family members. Here we tested the impact of alanine substitution of PEST amino acid residues on procaspase-7 proteolytic self-activation directly in Escherichia coli. The p20 and p10 subunit cleavage were significantly delayed in double caspase-7 mutants in the prodomain (N18A/P26A) and intersubunit linker (S199A/P201A), compared with the wild-type caspase-7. The S199A/P201A mutants effectively inhibited the p10 small subunit cleavage. However, the mutations did not change the kinetic parameters (k cat /K M ) and optimal tetrapeptide specificity (DEVD) of the purified mutant enzymes. The results suggest a role of PEST-amino acid residues in the molecular mechanism for prodomain and intersubunit cleavage and caspase-7 self-activation.

  11. Micromachined silicon acoustic delay line with 3D-printed micro linkers and tapered input for improved structural stability and acoustic directivity

    International Nuclear Information System (INIS)

    Cho, Y; Kumar, A; Xu, S; Zou, J

    2016-01-01

    Recent studies have shown that micromachined silicon acoustic delay lines can provide a promising solution to achieve real-time photoacoustic tomography without the need for complex transducer arrays and data acquisition electronics. To achieve deeper imaging depth and wider field of view, a longer delay time and therefore delay length are required. However, as the length of the delay line increases, it becomes more vulnerable to structural instability due to reduced mechanical stiffness. In this paper, we report the design, fabrication, and testing of a new silicon acoustic delay line enhanced with 3D printed polymer micro linker structures. First, mechanical deformation of the silicon acoustic delay line (with and without linker structures) under gravity was simulated by using finite element method. Second, the acoustic crosstalk and acoustic attenuation caused by the polymer micro linker structures were evaluated with both numerical simulation and ultrasound transmission testing. The result shows that the use of the polymer micro linker structures significantly improves the structural stability of the silicon acoustic delay lines without creating additional acoustic attenuation and crosstalk. In addition, the improvement of the acoustic acceptance angle of the silicon acoustic delay lines was also investigated to better suppress the reception of unwanted ultrasound signals outside of the imaging plane. These two improvements are expected to provide an effective solution to eliminate current limitations on the achievable acoustic delay time and out-of-plane imaging resolution of micromachined silicon acoustic delay line arrays. (paper)

  12. Synthetic incorporation of Nile Blue into DNA using 2′-deoxyriboside substitutes: Representative comparison of (R- and (S-aminopropanediol as an acyclic linker

    Directory of Open Access Journals (Sweden)

    Daniel Lachmann

    2010-02-01

    Full Text Available The Nile Blue chromophore was incorporated into oligonucleotides using “click” chemistry for the postsynthetic modification of oligonucleotides. These were synthesized using DNA building block 3 bearing an alkyne group and reacted with the azide 4. (R-3-amino-1,2-propanediol was applied as the linker between the phosphodiester bridges. Two sets of DNA duplexes were prepared. One set carried the chromophore in an A-T environment, the second set in a G-C environment. Both were characterized by optical spectroscopy. Sequence-dependent fluorescence quenching was applied as a sensitive tool to compare the stacking interactions with respect to the chirality of the acyclic linker attachment. The results were compared to recent results from duplexes that carried the Nile Blue label in a sequentially and structurally identical context, except for the opposite chirality of the linker ((S-3-amino-1,2-propandiol. Only minor, negligible differences were observed. Melting temperatures, UV–vis absorption spectra together with fluorescence quenching data indicate that Nile Blue stacks perfectly between the adjacent base pairs regardless of whether it has been attached via an S- or R-configured linker. This result was supported by geometrically optimized DNA models.

  13. Radioiodination of protein using 2,3,5,6-tetrafluorophenyl 3-(nido-carboranyl) propionate (TCP) as a potential bi-functional linker: Synthesis and biodistribution in mice

    International Nuclear Information System (INIS)

    Lin Rushan; Liu Ning; Yang Yuanyou; Li Bing; Liao Jiali; Jin Jiannan

    2009-01-01

    2,3,5,6-Tetrafluorophenyl 3-(nido-carboranyl) propionate (TCP), as a new potential bi-functional linker for radiohalogenation of proteins or peptides, was synthesized. With this bi-functional linker, the first attempt to conjugate bovine serum albumin (BSA) with 125 I was made and the biodistribution of the conjugated BSA ( 125 I-TCP-BSA) was investigated in NIH strain mice. By the use of TCP as the linker, BSA was conjugated with 125 I in a labeling yield of 58-75% and with radiochemical purity of 99.8% after purification by Sephadex TM G-50. Even after being kept at room temperature for 72 h, the radiochemical purity of 125 I-TCP-BSA was still more than 98%, much higher than that of the directly 125 I-labeled BSA ( 125 I-BSA). Meanwhile, biodistribution experiments in mice indicated that the uptake of 125 I with 125 I-TCP-BSA into thyroid was obviously less than that with 125 I-BSA post-injection. All the results implied that the 125 I-conjugated BSA ( 125 I-TCP-BSA) was considerably stable in vivo as well as in vitro, and TCP was regarded as a promising bi-functional linker for radiohalogenation of proteins

  14. The ortho backbone amide linker (o-BAL) is an easily prepared and highly acid-labile handle for solid-phase synthesis

    DEFF Research Database (Denmark)

    Boas, Ulrik; Brask, Jesper; Christensen, J.B.

    2002-01-01

    The tris(alkoxy)benzyl backbone amide linker (BAL) has found widespread application in solid-phase synthesis. The key intermediate for preparation of para BAL (p-BAL) is 2,6-dimethoxy-4-hydroxybenzaldehyde; several reports on its synthesis have appeared. However, the ortho analogue of the handle (o...

  15. Diols and anions can control the formation of an exciplex between a pyridinium boronic acid with an aryl group connected via a propylene linker.

    Science.gov (United States)

    Huang, Yan-Jun; Jiang, Yun-Bao; Bull, Steven D; Fossey, John S; James, Tony D

    2010-11-21

    The exciplex formation between a pyridinium boronic acid and phenyl group connected via a propylene linker can be monitored using fluorescence. Addition of pinacol affords a cyclic boronate ester with enhanced Lewis acidity that increases the strength of its cation-π stacking interaction causing a four-fold fluorescence enhancement.

  16. Doxorubicin conjugation and drug linker chemistry alter the intravenous and pulmonary pharmacokinetics of a PEGylated Generation 4 polylysine dendrimer in rats.

    Science.gov (United States)

    Leong, Nathania J; Mehta, Dharmini; McLeod, Victoria M; Kelly, Brian D; Pathak, Rashmi; Owen, David J; Porter, Christopher Jh; Kaminskas, Lisa M

    2018-05-28

    PEGylated polylysine dendrimers have demonstrated potential as inhalable drug delivery systems that can improve the treatment of lung cancers. Their treatment potential may be enhanced by developing constructs that display prolonged lung retention, together with good systemic absorption, the capacity to passively target lung tumours from the blood and highly selective, yet rapid liberation in the tumour microenvironment. This study sought to characterise how the nature of cathepsin B cleavable peptide linkers, used to conjugate doxorubicin to a PEGylated (PEG570) G4 polylysine dendrimer, affect drug liberation kinetics and intravenous and pulmonary pharmacokinetics in rats. The construct bearing a self-emolative diglycolic acid-V-Citrulline linker exhibited faster doxorubicin release kinetics compared to constructs bearing self emolative diglycolic acid-GLFG, or non-self emolative glutaric acid-GLFG linkers. The V-Citrulline construct exhibited slower plasma clearance, but faster absorption from the lungs than a GLFG construct, although mucociliary clearance and urinary elimination were unchanged. Doxorubicin-conjugation enhanced localisation in the bronchoalveolar lavage fluid compared to lung tissue, suggesting that projection of doxorubicin from the dendrimer surface reduced tissue uptake. These data show that the linker chemistry employed to conjugate drugs to PEGylated carriers can affect drug release profiles and systemic and lung disposition. Copyright © 2018. Published by Elsevier Inc.

  17. Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Shiva K., E-mail: srastogi@uidaho.edu [University of Idaho, Department of Chemistry (United States); Denn, Benjamin D.; Branen, A. Larry [University of Idaho, Coeur D' Alene, Biosensors and Nanotechnology Application Laboratory (BNAL) (United States)

    2012-01-15

    This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N Prime -dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 {+-} 5 nm upon excitation at 345 {+-} 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV-vis absorption spectra, UV-vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.

  18. Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota, E-mail: dorota.maciejewska@wum.edu.pl

    2015-11-01

    Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, {sup 13}C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate

  19. The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

    Science.gov (United States)

    Anderson, Ian Mark

    Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented

  20. Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

    International Nuclear Information System (INIS)

    Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota

    2015-01-01

    Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, 13 C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate). - Highlights:

  1. Hyperbranched polymers from polymerization in solid state

    International Nuclear Information System (INIS)

    Tomaz, Vivian A.; Silva, Rafael; Muniz, Edvani C.; Rubira, Adley F.

    2009-01-01

    The macroscopic properties of polymers are directly related to the chemical characteristics of the monomeric units and also with the geometric arrangement of polymer chains. Thus, polymers were synthesized from two well-known chelators EDTA and EDA. We evaluated the conditions for the polymerization of the precursors in the solid state. The polymerization was carried out varying the proportions of reagents, aiming the polymers with different degrees of chain branching and the materials were characterized by FTIR. The materials obtained from the best condition for synthesis were purified by size-exclusion chromatography of and were subjected to characterization by FTIR and NMR of 1 H and 13 C. The content of end groups in these samples was determined by back titration. (author)

  2. Light-harvesting organic photoinitiators of polymerization.

    Science.gov (United States)

    Lalevée, Jacques; Tehfe, Mohamad-Ali; Dumur, Frédéric; Gigmes, Didier; Graff, Bernadette; Morlet-Savary, Fabrice; Fouassier, Jean-Pierre

    2013-02-12

    Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Studies on radiation-induced graft polymerization

    International Nuclear Information System (INIS)

    Omichi, Hideki

    1978-09-01

    Radiation-induced graft polymerization is used extensively to improve physical properties of polymers, but few processes are now commercialized. The reason for this is partly inadequate basic research on the reaction and partly the difficulty in developing the grafting process with large radiation source. Firstly, new techniques are proposed of studying kinetics of the graft polymerization in heterogeneous system. Based on the grafting yield, the molecular weight of graft chains, and the amount of radicals given by ESR and activation analysis, kinetic parameters are obtained and the reaction mechanism of grafting process is discussed. Secondly, the development of grafting process of poly (vinyl chloride)-butadiene is described. By study of the reaction, process design, construction and operation of the pilot plant, and economic analysis of the process, this process with 60 Co gamma ray sources is shown to be industrially promising. (author)

  4. Radiation-induced emulsion polymerization of tetrafluoroethylene

    International Nuclear Information System (INIS)

    Suwa, Takeshi

    1979-10-01

    The radiation-induced emulsifier-free emulsion polymerization of tetrafluoroethylene (TFE) has been studied at initial pressure 2 - 25 kg/cm 2 and temperature 30 0 - 110 0 C for dose rate 0.57 x 10 4 - 3.0 x 10 4 rad/hr. Polytetrafluoroethylene (PTFE), a hydrophobic polymer, forms as a stable latex in the absence of an emulsifier. Stability of the latex is governed by the dose rate/TFE pressure ratio; it increases with sufficient TFE monomer. PTFE particles produced in this polymerization system are stable due to the carboxyl end groups and adsorption of OH - and HF on the particles. PTFE latex of molecular weight higher than 2 x 10 7 is obtained by addition of a radical scavenger such as hydroquinone. The molecular weight of PTFE can be measured from the heat of crystallization conveniently with high reliability, which was found in the course of study on the melting and crystallization behavior. (author)

  5. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Hassager, Ole; Kristensen, Susanne Brogaard; Larsen, Johannes Ruben

    1999-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane. The polymeric material is described by an arbitrary combination of a viscoelastic and a purely viscous component to the stress. Some viscoelastic materials described by a Mooney......-Rivlin model show a monotone increasing pressure during inflation of a spherical membrane. These materials develop a homogeneous membrane thickness in agreement with the Considere-Pearson condition. Molecularly based models such as the neo-Hookean, Doi-Edwards or Tom-Pom model show a pressure maximum when...... inflated. Membranes described by these models develop a local thinning of the membrane which may lead to bursting in finite time. (C) 1999 Elsevier Science B.V. All rights reserved....

  6. Radiation polymerization of tetrafluoroethylene in freon-22

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Thompson, J.C.

    1979-02-01

    The radiation-induced solution-polymerization of tetrafluoroethylene in Freon-22 has been investigated over a temperature range of - 62 degrees celcius to 0 degrees celcius. The rate of polymerization for the in-source process was found to be directly propertional to monomer concentration and an activation energy of only 7,66 kj/mole was calculated. The number-average molecular mass of the product PTFE ranged from 2X10 4 to 6X10 4 and was relatively independent of the usual reaction parameters. The rate of postpolymerization was also found to be directly proportional to monomer concentration. The postpolyerization process did not result in any enchancement of the initial PTFE molecular mass [af

  7. Self-folding micropatterned polymeric containers.

    Science.gov (United States)

    Azam, Anum; Laflin, Kate E; Jamal, Mustapha; Fernandes, Rohan; Gracias, David H

    2011-02-01

    We demonstrate self-folding of precisely patterned, optically transparent, all-polymeric containers and describe their utility in mammalian cell and microorganism encapsulation and culture. The polyhedral containers, with SU-8 faces and biodegradable polycaprolactone (PCL) hinges, spontaneously assembled on heating. Self-folding was driven by a minimization of surface area of the liquefying PCL hinges within lithographically patterned two-dimensional (2D) templates. The strategy allowed for the fabrication of containers with variable polyhedral shapes, sizes and precisely defined porosities in all three dimensions. We provide proof-of-concept for the use of these polymeric containers as encapsulants for beads, chemicals, mammalian cells and bacteria. We also compare accelerated hinge degradation rates in alkaline solutions of varying pH. These optically transparent containers resemble three-dimensional (3D) micro-Petri dishes and can be utilized to sustain, monitor and deliver living biological components.

  8. Polymeric membrane studied using slow positron beam

    International Nuclear Information System (INIS)

    Hung, W.-S.; Lo, C.-H.; Cheng, M.-L.; Chen Hongmin; Liu Guang; Chakka, Lakshmi; Nanda, D.; Tung, K.-L.; Huang, S.-H.; Lee, Kueir-Rarn; Lai, J.-Y.; Sun Yiming; Yu Changcheng; Zhang Renwu; Jean, Y.C.

    2008-01-01

    A radioisotope slow positron beam has been built at the Chung Yuan Christian University in Taiwan for the research and development in membrane science and technology. Doppler broadening energy spectra and positron annihilation lifetime have been measured as a function of positron energy up to 30 keV in a polyamide membrane prepared by the interfacial polymerization between triethylenetetraamine (TETA) and trimesoyl chloride (TMC) on modified porous polyacrylonitrile (PAN) asymmetric membrane. The multilayer structures and free-volume depth profile for this asymmetric membrane system are obtained. Positron annihilation spectroscopy coupled with a slow beam could provide new information about size selectivity of transporting molecules and guidance for molecular designs in polymeric membranes

  9. Radiation-induced polymerization of hydrogen cyanide

    International Nuclear Information System (INIS)

    Mozhaev, P.S.; Kichigina, G.A.; Kiryukhin, D.P.

    1995-01-01

    The chain reaction of HCN polymerization in a γ-radiation field does not occur at 77 K. When irradiated HCN is warmed up to ambient temperature, a polymer is formed. The heat of polymerization of HCN is 44.0±6.0 kJ/mol and the polymer yield reaches 2.5% for a dose of 725 kGy. Amorphous polymer products (with yields increasing up to 33.5%) and needle crystals (presumably HCN tetramer) are formed upon storage of irradiated HCN at room temperature. The polymer is stable below 700 K, has a conductivity of 3x10 -5 Ω -1 cm -f1 , and displays an EPR spectrum typical of polyconjugated systems. A radical mechanism of the formation of conjugated chain -C=N-C=N- is suggested. The tetramer is produced by a combination of aminocyanocarbene biradicals

  10. RAFT polymerization and some of its applications.

    Science.gov (United States)

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

    2013-08-01

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

  11. Forming of Polymeric Tubular Micro-components

    DEFF Research Database (Denmark)

    Qin, Yi; Zhao, Jie; Anyasodor, Gerald

    2015-01-01

    platform for the production of functional polymeric tubular micro-components. The chapter gives background on the current market and process development trends, followed by description of materials, process configuration, tool design and machine development for each processing technology as well......This chapter is intended to provide an overview of three nontraditional shaping technologies for the forming of polymeric micro-tubes, which are hot embossing, blow molding, and cross rolling, as well as realization of a process chain and the integration of a modular machine-based manufacturing...... as strategy for integration of the technologies and equipment into a common platform. Finally, potential applications of the technologies and facilities developed are highlighted....

  12. Polyisoprene Nanoparticles Prepared by Polymerization in Microemulsion

    Directory of Open Access Journals (Sweden)

    Y. Apolinar

    2010-01-01

    Full Text Available Batch polymerization of isoprene was carried out at 25∘C in a normal microemulsion stabilized with sodium dodecyl sulfate and initiated with the redox couple tert-butyl hydroperoxide/tetraethylene-pentamine. Characterization by transmission electronic microscopy showed that polyisoprene nanoparticles with number-average diameter close to 20 nm were obtained. The low molecular weights obtained, as determined by gel permeation chromatography, were probably due to chain scission as inferred from the oxidative ambient at which polymerization was carried out. Microstructure calculated from infrared spectroscopy data indicates that the obtained polyisoprene contains around 80% total 1,4 units, which is in accordance with its glass transition temperature (-60.8∘C determined by differential scanning calorimetry.

  13. Pharmaceutical Applications of Polymeric Nano materials

    International Nuclear Information System (INIS)

    Wu, L.; Sun, L.

    2011-01-01

    With significant attention focused on nano science and nano technology in recent years, nano materials have been used in a wide variety of applications such as automotive, environmental, energy, catalysis, biomedical, drug delivery, and polymeric industries. Among those fields, the application of nano materials with pharmaceutical science is an emerging and rapidly growing field and has drawn increasing attention recently. Research and development in this field is mainly focused on several aspects such as the discoveries of novel functional nano materials, exploration on nanoparticles with controlled and targeted drug delivery characteristics, and investigation of bio functionalized and diagnostic nano materials. In this special issue, we have invited a few papers related to recent advances in pharmaceutical application of polymeric nano materials

  14. Structural and Functional Analysis of the Signal-Transducing Linker in the pH-Responsive One-Component System CadC of Escherichia coli.

    Science.gov (United States)

    Buchner, Sophie; Schlundt, Andreas; Lassak, Jürgen; Sattler, Michael; Jung, Kirsten

    2015-07-31

    The pH-responsive one-component signaling system CadC in Escherichia coli belongs to the family of ToxR-like proteins, whose members share a conserved modular structure, with an N-terminal cytoplasmic winged helix-turn-helix DNA-binding domain being followed by a single transmembrane helix and a C-terminal periplasmic pH-sensing domain. In E. coli CadC, a cytoplasmic linker comprising approximately 50 amino acids is essential for transmission of the signal from the sensor to the DNA-binding domain. However, the mechanism of transduction is poorly understood. Using NMR spectroscopy, we demonstrate here that the linker region is intrinsically disordered in solution. Furthermore, mutational analyses showed that it tolerates a range of amino acid substitutions (altering polarity, rigidity and α-helix-forming propensity), is robust to extension but is sensitive to truncation. Indeed, truncations either reversed the expression profile of the target operon cadBA or decoupled expression from external pH altogether. CadC dimerizes via its periplasmic domain, but light-scattering analysis provided no evidence for dimerization of the isolated DNA-binding domain, with or without the linker region. However, bacterial two-hybrid analysis revealed that CadC forms stable dimers in a stimulus- and linker-dependent manner, interacting only at pHpH. Thus, we propose that the disordered CadC linker is required for transducing the pH-dependent response of the periplasmic sensor into a structural rearrangement that facilitates dimerization of the cytoplasmic CadC DNA-binding domain. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.

    Science.gov (United States)

    Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva; Tyagi, Madhusudan; Chen, Ping; Yildirim, Taner; Zhou, Wei

    2013-07-17

    UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure, each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique, we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects, an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high, ∼10% in our sample, effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time, the linker vacancies can be tuned systematically, leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm(3)/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m(2)/g, the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal, respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66, in particular CO2. Finally, comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66, we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant, non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements, and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations.

  16. Crystal structure of the Src family kinase Hck SH3-SH2 linker regulatory region supports an SH3-dominant activation mechanism.

    Science.gov (United States)

    Alvarado, John J; Betts, Laurie; Moroco, Jamie A; Smithgall, Thomas E; Yeh, Joanne I

    2010-11-12

    Most mammalian cell types depend on multiple Src family kinases (SFKs) to regulate diverse signaling pathways. Strict control of SFK activity is essential for normal cellular function, and loss of kinase regulation contributes to several forms of cancer and other diseases. Previous x-ray crystal structures of the SFKs c-Src and Hck revealed that intramolecular association of their Src homology (SH) 3 domains and SH2 kinase linker regions has a key role in down-regulation of kinase activity. However, the amino acid sequence of the Hck linker represents a suboptimal ligand for the isolated SH3 domain, suggesting that it may form the polyproline type II helical conformation required for SH3 docking only in the context of the intact structure. To test this hypothesis directly, we determined the crystal structure of a truncated Hck protein consisting of the SH2 and SH3 domains plus the linker. Despite the absence of the kinase domain, the structures and relative orientations of the SH2 and SH3 domains in this shorter protein were very similar to those observed in near full-length, down-regulated Hck. However, the SH2 kinase linker adopted a modified topology and failed to engage the SH3 domain. This new structure supports the idea that these noncatalytic regions work together as a "conformational switch" that modulates kinase activity in a manner unique to the SH3 domain and linker topologies present in the intact Hck protein. Our results also provide fresh structural insight into the facile induction of Hck activity by HIV-1 Nef and other Hck SH3 domain binding proteins and implicate the existence of innate conformational states unique to individual Src family members that "fine-tune" their sensitivities to activation by SH3-based ligands.

  17. EDOT polymerization at photolithographically patterned functionalized graphene

    Czech Academy of Sciences Publication Activity Database

    Kovaříček, Petr; Drogowska, Karolina; Melníková Komínková, Zuzana; Blechta, Václav; Bastl, Zdeněk; Gromadzki, Daniel; Fridrichová, Michaela; Kalbáč, Martin

    2017-01-01

    Roč. 113, MAR 2017 (2017), s. 33-39 ISSN 0008-6223 R&D Projects: GA MŠk LL1301; GA MŠk(CZ) LM2015073 Grant - others:AVČR PPPLZ(CZ) L200401551 Institutional support: RVO:61388955 Keywords : polymerization * electrochemical doping * graphene Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 6.337, year: 2016

  18. Emulsion polymerization with high energy radiation

    International Nuclear Information System (INIS)

    Stannett, V.T.; Stahel, E.P.

    1992-01-01

    High energy radiation, particularly that of cobalt-60 or caesium-137 gamma-rays, provides in principle an ideal initiator for emulsion polymerization. The high free radical yields from the radiolysis of the aqueous phase combined with the high kinetic chain lengths associated with emulsion polymerization lead to a highly effective utilization of the radiation. There are other important advantages compared with the use of chemical initiators such as potassium persulfate. These are outlined in the chapter, together with some attendant disadvantages. Radiation-induced initiation is temperature independent, and low temperature polymerizations can be conducted with ease. Monomers that mainly terminate their growing chains by chain transfer to monomer give higher molecular weights at lower temperatures. Industrially, vinyl acetate is an important example of such a monomer, and it has been studied using radiation initiation. Both laboratory and pilot plant studies have been carried out and reported. The results are summarized in this chapter. Styrene is the classical example of a material that under a number of conditions closely obeys the so-called ideal Smith-Ewart kinetics. It has been found that under similar conditions but substituting radiation for potassium persulfate as the initiator, ideal kinetics were closely followed. Most of the conventional and some non-standard vinyl and diene monomers have been studied to some extent with radiation-initiated polymerizations in emulsion. To conserve space however, this chapter presents and discusses the results obtained only with styrene and vinyl acetate, both in laboratory and pilot plant investigations. Other monomers and special situations are referenced either directly or to the other available reviews. (orig.)

  19. Personal Cooling Fabric Based on Polymeric Thermoelectrics

    Science.gov (United States)

    2016-07-28

    There are also concerns about environmental impact given their toxic heavy metal content. Despite these limitations and the lack of improvement in...polymeric TE materials were studied, they offered the additional advantages (over metallic materials) of low density, no toxic heavy metals (bismuth, lead...First, fluorene was reacted with two equivalents of bromoethane under basic conditions to afford 9,9’-diethyl fluorine , which was bromomethylated

  20. High-voltage polymeric insulated cables

    Energy Technology Data Exchange (ETDEWEB)

    Ross, A

    1987-01-01

    Reviews developments in high-voltage (here defined as 25 kV, 66 kV and 132 kV) polymeric insulated cables in the UK over the period 1979-1986, with particular reference to the experience of the Eastern Electricity Board. Outlines the background to the adoption of XPLE-insulated solid cable, and the design, testing, terminations, jointing and costs of 25 kV, 66 kV and 132 kV cables.

  1. Adaptive polymeric system for Hebbian type learning

    OpenAIRE

    2011-01-01

    Abstract We present the experimental realization of an adaptive polymeric system displaying a ?learning behaviour?. The system consists on a statistically organized networks of memristive elements (memory-resitors) based on polyaniline. In a such network the path followed by the current increments its conductivity, a property which makes the system able to mimic Hebbian type learning and have application in hardware neural networks. After discussing the working principle of ...

  2. Allylthioketone Mediated Free Radical Polymerization of Methacrylates

    Directory of Open Access Journals (Sweden)

    Feng Zhong

    2017-11-01

    Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

  3. Comparison of potentials for polymeric liquids

    International Nuclear Information System (INIS)

    Jung, Hae Young

    2002-01-01

    Many theories for polymeric liquids are based on the concepts of cell, hole, free volume of lattice etc. In this theories, van der Waals potential, Lennard-Jones 6-12 potential and their modified potentials are commonly used. In this work, Mie(p,6)potential was applied to the Continuous Lattice Fluid Theory (which extends the discrete lattices of Lattice Fluid Theory to classically continuous lattices) and Dee-Walsch's Cell Theory (which modifies Flory's Equation of State Theory). Both of them are known to be successful theories for polymeric liquids. Thus, PVT values changing with p (the exponent in the repulsion potential) were calculated and compared with experimental values. And, calculated values of Lattice Fluid theory, Flory's Equation of State Theory and Cho-Sanchez Theory using perturbation method were also compared. Through the calculated results, van der Waals potential, Lennard-Jones 6-12 potential and Mie(p,6) potential for polymeric liquids were compared with each other

  4. Polymerization initated at sidewalls of carbon nanotubes

    Science.gov (United States)

    Tour, James M. (Inventor); Hudson, Jared L. (Inventor); Krishnamoorti, Ramanan (Inventor); Yurekli, Koray (Inventor); Mitchell, Cynthia A. (Inventor)

    2011-01-01

    The present invention is directed to aryl halide (such as aryl bromide) functionalized carbon nanotubes that can be utilized in anionic polymerization processes to form polymer-carbon nanotube materials with improved dispersion ability in polymer matrices. In this process the aryl halide is reacted with an alkyllithium species or is reacted with a metal to replace the aryl-bromine bond with an aryl-lithium or aryl-metal bond, respectively. It has further been discovered that other functionalized carbon nanotubes, after deprotonation with a deprotonation agent, can similarly be utilized in anionic polymerization processes to form polymer-carbon nanotube materials. Additionally or alternatively, a ring opening polymerization process can be performed. The resultant materials can be used by themselves due to their enhanced strength and reinforcement ability when compared to their unbound polymer analogs. Additionally, these materials can also be blended with pre-formed polymers to establish compatibility and enhanced dispersion of nanotubes in otherwise hard to disperse matrices resulting in significantly improved material properties. The resultant polymer-carbon nanotube materials can also be used in drug delivery processes due to their improved dispersion ability and biodegradability, and can also be used for scaffolding to promote cellular growth of tissue.

  5. KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    Yong-zhong Bao; Cheng-xi Wang; Zhi-ming Huang; Zhi-xue Weng

    2004-01-01

    The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (Rp0) and steady-state polymerization rate (Rp) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: Rp0 ∝ [I]0.73[S]0.32 and Rp ∝ [I]0.71[S]0.23. The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methyl methacrylate) decreased as the polymerization temperature, [I] and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.

  6. Neutral Polymeric Micelles for RNA Delivery

    Science.gov (United States)

    Lundy, Brittany B.; Convertine, Anthony; Miteva, Martina; Stayton, Patrick S.

    2013-01-01

    RNA interference (RNAi) drugs have significant therapeutic potential but delivery systems with appropriate efficacy and toxicity profiles are still needed. Here, we describe a neutral, ampholytic polymeric delivery system based on conjugatable diblock polymer micelles. The diblock copolymer contains a hydrophilic poly[N-(2-hydroxypropyl) methacrylamide-co-N-(2-(pyridin-2- yldisulfanyl)ethyl)methacrylamide) (poly[HPMA-co-PDSMA]) segment to promote aqueous stability and facilitate thiol-disulfide exchange reactions, and a second ampholytic block composed of propyl acrylic acid (PAA), dimethylaminoethyl methacrylate (DMAEMA), and butyl methacrylate (BMA). The poly[(HPMA-co-PDSMA)-b-(PAA-co-DMAEMA-co-BMA)] was synthesized using Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with an overall molecular weight of 22,000 g/mol and a PDI of 1.88. Dynamic light scattering and fluorescence measurements indicated that the diblock copolymers self-assemble under aqueous conditions to form polymeric micelles with a hydrodynamic radius and critical micelle concentration of 25 nm and 25 μg/mL respectively. Red blood cell hemolysis experiments show that the neutral hydrophilic micelles have potent membrane destabilizing activity at endosomal pH values. Thiolated siRNA targeting glyceraldehyde 3-phosphate dehydrogenase (GAPDH) was directly conjugated to the polymeric micelles via thiol exchange reactions with the pyridal disulfide groups present in the micelle corona. Maximum silencing activity in HeLa cells was observed at a 1:10 molar ratio of siRNA to polymer following a 48 h incubation period. Under these conditions 90 % mRNA knockdown and 65 % and protein knockdown of at 48 h was achieved with negligible toxicity. In contrast the polymeric micelles lacking a pH-responsive endosomalytic segment demonstrated negligible mRNA and protein knockdown under these conditions. The potent mRNA knockdown and excellent biocompatibility of the neutral siRNA conjugates

  7. Biodegradable Polyelectrolyte Obtained by Radiation Polymerization

    International Nuclear Information System (INIS)

    Craciun, G.; Martin, D.; Manaila, E.; Nemtanu, M.; Brasoveanu, M.; Ighigeanu, D.

    2009-01-01

    Poly electrolytes are water-soluble polymers carrying ionic charge along the polymer chain. Depending upon the charge, these polymers are anionic or cationic. The inherent solid - liquid separating efficiency makes these poly electrolytes a unique class of polymers which find extensive application in potable water, industrial raw and process water, municipal sewage treatment, mineral processing and metallurgy, oil drilling and recovery, etc. Also, due to their ability to produce advanced induced coagulation, a considerable amount of bacteria and viruses are precipitated together with the suspended solids. Especially the acrylamide polymers are very efficacious for water treatment but acrylamide is a toxic monomer and therefore their use are governed by international standards that provide the residual acrylamide monomer content (RAMC) in them be less than 0.05%. Under these circumstances our attention was focused on the following research steps that are presented in this paper: 1) Preparation of a special class of poly electrolytes, named Pn, with very low RAMC values, based on electron beam (EB), microwave (MW) and EB + MW induced co-polymerization of aqueous solutions containing appropriate mixtures of acrylamide (AMD) and acrylic acid (AA) monomers (AMD - AA co-polymers). The Pn were obtained by radiation technology with very small RAMC (under 0.01%) as well as in a wide range of molecular weights and charge densities. Very low AMD monomer content of Pn is due to the major advantages of radiation induced polymerization in aqueous solution containing monomers. Due to water presence in the EB irradiated system, irradiated water radicals facilitate the polymerization process and increase rate and level of monomers conversion in co-polymers. Also, once again, by the presence of water, which absorbs MW energy very strongly, the MW polymerization reaction rate is much enhanced resulting in a reaction time about 50-100 times lowers than by conventional heating. Also

  8. A new lithography of functional plasma polymerized thin films

    International Nuclear Information System (INIS)

    Kim, Sung-O

    2001-01-01

    The preparation of the resist for the vacuum lithography was carried out by plasma polymerization. The resist manufactured by plasma polymerization is a monomer produced by MMA (Methyl methacrylate). The functional groups of MMA appeared in the PPMMA (Plasma Polymerized Methyl methacrylate) as well, and this was confirmed through an analysis using FT-IR. The polymerization rate increased as a function of the plasma power and decreased as a function of the system pressure. The sensitivity and contrast of the plasma polymerized thin films were 15 μC/cm2 and 4.3 respectively. The size of the pattern manufactured by Vacuum Lithography using the plasma polymerized thin films was 100 nm

  9. Measurement and Analysis of in vitro Actin Polymerization

    Science.gov (United States)

    Doolittle, Lynda K.; Rosen, Michael K.; Padrick, Shae B.

    2014-01-01

    Summary The polymerization of actin underlies force generation in numerous cellular processes. While actin polymerization can occur spontaneously, cells maintain control over this important process by preventing actin filament nucleation and then allowing stimulated polymerization and elongation by several regulated factors. Actin polymerization, regulated nucleation and controlled elongation activities can be reconstituted in vitro, and used to probe the signaling cascades cells use to control when and where actin polymerization occurs. Introducing a pyrene fluorophore allows detection of filament formation by an increase in pyrene fluorescence. This method has been used for many years and continues to be broadly used, owing to its simplicity and flexibility. Here we describe how to perform and analyze these in vitro actin polymerization assays, with an emphasis on extracting useful descriptive parameters from kinetic data. PMID:23868594

  10. Ultrafast preparation of a polyhedral oligomeric silsesquioxane-based ionic liquid hybrid monolith via photoinitiated polymerization, and its application to capillary electrochromatography of aromatic compounds.

    Science.gov (United States)

    Zhang, Bingyu; Lei, Xiaoyun; Deng, Lijun; Li, Minsheng; Yao, Sicong; Wu, Xiaoping

    2018-06-06

    An ionic liquid hybrid monolithic capillary column was prepared within 7 min via photoinitiated free-radical polymerization of an ionic liquid monomer (1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide); VBIMNTF 2 ) and a methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) acting as a cross-linker. The effects of composition of prepolymerization solution and initiation time on the porous structure and electroosmotic flow (EOF) of monolithic column were investigated. The hybrid monolith was characterized by scanning electron microscopy and FTIR. Owing to the introduction of a rigid nanosized POSS silica core and ionic liquids with multiple interaction sites, the monolithic column has a well-defined 3D skeleton morphology, good mechanical stability, and a stable anodic electroosmotic flow. The hybrid monolithic stationary phase was applied to the capillary electrochromatographic separation of various alkylbenzenes, phenols, anilines and polycyclic aromatic hydrocarbons (PAHs). The column efficiency is highest (98,000 plates/m) in case of alkylbenzenes. Mixed-mode retention mechanisms including hydrophobic interactions, π-π stacking, electrostatic interaction and electrophoretic mobility can be observed. This indicates the potential of this material in terms of efficient separation of analytes of different structural type. Graphical Abstract Preparation of a mixed-mode ionic liquid hybrid monolithic column via photoinitiated polymerization of methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) and 1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide (VBIMNTF 2 ) ionic liquid for use in capillary electrochromatography.

  11. Molecularly imprinted electrochemical sensing interface based on in-situ-polymerization of amino-functionalized ionic liquid for specific recognition of bovine serum albumin.

    Science.gov (United States)

    Wang, Yanying; Han, Miao; Liu, Guishen; Hou, Xiaodong; Huang, Yina; Wu, Kangbing; Li, Chunya

    2015-12-15

    A molecularly imprinted polymer film was in situ polymerized on a carboxyl functionalized multi-walled carbon nanotubes modified glassy carbon electrode surface under room temperature. This technique provides a promising imprinting approach for protein in an aqueous solution using 3-(3-aminopropyl)-1-vinylimidazolium tetrafluoroborate ionic liquid as functional monomer, N, N'-methylenebisacrylamide as crossing linker, ammonium persulfate and N,N,N',N'-tetramethylethylenediamine as initiator, and bovine serum albumin (BSA) as template. The molecularly imprinted polymerized ionic liquid film shows enhanced accessibility, high specificity and sensitivity towards BSA. Electrochemical sensing performance of the imprinted sensor was thoroughly investigated using K3Fe[CN]6/K4Fe[CN]6 as electroactive probes. Under optimal conditions, the current difference before and after specific recognition of BSA was found linearly related to its concentration in the range from 1.50×10(-9) to 1.50×10(-6) mol L(-1). The detection limit was calculated to be 3.91×10(-10) mol L(-1) (S/N=3). The practical application of the imprinted sensor was demonstrated by determining BSA in liquid milk samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Crystal structure of an orthomyxovirus matrix protein reveals mechanisms for self-polymerization and membrane association.

    Science.gov (United States)

    Zhang, Wenting; Zheng, Wenjie; Toh, Yukimatsu; Betancourt-Solis, Miguel A; Tu, Jiagang; Fan, Yanlin; Vakharia, Vikram N; Liu, Jun; McNew, James A; Jin, Meilin; Tao, Yizhi J

    2017-08-08

    Many enveloped viruses encode a matrix protein. In the influenza A virus, the matrix protein M1 polymerizes into a rigid protein layer underneath the viral envelope to help enforce the shape and structural integrity of intact viruses. The influenza virus M1 is also known to mediate virus budding as well as the nuclear export of the viral nucleocapsids and their subsequent packaging into nascent viral particles. Despite extensive studies on the influenza A virus M1 (FLUA-M1), only crystal structures of its N-terminal domain are available. Here we report the crystal structure of the full-length M1 from another orthomyxovirus that infects fish, the infectious salmon anemia virus (ISAV). The structure of ISAV-M1 assumes the shape of an elbow, with its N domain closely resembling that of the FLUA-M1. The C domain, which is connected to the N domain through a flexible linker, is made of four α-helices packed as a tight bundle. In the crystal, ISAV-M1 monomers form infinite 2D arrays with a network of interactions involving both the N and C domains. Results from liposome flotation assays indicated that ISAV-M1 binds membrane via electrostatic interactions that are primarily mediated by a positively charged surface loop from the N domain. Cryoelectron tomography reconstruction of intact ISA virions identified a matrix protein layer adjacent to the inner leaflet of the viral membrane. The physical dimensions of the virion-associated matrix layer are consistent with the 2D ISAV-M1 crystal lattice, suggesting that the crystal lattice is a valid model for studying M1-M1, M1-membrane, and M1-RNP interactions in the virion.

  13. Development and optimization of locust bean gum and sodium alginate interpenetrating polymeric network of capecitabine.

    Science.gov (United States)

    Upadhyay, Mansi; Adena, Sandeep Kumar Reddy; Vardhan, Harsh; Pandey, Sureshwar; Mishra, Brahmeshwar

    2018-03-01

    The objective of the study was to develop interpenetrating polymeric network (IPN) of capecitabine (CAP) using natural polymers locust bean gum (LBG) and sodium alginate (NaAlg). The IPN microbeads were optimized by Box-Behnken Design (BBD) to provide anticipated particle size with good drug entrapment efficiency. The comparative dissolution profile of IPN microbeads of CAP with the marketed preparation proved an excellent sustained drug delivery vehicle. Ionotropic gelation method utilizing metal ion calcium (Ca 2+ ) as a cross-linker was used to prepare IPN microbeads. The optimization study was done by response surface methodology based Box-Behnken Design. The effect of the factors on the responses of optimized batch was exhibited through response surface and contour plots. The optimized batch was analyzed for particle size, % drug entrapment, pharmacokinetic study, in vitro drug release study and further characterized by FTIR, XRD, and SEM. To study the water uptake capacity and hydrodynamic activity of the polymers, swelling studies and viscosity measurement were performed, respectively. The particle size and % drug entrapment of the optimized batch was 494.37 ± 1.4 µm and 81.39 ± 2.9%, respectively, closer to the value predicted by Minitab 17 software. The in vitro drug release study showed sustained release of 92% for 12 h and followed anomalous drug release pattern. The derived pharmacokinetic parameters of optimized batch showed improved results than pure CAP. Thus, the formed IPN microbeads of CAP proved to be an effective extended drug delivery vehicle for the water soluble antineoplastic drug.

  14. Directing the breathing behavior of pillared-layered metal-organic frameworks via a systematic library of functionalized linkers bearing flexible substituents.

    Science.gov (United States)

    Henke, Sebastian; Schneemann, Andreas; Wütscher, Annika; Fischer, Roland A

    2012-06-06

    Flexible metal-organic frameworks (MOFs), also referred to as soft porous crystals (SPCs), show reversible structural transitions dependent on the nature and quantity of adsorbed guest molecules. In recent studies it has been reported that covalent functionalization of the organic linker can influence or even integrate framework flexibility ("breathing") in MOFs. However, rational fine-tuning of such responsive properties is very desirable but challenging as well. Here we present a powerful approach for the targeted manipulation of responsiveness and framework flexibility of an important family of pillared-layered MOFs based on the parent structure [Zn(2)(bdc)(2)(dabco)](n) (bdc = 1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane). A library of functionalized bdc-type linkers (fu-bdc), which bear additional dangling side groups at different positions of the benzene core (alkoxy groups of varying chain length with diverse functionalities and polarity), was generated. Synthesis of the materials [Zn(2)(fu-bdc)(2)(dabco)](n) yields the respective collection of highly responsive MOFs. The parent MOF is only weakly flexible; however, the substituted frameworks of [Zn(2)(fu-bdc)(2)(dabco)](n) contract drastically upon guest removal and expand again upon adsorption of DMF (N,N-dimethylformamide), EtOH, or CO(2), etc., while N(2) is hardly adsorbed and does not open the narrow-pored form. These "breathing" dynamics are attributed to the dangling side chains that act as immobilized "guests", which interact with mobile guest molecules as well as with themselves and with the framework backbone. The structural details of the guest-free, contracted form and the gas sorption behavior (phase transition pressure, hysteresis loop) are highly dependent on the nature of the substituent at the linker and can therefore be adjusted using our approach. Combining our library of functionalized linkers with the concept of mixed-component MOFs (solid solutions) offers very rich

  15. Polypropylene/graphite nanocomposites by in situ polymerization

    International Nuclear Information System (INIS)

    Milani, Marceo A.; Galland, Giselda B.; Quijada, Raul

    2011-01-01

    This work presents the synthesis of nanocomposites of polypropylene/graphite by in situ polymerization using metallocene catalyst and graphene nanosheets. Initially was analyzed which of the metallocene catalysts rac-Et(Ind) 2 ZrCl 2 or rac-Me 2 Si(Ind) 2 ZrCl 2 produces polypropylene with mechanical properties more relevant. Then it were performed the in situ polymerization reactions to obtain the nanocomposites. The polymeric materials were characterized by XRD, DSC, GPC and DMTA. (author)

  16. Investigations in the field of solid state polymerization Pt. 38

    International Nuclear Information System (INIS)

    Hardy, Gy.; Cser, F.; Nyitrai, K.; Fedorova, N.

    1980-01-01

    The stuctural and radiation chemical data of vinyl monomers with long chain paraffinic or cholesteric side groups are critically reviewed. Based on their structural and polymerization kinetical characteristics the monomers may be classified into three groups. Oblique layers are favourable for homogeneous topotactic polymerization. This is characterized by a low activation energy and a radiochemical efficiency very similar to that measured in liquid state polymerization. The tilted layers are not favourable for homogeneous topotactic polymerization. Allyl monomers yield polymers with higher molecular weights in the layer structure than in liquid states. (author)

  17. Nanoporous Polymeric Grating-Based Optical Biosensors (Preprint)

    National Research Council Canada - National Science Library

    Hsiao, Vincent K; Waldeisen, John R; Lloyd, Pamela F; Bunning, Timothy J; Huang, Tony J

    2007-01-01

    .... The fabrication process of the nanoporous polymeric grating involves holographic interference patterning and a functionalized pre-polymer syrup that facilitates the immobilization of biomolecules...

  18. Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

    2007-01-01

    of polymer blocks by “click chemistry”. An all polymerization strategy would imply preparing polymers by living/controlled techniques in such a manner that one block after polymerization can be converted to a macroinitiator enabling the second block to polymerize. The coupling strategy invariably inserts...... a linking unit, 1,4-triazol, resulting from the catalyzed, irreversible 1,3-dipolar cycloaddition reaction between an alkyne and an azide. Thus, this strategy necessitates the proper end functionalization of the polymeric building blocks. Fortunately the 1,4-triazol unit is FDA approved already existing...

  19. STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

    Institute of Scientific and Technical Information of China (English)

    QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

    1983-01-01

    Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET>DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET>DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

  20. Online observation of emulsion polymerization by fluorescence technique

    CERN Document Server

    Rudschuck, S; Fuhrmann, J

    1999-01-01

    An online observation of local polarity via fluorescence spectroscopy was used to study the formation and growth of polymer particles during an emulsifier-free heterogeneous polymerization. The reaction mixture consisted of styrene dispersed in water and the polymerization was initiated by a macro-initiator (hydrolyzed propene-maleic acid copolymer with t-butyl perester groups). Pyrenyl probes were attached to the backbone of the initiator to analyze the heterogeneous reaction. The experimental results allow a clear distinction of different time regions during the heterogeneous polymerization. Information about the heating period, the latex formation, the particle growth and the final stage of the polymerization process (gel point) were obtained. (11 refs).

  1. Resveratrol immobilization and release in polymeric hydrogels

    International Nuclear Information System (INIS)

    Momesso, Roberta Grazzielli Ramos Alves Passarelli

    2010-01-01

    Resveratrol (3, 4', 5-trihydroxystilbene) is a polyphenolic produced by a wide variety of plants in response to injury and found predominantly in grape skins. This active ingredient has been shown to possess benefits for the health, such as the antioxidant capacity which is related to the prevention of several types of cancer and skin aging. However, the oral bioavailability of resveratrol is poor and makes its topical application interesting. The purpose of this study was to immobilize resveratrol in polymeric hydrogels to obtain a release device for topical use. The polymeric matrices composed of poli(N-vinyl-2-pyrrolidone) (PVP), poly(ethyleneglycol) (PEG) and agar or PVP and glycerol irradiated at 20 kGy dose were physical-chemically characterized by gel fraction and swelling tests and its preliminary biocompatibility by in vitro test of cytotoxicity using the technique of neutral red uptake. Due to low solubility of resveratrol in water, the addition of 2% ethanol to the matrices was verified. All matrices showed a high crosslinking degree, capacity of swelling and the preliminary cytotoxicity test showed nontoxicity effect. The devices were obtained by resveratrol immobilization in polymeric matrices, carried out in a one-or-two-steps process, that is, before or after irradiation, respectively. The one step resveratrol devices were characterized by gel fraction, swelling tests and preliminary biocompatibility, and their properties were maintained even after the resveratrol incorporation. The devices containing 0,05% of resveratrol obtained by one-step process and 0,1% of resveratrol obtained by two-steps process were submitted to the release test during 24 h. Resveratrol quantification was done by high performance liquid chromatography (HPLC). The results obtained in the kinetics of release showed that only the devices obtained by two-step process release the resveratrol, which demonstrate antioxidant capacity after the release. (author)

  2. Polymeric media for tritium fixation. Supplement I

    International Nuclear Information System (INIS)

    Franz, J.A.; Burger, L.L.

    1976-01-01

    Procedures for the fixation of tritium as TH or THO in two different polymeric media are described. The complete procedure for THO fixation in a polyureylene-polyurethane polumer, including polymer molding procedures and leach tests is presented. The catalytic tritiation of polystyrene under very mild conditions using a rhodium catalyst is also described. Thermal stabilities and cost estimates for the polymers examined under this program are discussed. Organic polymers were found to have attractive features for the fixation and storage of concentrated tritium wastes due to the convenience of fixation procedures and favorable properties of the resulting media

  3. Proteins and Peptides in Biomimetic Polymeric Membranes

    DEFF Research Database (Denmark)

    Perez, Alfredo Gonzalez

    2013-01-01

    This chapter discusses recent advances and the main advantages of block copolymers for functional membrane protein reconstitution in biomimetic polymeric membranes. A rational approach to the reconstitution of membrane proteins in a functional form can be addressed by a more holistic view by using...... other kind of nonbiological amphiphilic molecules. An interesting possibility could be the use of self-assembled proteins in a lipid-free membrane mimicking the capside of some viruses. The membrane proteins that have been more actively used in combination with block copolymer membranes are gramicidin...

  4. Polymeric biomaterials structure and function, v.1

    CERN Document Server

    Dumitriu, Severian

    2013-01-01

    Biomaterials have had a major impact on the practice of contemporary medicine and patient care. Growing into a major interdisciplinary effort involving chemists, biologists, engineers, and physicians, biomaterials development has enabled the creation of high-quality devices, implants, and drug carriers with greater biocompatibility and biofunctionality. The fast-paced research and increasing interest in finding new and improved biocompatible or biodegradable polymers has provided a wealth of new information, transforming this edition of Polymeric Biomaterials into a two-volume set. This volume

  5. Preparation of super absorbent by irradiation polymerization

    International Nuclear Information System (INIS)

    Hua Fengjun; Tan Chunhong; Qian Mengping

    1995-01-01

    A kind of absorbent is prepared by gamma-rays irradiated by reversed-phase suspension polymerization. Drying particles have 1400 (g/g) absorbency in de-ionic water. Effects of reactive conditions, e.g.: dose-rate, dose, monomer concentration, degree of monomer neutralization and crosslinking agents on absorbency in de-ionic water are discussed. The cause of absorbing de-ionic water by polymer is related to its network structure and ionic equilibrium in particle. Accordingly, a suit reactive condition is chosen for preparation of hydro gel spheres

  6. Immobilization of cellulase by radiation polymerization

    International Nuclear Information System (INIS)

    Kumakura, M.; Kaetsu, I.

    1983-01-01

    Immobilization of cellulase by radiation polymerization at low temperatures was studied. The enzymatic activity of immobilized cellulase pellets varied with the monomer, enzyme concentration, and the thickness of immobilized cellulase pellets. The optimum monomer concentration in the immobilization of cellulase was 30-50% at the pellet thickness of 1.0 mm, in which the enzymatic activity was 50%. The enzymatic activity of immobilized cellulase pellets was examined using various substrates such as cellobiose, carboxymethylcellulose, and paper pretreated by radiation. It was found that irradiated paper can be hydrolyzed by immobilized cellulase pellets. (author)

  7. Planar elongation of soft polymeric networks

    DEFF Research Database (Denmark)

    Jensen, Mette Krog; Hassager, Ole; Rasmussen, Henrik K.

    2010-01-01

    . To validate this new technique, soft polymeric networks of poly(propylene oxide) (PPO) were investigated during deformation. Particle tracking and video recording were used to detect to what extent the imposed strain rate and the sample perimeter remained constant. It was observed that, by using...... difference deviated more from the classical prediction due to the dynamic structures in the material. A modified Lodge model using characteristic parameters from linear viscoelastic measurements gave very good stress predictions at all Deborah numbers used in the quasi-linear regime....

  8. Polymeric Cantilever Arrays for Biosensing Applications

    DEFF Research Database (Denmark)

    Calleja, M.; Tamayo, J.; Johansson, Alicia

    2003-01-01

    We report the fabrication of arrays of polymeric cantilevers for biochemistry applications. The cantilevers are fabricated in the polymer SU-8. The use of a polymer as the component material for the cantilevers provides the sensors with very high sensitivity due to convenient mechanical material...... properties. The fabrication process is based on spin coating of the photosensitive polymer and near-ultraviolet exposure. The method allows obtaining well-controlled and uniform mechanical properties of the cantilevers. The elastic constant of the cantilevers was measured, and their dynamic response...

  9. Charpy Impact Test on Polymeric Molded Parts

    Directory of Open Access Journals (Sweden)

    Alexandra Raicu

    2012-09-01

    Full Text Available The paper presents the Charpy impact tests on the AcrylonitrileButadiene-Styrene (ABS polymeric material parts. The Charpy impact test, also known as the Charpy V-notch test, is a standardized strain rate test which determines the amount of energy absorbed by a material during fracture. This is a typical method described in ASTM Standard D 6110. We use for testing an Instron - Dynatup equipment which have a fully integrated hardware and software package that let us capture load information at very high speed from the impact tests.

  10. Polymeric materials for solar thermal applications

    CERN Document Server

    Köhl, Michael; Papillon, Philippe; Wallner, Gernot M; Saile, Sandrin

    2012-01-01

    Bridging the gap between basic science and technological applications, this is the first book devoted to polymers for solar thermal applications.Clearly divided into three major parts, the contributions are written by experts on solar thermal applications and polymer scientists alike. The first part explains the fundamentals of solar thermal energy especially for representatives of the plastics industry and researchers. Part two then goes on to provide introductory information on polymeric materials and processing for solar thermal experts. The third part combines both of these fields, dis

  11. Modelling degradation of bioresorbable polymeric medical devices

    CERN Document Server

    Pan, J

    2015-01-01

    The use of bioresorbable polymers in stents, fixation devices and tissue engineering is revolutionising medicine. Both industry and academic researchers are interested in using computer modelling to replace some experiments which are costly and time consuming. This book provides readers with a comprehensive review of modelling polymers and polymeric medical devices as an alternative to practical experiments. Chapters in part one provide readers with an overview of the fundamentals of biodegradation. Part two looks at a wide range of degradation theories for bioresorbable polymers and devices.

  12. Properties of immobilized papain by radiation polymerization

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Kaetsu, Isao

    1984-01-01

    Papain was immobilized by the radiation polymerization of various monomers at low temperatures and the effects of the polymer matrix on the enzyme activity and thermal stability of the immobilized enzymes were studied. The activity of the immobilized enzymes prepared from monofunctional (acrylate and methacrylate) monomers was higher than that from bifunctional (bismethacrylate) monomers and that from polyoxyethylene dimethacrylate monomers increased with an increase in the number of oxyethylene units. The thermal stability of the immobilized enzymes prepared from hydrophilic monomers was higher than that from hydrophobic monomers and increased markedly with increasing monomer concentration. (author)

  13. Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Sato, Nobuhiro, E-mail: sato-n@rri.kyoto-u.ac.j [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Matsuyama, Tomochika [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)

    2011-08-15

    The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through {gamma}-ray-induced graft polymerization were investigated with {sup 1}H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of {sup 1}H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of {gamma}-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

  14. A surface science model for the Phillips ethylene polymerization catalyst : thermal activation and polymerization activity

    NARCIS (Netherlands)

    Kimmenade, van E.M.E.; Kuiper, A.E.T.; Tamminga, Y.; Thuene, P.C.; Niemantsverdriet, J.W.

    2004-01-01

    A series of CrOx/SiO2/Si(100) model catalysts were tested for ethylene polymerization activity, varying chromium loading, and calcination temperature. Chromium coverage of the model catalyst, quantified by Rutherford backscattering spectrometry, decreases with increasing calcination temperature as

  15. Linker-free 3D assembly of nanocrystals with tunable unit size for reversible lithium ion storage

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Da; Lee, Jim Yang, E-mail: cheleejy@nus.edu.sg [Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, 119260 (Singapore)

    2011-09-02

    A simple and scalable procedure combining hydrothermal synthesis with post-synthesis calcination was developed to produce a linker-free, thermally stable, mesoscale 3D ordered assembly of spinel-type ZnCo{sub 2}O{sub 4} nanocrystals. The mesoscale assembly with distinctively sharp edges was formed by close-packing the ZnCo{sub 2}O{sub 4} nanocrystal building blocks with a unit size changeable by the synthesis temperature. A self-templating mechanism based on the topotactic transformation of an oxalato-bridged precursor coordination compound was proposed for the assembly. The packaging of crystalline ZnCo{sub 2}O{sub 4} nanoparticles, an active lithium ion storage compound, into a dense organized structure is an effective way to increase the volumetric capacity of ZnCo{sub 2}O{sub 4} nanoparticles for reversible lithium ion storage. The highly ordered 3D assembly of ZnCo{sub 2}O{sub 4} demonstrated excellent reversible lithium ion storage properties and a specific capacity ({approx}800 mAh g{sup -1}) much higher than that of carbon (typically {approx} 350 mAh g{sup -1}).

  16. Multivalent peptidic linker enables identification of preferred sites of conjugation for a potent thialanstatin antibody drug conjugate.

    Directory of Open Access Journals (Sweden)

    Sujiet Puthenveetil

    Full Text Available Antibody drug conjugates (ADCs are no longer an unknown entity in the field of cancer therapy with the success of marketed ADCs like ADCETRIS and KADCYLA and numerous others advancing through clinical trials. The pursuit of novel cytotoxic payloads beyond the mictotubule inhibitors and DNA damaging agents has led us to the recent discovery of an mRNA splicing inhibitor, thailanstatin, as a potent ADC payload. In our previous work, we observed that the potency of this payload was uniquely tied to the method of conjugation, with lysine conjugates showing much superior potency as compared to cysteine conjugates. However, the ADC field is rapidly shifting towards site-specific ADCs due to their advantages in manufacturability, characterization and safety. In this work we report the identification of a highly efficacious site-specific thailanstatin ADC. The site of conjugation played a critical role on both the in vitro and in vivo potency of these ADCs. During the course of this study, we developed a novel methodology of loading a single site with multiple payloads using an in situ generated multi-drug carrying peptidic linker that allowed us to rapidly screen for optimal conjugation sites. Using this methodology, we were able to identify a double-cysteine mutant ADC delivering four-loaded thailanstatin that was very efficacious in a gastric cancer xenograft model at 3mg/kg and was also shown to be efficacious against T-DM1 resistant and MDR1 overexpressing tumor cell lines.

  17. Multivalent peptidic linker enables identification of preferred sites of conjugation for a potent thialanstatin antibody drug conjugate.

    Science.gov (United States)

    Puthenveetil, Sujiet; He, Haiyin; Loganzo, Frank; Musto, Sylvia; Teske, Jesse; Green, Michael; Tan, Xingzhi; Hosselet, Christine; Lucas, Judy; Tumey, L Nathan; Sapra, Puja; Subramanyam, Chakrapani; O'Donnell, Christopher J; Graziani, Edmund I

    2017-01-01

    Antibody drug conjugates (ADCs) are no longer an unknown entity in the field of cancer therapy with the success of marketed ADCs like ADCETRIS and KADCYLA and numerous others advancing through clinical trials. The pursuit of novel cytotoxic payloads beyond the mictotubule inhibitors and DNA damaging agents has led us to the recent discovery of an mRNA splicing inhibitor, thailanstatin, as a potent ADC payload. In our previous work, we observed that the potency of this payload was uniquely tied to the method of conjugation, with lysine conjugates showing much superior potency as compared to cysteine conjugates. However, the ADC field is rapidly shifting towards site-specific ADCs due to their advantages in manufacturability, characterization and safety. In this work we report the identification of a highly efficacious site-specific thailanstatin ADC. The site of conjugation played a critical role on both the in vitro and in vivo potency of these ADCs. During the course of this study, we developed a novel methodology of loading a single site with multiple payloads using an in situ generated multi-drug carrying peptidic linker that allowed us to rapidly screen for optimal conjugation sites. Using this methodology, we were able to identify a double-cysteine mutant ADC delivering four-loaded thailanstatin that was very efficacious in a gastric cancer xenograft model at 3mg/kg and was also shown to be efficacious against T-DM1 resistant and MDR1 overexpressing tumor cell lines.

  18. Biocompatible Porous Polyester-Ether Hydrogel Scaffolds with Cross-Linker Mediated Biodegradation and Mechanical Properties for Tissue Augmentation

    Directory of Open Access Journals (Sweden)

    Berkay Ozcelik

    2018-02-01

    Full Text Available Porous polyester-ether hydrogel scaffolds (PEHs were fabricated using acid chloride/alcohol chemistry and a salt templating approach. The PEHs were produced from readily available and cheap commercial reagents via the reaction of hydroxyl terminated poly(ethylene glycol (PEG derivatives with sebacoyl, succinyl, or trimesoyl chloride to afford ester cross-links between the PEG chains. Through variation of the acid chloride cross-linkers used in the synthesis and the incorporation of a hydrophobic modifier (poly(caprolactone (PCL, it was possible to tune the degradation rates and mechanical properties of the resulting hydrogels. Several of the hydrogel formulations displayed exceptional mechanical properties, remaining elastic without fracture at compressive strains of up to 80%, whilst still displaying degradation over a period of weeks to months. A subcutaneous rat model was used to study the scaffolds in vivo and revealed that the PEHs were infiltrated with well vascularised tissue within two weeks and had undergone significant degradation in 16 weeks without any signs of toxicity. Histological evaluation for immune responses revealed that the PEHs incite only a minor inflammatory response that is reduced over 16 weeks with no evidence of adverse effects.

  19. Optimization and characterization of biomolecule immobilization on silicon substrates using (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde linker

    International Nuclear Information System (INIS)

    Gunda, Naga Siva Kumar; Singh, Minashree; Norman, Lana; Kaur, Kamaljit; Mitra, Sushanta K.

    2014-01-01

    In the present work, we developed and optimized a technique to produce a thin, stable silane layer on silicon substrate in a controlled environment using (3-aminopropyl)triethoxysilane (APTES). The effect of APTES concentration and silanization time on the formation of silane layer is studied using spectroscopic ellipsometry and Fourier transform infrared spectroscopy (FTIR). Biomolecules of interest are immobilized on optimized silane layer formed silicon substrates using glutaraldehyde linker. Surface analytical techniques such as ellipsometry, FTIR, contact angle measurement system, and atomic force microscopy are employed to characterize the bio-chemically modified silicon surfaces at each step of the biomolecule immobilization process. It is observed that a uniform, homogenous and highly dense layer of biomolecules are immobilized with optimized silane layer on the silicon substrate. The developed immobilization method is successfully implemented on different silicon substrates (flat and pillar). Also, different types of biomolecules such as anti-human IgG (rabbit monoclonal to human IgG), Listeria monocytogenes, myoglobin and dengue capture antibodies were successfully immobilized. Further, standard sandwich immunoassay (antibody–antigen–antibody) is employed on respective capture antibody coated silicon substrates. Fluorescence microscopy is used to detect the respective FITC tagged detection antibodies bound to the surface after immunoassay.

  20. Silica-bound copper(II)triazacyclononane as a phosphate esterase: effect of linker length and surface hydrophobicity.

    Science.gov (United States)

    Bodsgard, Brett R; Clark, Robert W; Ehrbar, Anthony W; Burstyn, Judith N

    2009-04-07

    A series of silica-bound Cu(ii) triazacyclononane materials was prepared to study the effect of linker length and surface hydrophobicity on the hydrolysis of phosphate esters. The general synthetic approach for these heterogeneous reagents was rhodium-catalyzed hydrosilation between an alkenyl-modified triazacyclononane and hydride-modified silica followed by metallation with a Cu(ii) salt. Elemental analysis confirmed that organic functionalization of the silica gel was successful and provided an estimate of the surface concentration of triazacyclononane. EPR spectra were consistent with square pyramidal Cu(ii), indicating that Cu(ii) ions were bound to the immobilized macrocycles. The hydrolytic efficacies of these heterogeneous reagents were tested with bis(p-nitrophenyl)phosphate (BNPP) and diethyl 4-nitrophenyl phosphate (paraoxon). The agent that performed best was an octyl-linked, propanol-blocked material. This material had the most hydrophilic surface and the most accessible active site, achieving a rate maximum on par with the other materials, but in fewer cycles and without an induction period.

  1. Solid phase synthesis of mitochondrial triphenylphosphonium-vitamin E metabolite using a lysine linker for reversal of oxidative stress.

    Directory of Open Access Journals (Sweden)

    Mohanad Mossalam

    Full Text Available Mitochondrial targeting of antioxidants has been an area of interest due to the mitochondria's role in producing and metabolizing reactive oxygen species. Antioxidants, especially vitamin E (α-tocopherol, have been conjugated to lipophilic cations to increase their mitochondrial targeting. Synthetic vitamin E analogues have also been produced as an alternative to α-tocopherol. In this paper, we investigated the mitochondrial targeting of a vitamin E metabolite, 2,5,7,8-tetramethyl-2-(2'-carboxyethyl-6-hydroxychroman (α-CEHC, which is similar in structure to vitamin E analogues. We report a fast and efficient method to conjugate the water-soluble metabolite, α-CEHC, to triphenylphosphonium cation via a lysine linker using solid phase synthesis. The efficacy of the final product (MitoCEHC to lower oxidative stress was tested in bovine aortic endothelial cells. In addition the ability of MitoCEHC to target the mitochondria was examined in type 2 diabetes db/db mice. The results showed mitochondrial accumulation in vivo and oxidative stress decrease in vitro.

  2. The bacterial tubulin FtsZ requires its intrinsically disordered linker to direct robust cell wall construction.

    Science.gov (United States)

    Sundararajan, Kousik; Miguel, Amanda; Desmarais, Samantha M; Meier, Elizabeth L; Casey Huang, Kerwyn; Goley, Erin D

    2015-06-23

    The bacterial GTPase FtsZ forms a cytokinetic ring at midcell, recruits the division machinery and orchestrates membrane and peptidoglycan cell wall invagination. However, the mechanism for FtsZ regulation of peptidoglycan metabolism is unknown. The FtsZ GTPase domain is separated from its membrane-anchoring C-terminal conserved (CTC) peptide by a disordered C-terminal linker (CTL). Here we investigate CTL function in Caulobacter crescentus. Strikingly, production of FtsZ lacking the CTL (ΔCTL) is lethal: cells become filamentous, form envelope bulges and lyse, resembling treatment with β-lactam antibiotics. This phenotype is produced by FtsZ polymers bearing the CTC and a CTL shorter than 14 residues. Peptidoglycan synthesis still occurs downstream of ΔCTL; however, cells expressing ΔCTL exhibit reduced peptidoglycan crosslinking and longer glycan strands than wild type. Importantly, midcell proteins are still recruited to sites of ΔCTL assembly. We propose that FtsZ regulates peptidoglycan metabolism through a CTL-dependent mechanism that extends beyond simple protein recruitment.

  3. Synthesis of Cassava Waste Pulp-Acrylamide Super Absorbent: Effect of Initiator and Cross-Linker Concentration

    Directory of Open Access Journals (Sweden)

    Zainal Alim Mas’ud

    2013-05-01

    Full Text Available Cassava waste pulp (CWP contains high carbohydrates that can be modified into super absorbent polymer (SAP through grafting and cross-linking copolymerization. Acrylamide (AM was grafted onto CWP with ammonium persulfate (APS as the initiator and N,N'-methylene-bis-acrylamide (MBA as the cross-linker under atmospheric nitrogen. The effect of APS and MBA concentrations on water absorption capacity of saponified SAP was studied, while the evaluation of grafting ratio (GR and grafting efficiency (GRE was conducted on unsaponified SAP. The grafting success was indicated by the occurrence of IR peaks at wave numbers of 573, 765, 858, and 1667 cm-1. In the saponified SAP, the very intense characteristic band at 1562 cm-1 is due to C=O asymmetric stretching in the carboxylate anion. Saponification increases significantly water absorption capacity compared to that of unsaponified SAP (from 39.79 g/g to 578.23 g/g. The highest water absorption capacity is reached at 0.74% APS and 0.09% MBA. The percentage of GRE and GR tends to increase with increasing APS concentration until reaching the highest value and then decreases. Effect of MBA concentration on water absorption capacity, GR, and on GRE is similar to the effect of initiator concentration on GR and GRE.

  4. NIR-Cyanine Dye Linker: a Promising Candidate for Isochronic Fluorescence Imaging in Molecular Cancer Diagnostics and Therapy Monitoring.

    Science.gov (United States)

    Komljenovic, Dorde; Wiessler, Manfred; Waldeck, Waldemar; Ehemann, Volker; Pipkorn, Ruediger; Schrenk, Hans-Hermann; Debus, Jürgen; Braun, Klaus

    2016-01-01

    Personalized anti-cancer medicine is boosted by the recent development of molecular diagnostics and molecularly targeted drugs requiring rapid and efficient ligation routes. Here, we present a novel approach to synthetize a conjugate able to act simultaneously as an imaging and as a chemotherapeutic agent by coupling functional peptides employing solid phase peptide synthesis technologies. Development and the first synthesis of a fluorescent dye with similarity in the polymethine part of the Cy7 molecule whose indolenine-N residues were substituted with a propylene linker are described. Methylating agent temozolomide is functionalized with a tetrazine as a diene component whereas Cy7-cell penetrating peptide conjugate acts as a dienophilic reaction partner for the inverse Diels-Alder click chemistry-mediated ligation route yielding a theranostic conjugate, 3-mercapto-propionic-cyclohexenyl-Cy7-bis-temozolomide-bromide-cell penetrating peptide. Synthesis route described here may facilitate targeted delivery of the therapeutic compound to achieve sufficient local concentrations at the target site or tissue. Its versatility allows a choice of adequate imaging tags applicable in e.g. PET, SPECT, CT, near-infrared imaging, and therapeutic substances including cytotoxic agents. Imaging tags and therapeutics may be simultaneously bound to the conjugate applying click chemistry. Theranostic compound presented here offers a solid basis for a further improvement of cancer management in a precise, patient-specific manner.

  5. Linker-free 3D assembly of nanocrystals with tunable unit size for reversible lithium ion storage

    International Nuclear Information System (INIS)

    Deng, Da; Lee, Jim Yang

    2011-01-01

    A simple and scalable procedure combining hydrothermal synthesis with post-synthesis calcination was developed to produce a linker-free, thermally stable, mesoscale 3D ordered assembly of spinel-type ZnCo 2 O 4 nanocrystals. The mesoscale assembly with distinctively sharp edges was formed by close-packing the ZnCo 2 O 4 nanocrystal building blocks with a unit size changeable by the synthesis temperature. A self-templating mechanism based on the topotactic transformation of an oxalato-bridged precursor coordination compound was proposed for the assembly. The packaging of crystalline ZnCo 2 O 4 nanoparticles, an active lithium ion storage compound, into a dense organized structure is an effective way to increase the volumetric capacity of ZnCo 2 O 4 nanoparticles for reversible lithium ion storage. The highly ordered 3D assembly of ZnCo 2 O 4 demonstrated excellent reversible lithium ion storage properties and a specific capacity (∼800 mAh g -1 ) much higher than that of carbon (typically ∼ 350 mAh g -1 ).

  6. Construction, Structural Diversity and Properties of Five Coordination Polymers Based on 5-Nitroisophthalate and Bis(imidazole) Linkers

    Science.gov (United States)

    Arıcı, Mürsel

    2018-06-01

    Five coordination polymers, namely, [Cd(μ3-5-nip)(μ-obix)]n (1), [Co(μ3-5-nip)(μ-obix)]n (2), [Zn(μ-5-nip)(μ-obix)]n (3 and 4) and [Cd(μ-5-nip)(μ-bisobix)]n (5) (5-nip: 5-nitroisophthalate, obix: 1,2-bis(imidazol-1ylmethyl)benzene, bisobix: 1,2-bis(2-isopropylimidazol-1ylmethyl)benzene) were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). X-ray results showed that the complexes displayed structural diversity depending on metal ions and conformations of bis(imidazole) linkers. Complexes 1 and 2 were 1D structures and obix ligand displayed cis-conformation. Complexes 3 and 4 exhibited 2D and 3D structures with same components depending on obix conformation. In complex 5, 3D+3D→3D interpenetrated structure was obtained with dia topology when bisobix having sterically hindered groups on imidazole rings was used. Moreover, thermal, photoluminescence and optical properties of the complexes were also investigated.

  7. Demonstration of Improved Charge Transfer in Graphene/Au Nanorods Plasmonic Hybrids Stabilized by Benzyl Thiol Linkers

    Directory of Open Access Journals (Sweden)

    Giuseppe Valerio Bianco

    2016-01-01

    Full Text Available Hybrids based on graphene decorated with plasmonic gold (Au nanostructures are being investigated as possible materials combination to add to graphene functionalities of tunable plasmon resonance and enhanced absorption at selected wavelength in the visible-near-infrared region of the spectrum. Here, we report a solution drop-casting approach for fabricating stable hybrids based on chemical vapor deposition (CVD graphene and Au nanorods, which are able to activate effective charge transfer from graphene. We demonstrate that CVD graphene functionalization by benzyl thiol (BZT provides the linker to strong anchoring, via S-Au bonds, Au nanorods to graphene. Optical measurements by spectroscopic ellipsometry give evidence of the introduction of plasmon resonances at 1.85 and 2.25 eV in the Au nanorods/BZT/graphene hybrids, which enable surface enhanced Raman scattering (SERS detection. Furthermore, an effective electron transfer from graphene to Au nanorods, resulting in an enhancement of p-type doping of graphene with a consequent decrease of its sheet resistance, is probed by Raman spectroscopy and corroborated by electrical measurements.

  8. Phosphonate self-assembled monolayers as organic linkers in solid-state quantum dot sensetized solar cells

    KAUST Repository

    Ardalan, Pendar

    2010-06-01

    We have employed X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) spectroscopy, infrared (IR) spectroscopy, water contact angle (WCA) measurements, ellipsometry, and electrical measurements to study the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state quantum dot sensitized solar cells (QDSSCs). ∼2 to ∼6 nm size CdS quantum dots (QDs) were grown on the SAM-passivated TiO2 surfaces by successive ionic layer adsorption and reaction (SILAR). Our results show differences in the bonding of the CdS QDs at the TiO2 surfaces with a SAM linker. Moreover, our data indicate that presence of a SAM increases the CdS uptake on TiO2 as well as the performance of the resulting devices. Importantly, we observe ∼2 times higher power conversion efficiencies in the devices with a SAM compared to those that lack a SAM. © 2010 IEEE.

  9. Optimization and characterization of biomolecule immobilization on silicon substrates using (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde linker

    Energy Technology Data Exchange (ETDEWEB)

    Gunda, Naga Siva Kumar [Department of Mechanical Engineering, University of Alberta, Edmonton, Canada T6G 2G8 (Canada); Singh, Minashree [Department of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Canada T6G 1C9 (Canada); Norman, Lana [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 2V4 (Canada); Kaur, Kamaljit [Department of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Canada T6G 1C9 (Canada); Mitra, Sushanta K., E-mail: sushanta.mitra@ualberta.ca [Department of Mechanical Engineering, University of Alberta, Edmonton, Canada T6G 2G8 (Canada)

    2014-06-01

    In the present work, we developed and optimized a technique to produce a thin, stable silane layer on silicon substrate in a controlled environment using (3-aminopropyl)triethoxysilane (APTES). The effect of APTES concentration and silanization time on the formation of silane layer is studied using spectroscopic ellipsometry and Fourier transform infrared spectroscopy (FTIR). Biomolecules of interest are immobilized on optimized silane layer formed silicon substrates using glutaraldehyde linker. Surface analytical techniques such as ellipsometry, FTIR, contact angle measurement system, and atomic force microscopy are employed to characterize the bio-chemically modified silicon surfaces at each step of the biomolecule immobilization process. It is observed that a uniform, homogenous and highly dense layer of biomolecules are immobilized with optimized silane layer on the silicon substrate. The developed immobilization method is successfully implemented on different silicon substrates (flat and pillar). Also, different types of biomolecules such as anti-human IgG (rabbit monoclonal to human IgG), Listeria monocytogenes, myoglobin and dengue capture antibodies were successfully immobilized. Further, standard sandwich immunoassay (antibody–antigen–antibody) is employed on respective capture antibody coated silicon substrates. Fluorescence microscopy is used to detect the respective FITC tagged detection antibodies bound to the surface after immunoassay.

  10. Influence of vibronic contribution on light harvesting efficiency of NKX-2587 derivatives with oligothiophene as π-conjugated linker

    Science.gov (United States)

    Yang, Pan; Zhang, Yang; Li, Ming; Shen, Wei; He, Rongxing

    2018-01-01

    Based on the NKX-2587 molecule we designed ten sensitizers with 1-10 thiophene moieties to investigate how the number of thiophene unit in the spacer influences the absorption spectra of sensitizer in dye sensitized solar cells (DSSCs). The parameters of short-circuit current density (Jsc), open circuit voltage (Voc), the light harvesting efficiency (LHE), injection driving force (Δ Ginject), and transferred electron number (nc), were calculated and discussed in detail. Results indicated that the increasing of thiophene units makes for the enhancement of oscillator strengths (f), although the red shift of vertical electronic absorption spectra is small. For the designed sensitizers with 1-5 thiophene units, their ΔGinject and nc raise gradually with the increasing of thiophene number. However, for those sensitizers with 6-10 thiophene units, the ΔGinject and nc decrease continuously with the increasing of thiophene units. In order to study how the oligothiophene as π-conjugated linker affects light harvesting efficiency of DSSCs, the vibrationally resolved electronic spectra of five metal-free NKX-2587 derivatives with 1-5 thiophene units were simulated within the Franck-Condon approximation including the Herzberg-Teller and Duschinsky effects. The present theoretical results provided helpful guidance for understanding the sources of spectral intensities of dye molecules, and a valuable method for rational design of new molecules to improve the energy conversion efficiency (η) of DSSCs.

  11. Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid.

    Science.gov (United States)

    Reinsch, Helge; Pillai, Renjith S; Siegel, Renée; Senker, Jürgen; Lieb, Alexandra; Maurin, Guillaume; Stock, Norbert

    2016-03-14

    The new aluminium based metal-organic framework [Al(OH)(O2C-C4H8-CO2)]·H2O denoted as Al-MIL-53-ADP-lp (lp stands for large pore) was synthesised under solvothermal conditions. This solid is an analogue of the archetypical aluminium terephthalate Al-MIL-53 based on the aliphatic single-chain linker molecule adipic acid (H2ADP, hexanedioic acid). In contrast to its aromatic counterparts, Al-MIL-53-ADP exhibits a structural breathing behaviour solely upon dehydration/rehydration. The crystal structure of the anhydrous compound denoted as Al-MIL-53-ADP-np (np stands for narrow pore) was determined by a combination of forcefield-based computations and Rietveld refinement of the powder X-ray diffraction data while the structure of the hydrated form Al-MIL-53-ADP-lp was derived computationally by a combination of force field based methods and Density Functional Theory calculations. Both structures were further supported by (1)H, (13)C and (27)Al high-resolution NMR MAS 1D data coupled again with simulations. Al-MIL-53-ADP was further characterised by means of vibrational spectroscopy, elemental analysis, thermogravimetry and water vapour sorption.

  12. Molecularly imprinted polymeric stir bar: Preparation and application for the determination of naftopidil in plasma and urine samples.

    Science.gov (United States)

    Peng, Jun; Xiao, Deli; He, Hua; Zhao, Hongyan; Wang, Cuixia; Shi, Tian; Shi, Kexin

    2016-01-01

    In this study, molecularly imprinting technology and stir bar absorption technology were combined to develop a microextraction approach based on a molecularly imprinted polymeric stir bar. The molecularly imprinted polymer stir bar has a high performance, is specific, economical, and simple to prepare. The obtained naftopidil-imprinted polymer-coated bars could simultaneously agitate and adsorb naftopidil in the sample solution. The ratio of template/monomer/cross-linker and conditions of template removal were optimized to prepare a stir bar with highly efficient adsorption. Fourier transform infrared spectroscopy, scanning electron microscopy, selectivity, and extraction capacity experiments showed that the molecularly imprinted polymer stir bar was prepared successfully. To utilize the molecularly imprinted polymer stir bar for the determination of naftopidil in complex body fluid matrices, the extraction time, stirring speed, eluent, and elution time were optimized. The limits of detection of naftopidil in plasma and urine sample were 7.5 and 4.0 ng/mL, respectively, and the recoveries were in the range of 90-112%. The within-run precision and between-run precision were acceptable (relative standard deviation bar based microextraction with high-performance liquid chromatography was a convenient, rapid, efficient, and specific method for the precise determination of trace naftopidil in clinical analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A Dual-Purpose Linker for Alpha Helix Stabilization and Imaging Agent Conjugation to Glucagon-Like Peptide-1 Receptor Ligands

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Liao, Jianshan; Thurber, Greg M.

    2016-01-01

    Peptides display many characteristics of efficient imaging agents such as rapid targeting, fast background clearance, and low non-specific cellular uptake. However, poor stability, low affinity, and loss of binding after labeling often preclude their use in vivo. Using the glucagon-like peptide-1 receptor (GLP-1R) ligands exendin and GLP-1 as a model system, we designed a novel alpha helix stabilizing linker to simultaneously address these limitations. The stabilized and labeled peptides showed an increase in helicity, improved protease resistance, negligible loss or an improvement in binding affinity, and excellent in vivo targeting. The ease of incorporating azidohomoalanine in peptides and efficient reaction with the dialkyne linker enables this technique to potentially be used as a general method for labeling alpha helices. This strategy should be useful for imaging beta cells in diabetes research and in developing and testing other peptide targeting agents. PMID:25594741

  14. Mutation of Gly717Phe in human topoisomerase 1B has an effect on enzymatic function, reactivity to the camptothecin anticancer drug and on the linker domain orientation

    DEFF Research Database (Denmark)

    Wang, Zhenxing; D'Annessa, Ilda; Tesauro, Cinzia

    2015-01-01

    –DNA covalent adduct. In this work the role of the Gly717 residue, located in a α-helix structure bridging the active site and the linker domain, has been investigated mutating it in Phe. The mutation gives rise to drug resistance in vivo as observed through a viability assay of yeast cells. In vitro activity...... assays show that the mutant is characterized by a fast religation rate, only partially reduced by the presence of the drug. Comparative molecular dynamics simulations of the native and mutant proteins indicate that the mutation of Gly717 affects the motion orientation of the linker domain, changing its...... interaction with the DNA substrate, likely affecting the strand rotation and religation rate. The mutation also causes a slight rearrangement of the active site and of the drug binding site, providing an additional explanation for the lowered effect of camptothecin toward the mutant....

  15. Learning a weighted sequence model of the nucleosome core and linker yields more accurate predictions in Saccharomyces cerevisiae and Homo sapiens.

    Directory of Open Access Journals (Sweden)

    Sheila M Reynolds

    2010-07-01

    Full Text Available DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence-301 base pairs, centered at the position to be scored-with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the

  16. Learning a weighted sequence model of the nucleosome core and linker yields more accurate predictions in Saccharomyces cerevisiae and Homo sapiens.

    Science.gov (United States)

    Reynolds, Sheila M; Bilmes, Jeff A; Noble, William Stafford

    2010-07-08

    DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence-301 base pairs, centered at the position to be scored-with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the bulk of the

  17. Epigenetics and autism spectrum disorder: A report of an autism case with mutation in H1 linker histone HIST1H1e and literature review.

    Science.gov (United States)

    Duffney, Lara J; Valdez, Purnima; Tremblay, Martine W; Cao, Xinyu; Montgomery, Sarah; McConkie-Rosell, Allyn; Jiang, Yong-Hui

    2018-04-27

    Genetic mutations in genes encoding proteins involved in epigenetic machinery have been reported in individuals with autism spectrum disorder (ASD), intellectual disability, congenital heart disease, and other disorders. H1 histone linker protein, the basic component in nucleosome packaging and chromatin organization, has not been implicated in human disease until recently. We report a de novo deleterious mutation of histone cluster 1 H1 family member e (HIST1H1E; c.435dupC; p.Thr146Hisfs*50), encoding H1 histone linker protein H1.4, in a 10-year-old boy with autism and intellectual disability diagnosed through clinical whole exome sequencing. The c.435dupC at the 3' end of the mRNA leads to a frameshift and truncation of the positive charge in the carboxy-terminus of the protein. An expression study demonstrates the mutation leads to reduced protein expression, supporting haploinsufficiency of HIST1H1E protein and loss of function as an underlying mechanism of dysfunction in the brain. Taken together with other recent cases with mutations of HIST1H1E in intellectual disability, the evidence supporting the link to causality in disease is strong. Our finding implicates the deficiency of H1 linker histone protein in autism. The systematic review of candidate genes implicated in ASD revealed that 42 of 215 (19.5%) genes are directly involved in epigenetic regulations and the majority of these genes belong to histone writers, readers, and erasers. While the mechanism of how haploinsufficiency of HIST1H1E causes autism is entirely unknown, our report underscores the importance of further study of the function of this protein and other histone linker proteins in brain development. © 2018 Wiley Periodicals, Inc.

  18. Funktionalisierte Linker für Metallorganische Gerüstverbindungen, deren postsynthetische Modifikation und polar markierte Schutzgruppen für terminale Alkine

    OpenAIRE

    Roy, Pascal

    2011-01-01

    Metal-organic frameworks (MOFs) form the class of porous materials with the highest surface areas. This characteristic property combined with the variability of both building blocks, the inorganic node and the organic linker, makes many scientists dream of materials with very special chemical, electronic, optic and/or magnetic properties. For individual applications both building blocks, but also possibly in the framework embedded guests, play a crucial role. This work describes the synthe...

  19. Assessing the adsorption selectivity of linker functionalized, moisture-stable metal-organic framework thin films by means of an environment-controlled quartz crystal microbalance.

    Science.gov (United States)

    Bétard, Angélique; Wannapaiboon, Suttipong; Fischer, Roland A

    2012-11-04

    The stepwise thin film deposition of the robust, hydrophobic [Zn(4)O(dmcapz)(3)](n) (dmcapz = 3,5-dimethyl-4-carboxy-pyrazolato) is reported. The adsorption of small organic probe molecules, including alkanols, toluene, aniline and xylenes, was monitored by an environment-controlled quartz crystal microbalance setup. The adsorption selectivity was tuned by introducing alkyl side chains in the dmcapz linker.

  20. Learning a Weighted Sequence Model of the Nucleosome Core and Linker Yields More Accurate Predictions in Saccharomyces cerevisiae and Homo sapiens

    Science.gov (United States)

    Reynolds, Sheila M.; Bilmes, Jeff A.; Noble, William Stafford

    2010-01-01

    DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence—301 base pairs, centered at the position to be scored—with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the bulk of the

  1. Identification of unique interactions between the flexible linker and the RecA-like domains of DEAD-box helicase Mss116

    International Nuclear Information System (INIS)

    Zhang, Yuan; Palla, Mirkó; Liao, Jung-Chi; Sun, Andrew

    2013-01-01

    DEAD-box RNA helicases are ATP-dependent proteins implicated in nearly all aspects of RNA metabolism. The yeast DEAD-box helicase Mss116 is unique in its functions of splicing group I and group II introns and activating mRNA translation, but the structural understanding of why it performs these unique functions remains unclear. Here we used sequence analysis and molecular dynamics simulation to identify residues in the flexible linker specific for yeast Mss116, potentially associated with its unique functions. We first identified residues that are 100% conserved in Mss116 of different species of the Saccharomycetaceae family. The amino acids of these conserved residues were then compared with the amino acids of the corresponding residue positions of other RNA helicases to identify residues that have distinct amino acids from other DEAD-box proteins. Four residues in the flexible linker, i.e. N334, E335, P336 and H339, are conserved and Mss116-specific. Molecular dynamics simulation was conducted for the wild-type Mss116 structure and mutant models to examine mutational effects of the linker on the conformational equilibrium. Relatively short MD simulation runs (within 20 ns) were enough for us to observe mutational effects, suggesting serious structural perturbations by these mutations. The mutation of E335 depletes the interactions between E335 and K95 in domain 1. The interactions between N334/P336 and N496/I497 of domain 2 are also abolished by mutation. Our results suggest that tight interactions between the Mss116-specific flexible linker and the two RecA-like domains may be mechanically required to crimp RNA for the unique RNA processes of yeast Mss116. (paper)

  2. Identification of unique interactions between the flexible linker and the RecA-like domains of DEAD-box helicase Mss116

    Science.gov (United States)

    Zhang, Yuan; Palla, Mirkó; Sun, Andrew; Liao, Jung-Chi

    2013-09-01

    DEAD-box RNA helicases are ATP-dependent proteins implicated in nearly all aspects of RNA metabolism. The yeast DEAD-box helicase Mss116 is unique in its functions of splicing group I and group II introns and activating mRNA translation, but the structural understanding of why it performs these unique functions remains unclear. Here we used sequence analysis and molecular dynamics simulation to identify residues in the flexible linker specific for yeast Mss116, potentially associated with its unique functions. We first identified residues that are 100% conserved in Mss116 of different species of the Saccharomycetaceae family. The amino acids of these conserved residues were then compared with the amino acids of the corresponding residue positions of other RNA helicases to identify residues that have distinct amino acids from other DEAD-box proteins. Four residues in the flexible linker, i.e. N334, E335, P336 and H339, are conserved and Mss116-specific. Molecular dynamics simulation was conducted for the wild-type Mss116 structure and mutant models to examine mutational effects of the linker on the conformational equilibrium. Relatively short MD simulation runs (within 20 ns) were enough for us to observe mutational effects, suggesting serious structural perturbations by these mutations. The mutation of E335 depletes the interactions between E335 and K95 in domain 1. The interactions between N334/P336 and N496/I497 of domain 2 are also abolished by mutation. Our results suggest that tight interactions between the Mss116-specific flexible linker and the two RecA-like domains may be mechanically required to crimp RNA for the unique RNA processes of yeast Mss116.

  3. Numerical simulation of anisotropic polymeric foams

    Directory of Open Access Journals (Sweden)

    Volnei Tita

    Full Text Available This paper shows in detail the modelling of anisotropic polymeric foam under compression and tension loadings, including discussions on isotropic material models and the entire procedure to calibrate the parameters involved. First, specimens of poly(vinyl chloride (PVC foam were investigated through experimental analyses in order to understand the mechanical behavior of this anisotropic material. Then, isotropic material models available in the commercial software AbaqusTM were investigated in order to verify their ability to model anisotropic foams and how the parameters involved can influence the results. Due to anisotropy, it is possible to obtain different values for the same parameter in the calibration process. The obtained set of parameters are used to calibrate the model according to the application of the structure. The models investigated showed minor and major limitations to simulate the mechanical behavior of anisotropic PVC foams under compression, tension and multi-axial loadings. Results show that the calibration process and the choice of the material model applied to the polymeric foam can provide good quantitative results and save project time. Results also indicate what kind and order of error one will get if certain choices are made throughout the modelling process. Finally, even though the developed calibration procedure is applied to specific PVC foam, it still outlines a very broad drill to analyze other anisotropic cellular materials.

  4. Functionalized nanoparticle interactions with polymeric membranes.

    Science.gov (United States)

    Ladner, D A; Steele, M; Weir, A; Hristovski, K; Westerhoff, P

    2012-04-15

    A series of experiments was performed to measure the retention of a class of functionalized nanoparticles (NPs) on porous (microfiltration and ultrafiltration) membranes. The findings impact engineered water and wastewater treatment using membrane technology, characterization and analytical schemes for NP detection, and the use of NPs in waste treatment scenarios. The NPs studied were composed of silver, titanium dioxide, and gold; had organic coatings to yield either positive or negative surface charge; and were between 2 and 10nm in diameter. NP solutions were applied to polymeric membranes composed of different materials and pore sizes (ranging from ≈ 2 nm [3 kDa molecular weight cutoff] to 0.2 μm). Greater than 99% rejection was observed of positively charged NPs by negatively charged membranes even though pore diameters were up to 20 times the NP diameter; thus, sorption caused rejection. Negatively charged NPs were less well rejected, but behavior was dependent not only on surface functionality but on NP core material (Ag, TiO(2), or Au). NP rejection depended more upon NP properties than membrane properties; all of the negatively charged polymeric membranes behaved similarly. The NP-membrane interaction behavior fell into four categories, which are defined and described here. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Degradable polymeric materials for osteosynthesis: Tutorial

    Directory of Open Access Journals (Sweden)

    D Eglin

    2008-12-01

    Full Text Available This report summarizes the state of the art and recent developments and advances in the use of degradable polymers devices for osteosynthesis. The current generation of biodegradable polymeric implants for bone repair utilising designs copied from metal implants, originates from the concept that devices should be supportive and as “inert” substitute to bone tissue. Today degradable polymeric devices for osteosynthesis are successful in low or mild load bearing applications. However, the lack of carefully controlled randomized prospective trials that document their efficacy in treating a particular fracture pattern is still an issue. Then, the choice between degradable and non-degradable devices must be carefully weighed and depends on many factors such as the patient age and condition, the type of fracture, the risk of infection, etc. The improvement of the biodegradable devices mechanical properties and their degradation behaviour will have to be achieved to broaden their use. The next generation of biodegradable implants will probably see the implementation of the recent gained knowledge in cell-material interactions and cells therapy, with a better control of the spatial and temporal interfaces between the material and the surrounding bone tissue.

  6. Chemical polymerization of aniline in phenylphosphinic acid

    Directory of Open Access Journals (Sweden)

    NICOLETA PLESU

    2005-10-01

    Full Text Available The chemical polymerization of aniline was performed in phenylphosphinic acid (APP medium using ammonium peroxidisulfate as the oxidizing agent, at 0 ºC and 25 ºC. The yield of polyaniline (PANI was about 60–69 %. The polymerization process required an induction time 8–10 times greater than in other acids (hydrochloric, sulfuric. The average density of the obtained polymer was 1.395 g cm-3 for PANI-salt and 1.203 g cm-3 for PANI-base. The acid capacity of PANI depends on the synthesis parameters and the maximum value was 15.02 meq/g polymer. The inherent viscosity of PANI was 0.662 dl/g at aniline/oxidant molar ratios >2 and 0 ºC. The oxidation state was a function of the synthesis parameters and lay between 0.553–0.625, as determined from UV-VIS and titration with TiCl3 data. The PANI samples were characterized by measurements of their density, inherent viscosity, conductivity, acid capacity, FTIR and UV-VIS spectrum, and thermogravimetric data.

  7. Novel distributed strain sensing in polymeric materials

    International Nuclear Information System (INIS)

    Abot, Jandro L; Song, Yi; Medikonda, Sandeep; Rooy, Nathan; Schulz, Mark J

    2010-01-01

    Monitoring the state of strain throughout an entire structure is essential to determine its state of stress, detect potential residual stresses after fabrication, and also to help to establish its integrity. Several sensing technologies are presently available to determine the strain in the surface or inside a structure. Large sensor dimensions, complex signal conditioning equipment, and difficulty in achieving a widely distributed system have however hindered their development into robust structural health monitoring techniques. Recently, carbon nanotube forests were spun into a microscale thread that is electrically conductive, tough, and easily tailorable. The thread was integrated into polymeric materials and used for the first time as a piezoresistive sensor to monitor strain and also to detect damage in the material. It is revealed that the created self-sensing polymeric materials are sensitive to normal strains above 0.07% and that the sensor thread exhibits a perfectly linear delta resistance–strain response above 0.3%. The longitudinal gauge factors were determined to be in the 2–5 range. This low cost and simple built-in sensor thread may provide a new integrated and distributed sensor technology that enables robust real-time health monitoring of structures

  8. Metallophilic interactions in polymeric group 11 thiols

    Science.gov (United States)

    Kolari, Kalle; Sahamies, Joona; Kalenius, Elina; Novikov, Alexander S.; Kukushkin, Vadim Yu.; Haukka, Matti

    2016-10-01

    Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2- counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the AgṡṡṡAg distance was found to be less than sum of the Bondi's van der Waals radius of silver.

  9. A pulse radiolysis study of emulsion polymerization

    International Nuclear Information System (INIS)

    McAskill, N.A.

    1976-01-01

    The emulsion polymerisation of slightly water soluble monomers such as styrene occurs initially in micelles of surfactant swollen with monomer and later in larger particles consisting of polymer swollen with monomer and stabilized with an outer layer of surfactant. There is considerable controversy on whether the reaction sites of polymerization are inside or on the surface of the particle or micelle. The relative amounts of micelle and particles present at various stages of the polymerization are also nuclear. In the present study the OH radical formed by pulse radiolysis has been used as a probe to investigate the site of solubilization of styrene in various surfactant micelles. Two products can be distinguished by UV spectrometry, a benzyl type radical formed by OH addition to the side chain of styrene and a cyclohexadienyl type radical formed by addition to the ring. Wide differences in the relative amounts of each product were observed suggesting that in some surfactants the styrene ring is buried inside the micelle whilst in other systems the styrene appears to be so solubilized at the interface leaving both the ring and the side chain open to attack by the OH radical. (author)

  10. Optimization of the Alkyl Linker of TO Base Surrogate in Triplex-Forming PNA for Enhanced Binding to Double-Stranded RNA.

    Science.gov (United States)

    Sato, Takaya; Sato, Yusuke; Nishizawa, Seiichi

    2017-03-23

    A series of triplex-forming peptide nucleic acid (TFP) probes carrying a thiazole orange (TO) base surrogate through an alkyl linker was synthesized, and the interactions between these so-called tFIT probes and purine-rich sequences within double-stranded RNA (dsRNA) were examined. We found that the TO base surrogate linker significantly affected both the binding affinity and the fluorescence response upon triplex formation with the target dsRNA. Among the probes examined, the TO base surrogate connected through the propyl linker in the tFIT probes increased the binding affinity by a factor of ten while maintaining its function as the fluorescent universal base. Isothermal titration calorimetry experiments revealed that the increased binding affinity resulted from the gain in the binding enthalpy, which could be explained by the enhanced π-stacking interaction between the TO base surrogate and the dsRNA part of the triplex. We expect that these results will provide a molecular basis for designing strong binding tFIT probes for fluorescence sensing of various kinds of purine-rich dsRNAs sequences including those carrying a pyrimidine-purine inversion. The obtained data also offers a new insight into further development of the universal bases incorporated in TFP. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The role of H1 linker histone subtypes in preserving the fidelity of elaboration of mesendodermal and neuroectodermal lineages during embryonic development.

    Directory of Open Access Journals (Sweden)

    Giang D Nguyen

    Full Text Available H1 linker histone proteins are essential for the structural and functional integrity of chromatin and for the fidelity of additional epigenetic modifications. Deletion of H1c, H1d and H1e in mice leads to embryonic lethality by mid-gestation with a broad spectrum of developmental alterations. To elucidate the cellular and molecular mechanisms underlying H1 linker histone developmental functions, we analyzed embryonic stem cells (ESCs depleted of H1c, H1d and H1e subtypes (H1-KO ESCs by utilizing established ESC differentiation paradigms. Our study revealed that although H1-KO ESCs continued to express core pluripotency genes and the embryonic stem cell markers, alkaline phosphatase and SSEA1, they exhibited enhanced cell death during embryoid body formation and during specification of mesendoderm and neuroectoderm. In addition, we demonstrated deregulation in the developmental programs of cardiomyocyte, hepatic and pancreatic lineage elaboration. Moreover, ectopic neurogenesis and cardiomyogenesis occurred during endoderm-derived pancreatic but not hepatic differentiation. Furthermore, neural differentiation paradigms revealed selective impairments in the specification and maturation of glutamatergic and dopaminergic neurons with accelerated maturation of glial lineages. These impairments were associated with deregulation in the expression profiles of pro-neural genes in dorsal and ventral forebrain-derived neural stem cell species. Taken together, these experimental observations suggest that H1 linker histone proteins are critical for the specification, maturation and fidelity of organ-specific cellular lineages derived from the three cardinal germ layers.

  12. Surface expression and subunit specific control of steady protein levels by the Kv7.2 helix A-B linker.

    Directory of Open Access Journals (Sweden)

    Paloma Aivar

    Full Text Available Kv7.2 and Kv7.3 are the main components of the neuronal voltage-dependent M-current, which is a subthreshold potassium conductance that exerts an important control on neuronal excitability. Despite their predominantly intracellular distribution, these channels must reach the plasma membrane in order to control neuronal activity. Thus, we analyzed the amino acid sequence of Kv7.2 to identify intrinsic signals that may control its surface expression. Removal of the interlinker connecting helix A and helix B of the intracellular C-terminus produces a large increase in the number of functional channels at the plasma membrane. Moreover, elimination of this linker increased the steady-state amount of protein, which was not associated with a decrease of protein degradation. The magnitude of this increase was inversely correlated with the number of helix A - helix B linkers present in the tetrameric channel assemblies. In contrast to the remarkable effect on the amount of Kv7.2 protein, removal of the Kv7.2 linker had no detectable impact on the steady-state levels of Kv7.3 protein.

  13. Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

    NARCIS (Netherlands)

    Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, Gyula J.

    2013-01-01

    Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer

  14. Colloidal templating : a route towards controlled synthesis of functional polymeric nanoparticles

    NARCIS (Netherlands)

    Ali, S.I.

    2010-01-01

    Template-directed synthesis of polymeric nanoparticles offers better control over particle morphology, shape, structure, composition and properties compare to the conventional emulsion polymerization routes. For the production of anisotropic polymer-clay composite latex particles and polymeric

  15. Photocontrol in Complex Polymeric Materials: Fact or Illusion?

    Science.gov (United States)

    Jerca, Valentin Victor; Hoogenboom, Richard

    2018-06-04

    Photoswitches: Exciting recent progress realized in the field of light-controlled polymeric materials is highlighted. It is discussed how the rational choice of azobenzene molecules and their incorporation into complex materials by making use of physical interactions can lead to genuine photocontrollable polymeric systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Anisotropic microporous supports impregnated with polymeric ion-exchange materials

    Science.gov (United States)

    Friesen, Dwayne; Babcock, Walter C.; Tuttle, Mark

    1985-05-07

    Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets.

  17. Continuous fabrication of polymeric vesicles and nanotubes with fluidic channe

    NARCIS (Netherlands)

    Peng, F.; Deng, N.-N.; Tu, Y.; van Hest, J.C.M.; Wilson, D.A.

    2017-01-01

    Fluidic channels were employed to induce the self-assembly of poly(ethylene glycol)-b-polystyrene into polymeric vesicles and nanotubes. The laminar flow in the device enables controlled diffusion of two miscible liquids at the phase boundary, leading to the formation of homogeneous polymeric

  18. electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to ...

  19. Electrocatalytic reduction of oxygen at vapor phase polymerized ...

    African Journals Online (AJOL)

    We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

  20. Polymerization Simulator for Introductory Polymer and Material Science Courses

    Science.gov (United States)

    Chirdon, William M.

    2010-01-01

    This work describes how molecular simulation of polymerization reactions can be used to enrich introductory polymer or material science courses to give students a deeper understanding of free-radical chain and stepwise growth polymerization reactions. These simulations have proven to be effective media for instruction that do not require material…

  1. Synthesis of Terpyridine-Terminated Polymers by Anionic Polymerization

    NARCIS (Netherlands)

    Guerrero-Sanchez, C.A.; Lohmeijer, B.G.G.; Meier, M.A.R.; Schubert, U.S.

    2005-01-01

    The synthesis of terpyridine-functionalized polystyrene was achieved by reacting 4‘-chloro-2,2‘:6‘,2‘ ‘-terpyridine (terminating agent) with "living" polymeric carbanions synthesized by anionic polymerization. The obtained polymers were characterized by gel permeation chromatography, nuclear

  2. Macromolecular Architectures Designed by Living Radical Polymerization with Organic Catalysts

    Directory of Open Access Journals (Sweden)

    Miho Tanishima

    2014-01-01

    Full Text Available Well-defined diblock and triblock copolymers, star polymers, and concentrated polymer brushes on solid surfaces were prepared using living radical polymerization with organic catalysts. Polymerizations of methyl methacrylate, butyl acrylate, and selected functional methacrylates were performed with a monofunctional initiator, a difunctional initiator, a trifunctional initiator, and a surface-immobilized initiator.

  3. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative...

  4. Polymerization of methyl methacrylate by diphenylamido bis (methylcyclopentadienyl) ytterbium complex

    Institute of Scientific and Technical Information of China (English)

    WANG, Yao-Rong(王耀荣); SHEN, Qi(沈琪); MA, Jia-Le(马家乐); ZHAO, Qun(赵群)

    2000-01-01

    Methyl methacrylate (MMA) was effectively polymerized by diphenylamido bis(methyicyclopentadienyl) ytterbium complex (MeCp)2YbNPh2(THF). Tne reaction can be carried out over a range of polymerization temperature from - 40℃ to 40℃ and gives the polyMMA with high molecular weights.The initiation mechanism was demonstrated by diphenylamidoterminated methyl methacrylate oligomer.

  5. Redox Polymerization of Methyl Methacrylate in the Fluorous Triphasic System

    Institute of Scientific and Technical Information of China (English)

    Shi Zhen CHEN; Yun Peng BAI; Zhao Long LI

    2006-01-01

    Methyl methacrylate (MMA) was polymerized by using of benzoyl peroxide (BPO) and N, N-dimethylaniline (DMA) as an redox initiator in fluorous triphasic system at room temperature.The polymerization was occurred in both initiator layer and monomer layer in a U-tube. It was found that PMMA obtained from the initiator layer with relatively narrow polydispersity.(PDI =1.38)

  6. Variables and advantages of the polymerization process in plasma

    International Nuclear Information System (INIS)

    Rojas, Andres F; Ortiz, Jairo A; Restrepo, Elizabeth; Devia Alfonso

    1998-01-01

    They are given to know the parameters that affect the polymerization process in plasma like they are: the kinetics, the electric joining, the variables related to the substrata and the interaction plasma/surface. Some advantages of the polymerization process are also presented with regard to the conventional processes

  7. Propene bulk polymerization kinetics: Role of prepolymerization and hydrogen

    NARCIS (Netherlands)

    Pater, J.T.M.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2003-01-01

    An experimental setup for the polymerization of liquid propylene was used to carry out main polymerizations with and without a prepolymerization step. Two types of prepolymerization are introduced: at a constant temperature and at rapidly increasing reactor temperatures. With the present catalyst

  8. prepared via atom transfer radical polymerization, reverse atom

    Indian Academy of Sciences (India)

    Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

  9. Radiation-induced polymerization and radiation effect on polymers

    International Nuclear Information System (INIS)

    Seguchi, Tadao

    1977-12-01

    The processes of radiation-induced polymerization of monomers and also radiation effects on polymers have been studied by instrumental analyses of electron spin resonance (ESR), nuclear magnetic resonance (NMR) and electron microscopy. In radiation-induced polymerization, graft-copolymerization and absorbed state polymerization were taken up. For graft-copolymerization, monomers such as methylmethacrylate and butadiene were made to react with irradiated polyethylene, and behaviors of the initiating radicals and propagating radicals were followed under the reaction by ESR. For absorbed state polymerization, acrylonitrile/zeolite and methylmethacrylate/zeolite were chosen. Absorbed monomers were irradiated at 77 0 K and polymerized at room temperature. Active species and the concentrations were measured by ESR and the yields of polymer were observed by NMR. In radiation effect on polymers, polyvinylfluoride, polyvinylidenfluoride and polytetrafluoroethylene were taken up. Active species trapped in the polymer matrixes were identified and decay and reactivity of the species were also studied. On the basis of information from the electron microscopy and x-ray analysis, radiation effects on these polymers are described. In polytetrafluoroethylene produced by radiation polymerization, the relation between morphology and polymerization conditions and also the process of crystallization during polymerization were studied. (auth.)

  10. Preparation of polymer microspheres by radiation-induced polymerization

    International Nuclear Information System (INIS)

    Naka, Y.; Yamamoto, Y.; Yoshida, Y.; Tagawa, S.

    1995-01-01

    Cross-liking monomer, diethylene glycol dimethacrylate gives microspheres from organic solution by radiation-induced polymerization. /One of the remarkable result is that the number of the microspheres is not changing during the polymerization. Ethyl methacrylate, maleic anhydride, styrene and acrylamide are used as comonomers. These comonomers give the microspheres in the range of 0 to 0.4 as mol fractions. (author)

  11. Initiation of MMA polymerization by iniferters based on dithiocarbamates

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2005-01-01

    Full Text Available Twelve modified dithiocarbamates and a thiuramdisulfide used for the initiation of methyl methacrylate (MMA polymerization were synthesized in this study. The polymerization of MMA was followed by determine the yield and molar mass of the obtained PMMA as a function of polymerization time. Four of the synthesized dithiocarbamates S-benzyl-N,N-dibenzyldithiocarbamate, S-allyl-N,N-dibenzyldithiocarbamate S-benzyl-N,N-diisobutyldithiocarbamate and S-benzoyl-N,N-diisobutyldithiocarbamate, as well as N,N,N',N'-tetrabenzylthiuramdisulfide acted as iniferters. They were active as the initiators of the photo and/or thermally initiated radical polymerization of MMA in bulk and inert solvents (benzene and toluene. S Benzyl - N,N - dibenzyldithiocarbamate can be successfully used for the initiation of MMA polymerization in a polar solvent such as dimethylacetamide.

  12. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...... properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel...

  13. Modelling the Load Torques of Electric Drive for Polymerization Process

    Directory of Open Access Journals (Sweden)

    Andrzej Popenda

    2007-01-01

    Full Text Available The problems of mathematical modelling the load torques on shaft of driving motor designed for applications in polymerization reactors are presented in the paper. The real load of polymerization drive is determined as a function of angular velocity. Mentioned function results from friction in roll-formed slide bearing as well as from friction of ethylene molecules with mixer arms in polymerization reactor chamber. Application of mathematical formulas concerning the centrifugal ventilator is proposed to describe the mixer in reactor chamber. The analytical formulas describing the real loads of polymerization drive are applied in mathematical modelling the power unit of polymerization reactor with specially designed induction motor. The numerical analysis of transient states was made on the basis of formulated mathematical model. Examples of transient responses and trajectories resulting from analysis are presented in the paper.

  14. Studies on the polymerization of acrolein oxime, 6

    International Nuclear Information System (INIS)

    Masuda, Seizo; Tamai, Harumi; Ota, Tadatoshi; Torii, Munetomo; Tanaka, Masami.

    1979-01-01

    Radiation-induced polymerization and copolymerization of acrolein oxime are investigated in different solvents and at a wide range of temperature for obtaining information on the reaction mechanism. Acrolein oxime is polymerized ionically, irrespective of dryness of the sample. Arrhenius plots for the polymerization rate, which do not yield a linear relation, can be adequately approximated by two straight lines. An anionic mechanism is operative above the room temperature, while a cationic mechanism predominates below -23 0 C. The reaction in the intermediate temperature range proceeds by a competitive mechanism, and the rate of the anionic and cationic polymerizations becomes equal at the temperature near -5 0 C. The reaction rate is proportional to the square root of dose rate at room temperature and -23 0 C. On the basis of these data, it is proposed that the polymerization of acrolein oxime by γ-irradiation proceeds by free-ionic mechanisms. (author)

  15. Fabrication and manipulation of polymeric magnetic particles with magnetorheological fluid

    International Nuclear Information System (INIS)

    Rodríguez-López, Jaime; Shum, Ho Cheung; Elvira, Luis; Montero de Espinosa, Francisco; Weitz, David A.

    2013-01-01

    Polymeric magnetic microparticles have been created using a microfluidic device via ultraviolet (UV) polymerization of double emulsions, resulting in cores of magnetorheological (MR) fluids surrounded by polymeric shells. We demonstrate that the resultant particles can be manipulated magnetically to achieve triggered rupture of the capsules. This illustrates the great potential of our capsules for triggered release of active ingredients encapsulated in the polymeric magnetic microparticles. - Highlights: ► Polymeric microparticles encapsulating MR fluids have been fabricated. ► A double-emulsion-templated approach using microfluidic techniques has been used. ► The monodisperse microparticles obtained are easily manipulated under magnetic field. ► These microparticles have great potential for encapsulation-and-release applications.

  16. Dynamic bioactive stimuli-responsive polymeric surfaces

    Science.gov (United States)

    Pearson, Heather Marie

    This dissertation focuses on the design, synthesis, and development of antimicrobial and anticoagulant surfaces of polyethylene (PE), polypropylene (PP), and poly(tetrafluoroethylene) (PTFE) polymers. Aliphatic polymeric surfaces of PE and PP polymers functionalized using click chemistry reactions by the attachment of --COOH groups via microwave plasma reactions followed by functionalization with alkyne moieties. Azide containing ampicillin (AMP) was synthesized and subsequently clicked into the alkyne prepared PE and PP surfaces. Compared to non-functionalized PP and PE surfaces, the AMP clicked surfaces exhibited substantially enhanced antimicrobial activity against Staphylococcus aureus bacteria. To expand the biocompatibility of polymeric surface anticoagulant attributes, PE and PTFE surfaces were functionalized with pH-responsive poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) polyelectrolyte tethers terminated with NH2 and COOH groups. The goal of these studies was to develop switchable stimuli-responsive polymeric surfaces that interact with biological environments and display simultaneous antimicrobial and anticoagulant properties. Antimicrobial AMP was covalently attached to --COOH terminal ends of protected PAA, while anticoagulant heparin (HEP) was attached to terminal --NH2 groups of P2VP. When pH 5.5, they collapse while the PAA segments extend. Such surfaces, when exposed to Staphylococcus aureus, inhibit bacterial growth due to the presence of AMP, as well as are effective anticoagulants due to the presence of covalently attached HEP. Comparison of these "dynamic" pH responsive surfaces with "static" surfaces terminated with AMP entities show significant enhancement of longevity and surface activity against microbial film formation. The last portion of this dissertation focuses on the covalent attachment of living T1 and Φ11 bacteriophages (phages) on PE and PTFE surface. This was accomplished by carbodiimide coupling between --COOH

  17. Development and characterization of polyclonal antibodies against the linker region of the telomere-binding protein TRF2

    Directory of Open Access Journals (Sweden)

    Nadya V. Ilicheva

    2018-03-01

    Full Text Available Background: TRF2 (telomeric repeat binding factor 2 is an essential component of the telomere-binding protein complex shelterin. TRF2 induces the formation of a special structure of telomeric DNA and counteracts activation of DNA damage-response pathways telomeres. TRF2 has a poorly characterized linker region (udTRF2 between its homodimerization and DNA-binding domains. Some lines of evidence have shown that this region could be involved in TRF2 interaction with nuclear lamina. Results: In this study, the fragment of the TERF2 gene encoding udTRF2 domain of telomere-binding protein TRF2 was produced by PCR and cloned into the pET32a vector. The resulting plasmid pET32a-udTRF2 was used for the expression of the recombinant udTRF2 in E. coli RosettaBlue (DE3. The protein was isolated and purified using ammonium sulfate precipitation followed by ion-exchange chromatography. The purified recombinant protein udTRF2 was injected into guinea pigs to generate polyclonal antibodies. The ability of anti-udTRF2 antibodies to bind endogenous TRF2 in human skin fibroblasts was tested by western blotting and immunofluorescent staining. Conclusions: In this study, the recombinant protein udTRF2 and antibodies to it were generated. Both protein and antibodies will provide a useful tool for investigation of the functions of the udTRF2 domain and its role in the interaction between TRF2 and nuclear lamina. Keywords: Chromosomes, Molecular cloning, Nuclear lamina, Nucleoprotein complexes, Polyclonal antibodies, Recombinant polypeptide, Shelterin, Telomere-binding protein TRF2, Telomeres, Telomeric DNA, TTAGGG repeats

  18. Stomach Chitinase from Japanese Sardine Sardinops melanostictus: Purification, Characterization, and Molecular Cloning of Chitinase Isozymes with a Long Linker

    Directory of Open Access Journals (Sweden)

    Satoshi Kawashima

    2016-01-01

    Full Text Available Fish express two different chitinases, acidic fish chitinase-1 (AFCase-1 and acidic fish chitinase-2 (AFCase-2, in the stomach. AFCase-1 and AFCase-2 have different degradation patterns, as fish efficiently degrade chitin ingested as food. For a comparison with the enzymatic properties and the primary structures of chitinase isozymes obtained previously from the stomach of demersal fish, in this study, we purified chitinase isozymes from the stomach of Japanese sardine Sardinops melanostictus, a surface fish that feeds on plankton, characterized the properties of these isozymes, and cloned the cDNAs encoding chitinases. We also predicted 3D structure models using the primary structures of S. melanostictus stomach chitinases. Two chitinase isozymes, SmeChiA (45 kDa and SmeChiB (56 kDa, were purified from the stomach of S. melanostictus. Moreover, two cDNAs, SmeChi-1 encoding SmeChiA, and SmeChi-2 encoding SmeChiB were cloned. The linker regions of the deduced amino acid sequences of SmeChi-1 and SmeChi-2 (SmeChi-1 and SmeChi-2 are the longest among the fish stomach chitinases. In the cleavage pattern groups toward short substrates and the phylogenetic tree analysis, SmeChi-1 and SmeChi-2 were classified into AFCase-1 and AFCase-2, respectively. SmeChi-1 and SmeChi-2 had catalytic domains that consisted of a TIM-barrel (β/α8–fold structure and a deep substrate-binding cleft. This is the first study showing the 3D structure models of fish stomach chitinases.

  19. Asymmetric aminolytic kinetic resolution of racemic epoxides using recyclable chiral polymeric Co(III)-salen complexes: a protocol for total utilization of racemic epoxide in the synthesis of (R)-Naftopidil and (S)-Propranolol.

    Science.gov (United States)

    Kumar, Manish; Kureshy, Rukhsana I; Shah, Arpan K; Das, Anjan; Khan, Noor-ul H; Abdi, Sayed H R; Bajaj, Hari C

    2013-09-20

    Chiral polymeric Co(III) salen complexes with chiral ((R)/(S)-BINOL, diethyl tartrate) and achiral (piperazine and trigol) linkers with varying stereogenic centers were synthesized for the first time and used as catalysts for aminolytic kinetic resolution (AKR) of a variety of terminal epoxides and glycidyl ethers to get enantio-pure epoxides (ee, 99%) and N-protected β-amino alcohols (ee, 99%) with quantitative yield in 16 h at RT under optimized reaction conditions. This protocol was also used for the synthesis of two enantiomerically pure drug molecules (R)-Naftopidil (α1-blocker) and (S)-Propranolol (β-blocker) as a key step via AKR of single racemic naphthylglycidyl ether with Boc-protected isoproylamine with 100% epoxide utilization at 1 g level. The catalyst 1 was successfully recycled for a number of times.

  20. Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization

    NARCIS (Netherlands)

    Peeters, J.W.; Palmans, A.R.A.; Veld, M.A.J.; Scheijen, F.J.E.; Heise, A.; Meijer, E.W.

    2004-01-01

    The enantioselective polymerization of methyl-substituted -caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl--caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the