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Sample records for sod1 monomer formation

  1. S-acylation of SOD1, CCS, and a stable SOD1-CCS heterodimer in human spinal cords from ALS and non-ALS subjects.

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    Antinone, Sarah E; Ghadge, Ghanashyam D; Ostrow, Lyle W; Roos, Raymond P; Green, William N

    2017-01-25

    Previously, we found that human Cu, Zn-superoxide dismutase (SOD1) is S-acylated (palmitoylated) in vitro and in amyotrophic lateral sclerosis (ALS) mouse models, and that S-acylation increased for ALS-causing SOD1 mutants relative to wild type. Here, we use the acyl resin-assisted capture (acyl-RAC) assay to demonstrate S-acylation of SOD1 in human post-mortem spinal cord homogenates from ALS and non-ALS subjects. Acyl-RAC further revealed that endogenous copper chaperone for SOD1 (CCS) is S-acylated in both human and mouse spinal cords, and in vitro in HEK293 cells. SOD1 and CCS formed a highly stable heterodimer in human spinal cord homogenates that was resistant to dissociation by boiling, denaturants, or reducing agents and was not observed in vitro unless both SOD1 and CCS were overexpressed. Cysteine mutations that attenuate SOD1 maturation prevented the SOD1-CCS heterodimer formation. The degree of S-acylation was highest for SOD1-CCS heterodimers, intermediate for CCS monomers, and lowest for SOD1 monomers. Given that S-acylation facilitates anchoring of soluble proteins to cell membranes, our findings suggest that S-acylation and membrane localization may play an important role in CCS-mediated SOD1 maturation. Furthermore, the highly stable S-acylated SOD1-CCS heterodimer may serve as a long-lived maturation intermediate in human spinal cord.

  2. Monomer-dependent secondary nucleation in amyloid formation.

    Science.gov (United States)

    Linse, Sara

    2017-08-01

    Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of a self-assembly process. Such monomer-dependent secondary nucleation occurs during the crystallization of small molecules or proteins and self-assembled materials, as well as in protein self-assembly into fibrous structures. Indications of secondary nucleation may come from analyses of kinetic experiments starting from pure monomers or monomers supplemented with a low concentration of pre-formed aggregates (seeds). More firm evidence requires additional experiments, for example those employing isotope labels to distinguish new aggregates arising from the monomer from those resulting from fragmentation of the seed. In cases of amyloid formation, secondary nucleation leads to the formation of toxic oligomers, and inhibitors of secondary nucleation may serve as starting points for therapeutic developments. Secondary nucleation displays a high degree of structural specificity and may be enhanced by mutations or screening of electrostatic repulsion.

  3. Redox susceptibility of SOD1 mutants is associated with the differential response to CCS over-expression in vivo.

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    Son, Marjatta; Fu, Qiao; Puttaparthi, Krishna; Matthews, Christina M; Elliott, Jeffrey L

    2009-04-01

    Over-expression of CCS in G93A SOD1 mice accelerates neurological disease and enhances mitochondrial pathology. We studied the effect of CCS over-expression in transgenic mice expressing G37R, G86R or L126Z SOD1 mutations in order to understand factors which influence mitochondrial dysfunction. Over-expression of CCS markedly decreased survival and produced mitochondrial vacuolation in G37R SOD1 mice but not in G86R or L126Z SOD1 mice. Moreover, CCS/G37R SOD1 spinal cord showed specific reductions in mitochondrial complex IV subunits consistent with an isolated COX deficiency, while no such reductions were detected in CCS/G86R or CCS/L126Z SOD1 mice. CCS over-expression increased the ratio of reduced to oxidized SOD1 monomers in the spinal cords of G37R SOD1 as well as G93A SOD1 mice, but did not influence the redox state of G86R or L126Z SOD1 monomers. The effects of CCS on disease are SOD1 mutation dependent and correlate with SOD1 redox susceptibility.

  4. Effects of monomer shape on the formation of aggregates from a power law monomer distribution

    International Nuclear Information System (INIS)

    Perry, J; Kimery, J; Matthews, L S; Hyde, T W

    2013-01-01

    The coagulation of dust aggregates is an important process in many physical systems such as the Earth's upper atmosphere, comet tails and protoplanetary discs. Numerical models which study the aggregation in these systems typically involve spherical monomers. There is evidence, however, via the polarization of sunlight in the interstellar medium, as well as optical and LIDAR observations of high-altitude particles in Earth's atmosphere (70–100 km), which indicate that dust monomers may not necessarily be spherical. This study investigates the influence of different ellipsoidal monomer shapes on the morphology of aggregates given various distributions of monomer sizes. Populations of aggregates are grown from a single monomer using a combination of ballistic particle–cluster aggregation and ballistic cluster–cluster aggregation regimes incorporating the rotation of monomers and aggregates. The resulting structures of the aggregates are then compared via the compactness factor, geometric cross-section and friction time. (paper)

  5. Prognostic role of ‘prion-like propagation’ in SOD1-linked familial ALS: an alternative view

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    Keizo eSugaya

    2014-10-01

    Full Text Available ‘Prion-like propagation’ has recently been proposed for disease spread in Cu/Zn superoxide dismutase 1 (SOD1-linked familial amyotrophic lateral sclerosis (ALS. Pathological SOD1 conformers are presumed to propagate via cell-to-cell transmission. In this model, the risk-based kinetics of neuronal cell loss over time appears to be represented by a sigmoidal function that reflects the kinetics of intercellular transmission. Here, we describe an alternative view of prion-like propagation in SOD1-linked ALS−its relation to disease prognosis under the protective-aggregation hypothesis. Nucleation-dependent polymerization has been widely accepted as the molecular mechanism of prion propagation. If toxic species of misfolded SOD1, as soluble oligomers, are formed as on-pathway intermediates of nucleation-dependent polymerization, further fibril extension via sequential addition of monomeric mutant SOD1 would be protective against neurodegeneration. This is because the concentration of unfolded mutant SOD1 monomers, which serve as precursor of nucleation and toxic species of mutant SOD1, would decline in proportion to the extent of aggregation. The nucleation process requires that native conformers exist in an unfolded state that may result from escaping the cellular protein quality control machinery. However, prion-like propagation−SOD1 aggregated form self-propagates by imposing its altered conformation on normal SOD1−appears to antagonize the protective role of aggregate growth. The cross-seeding reaction with normal SOD1 would lead to a failure to reduce the concentration of unfolded mutant SOD1 monomers, resulting in continuous nucleation and subsequent generation of toxic species, and influence disease prognosis. In this alternative view, the kinetics of neuronal loss appears to be represented by an exponential function, with decreasing risk reflecting the protective role of aggregate and the potential for cross-seeding reactions between

  6. ALS mutant SOD1 interacts with G3BP1 and affects stress granule dynamics.

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    Gal, Jozsef; Kuang, Lisha; Barnett, Kelly R; Zhu, Brian Z; Shissler, Susannah C; Korotkov, Konstantin V; Hayward, Lawrence J; Kasarskis, Edward J; Zhu, Haining

    2016-10-01

    Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease. Mutations in Cu/Zn superoxide dismutase (SOD1) are responsible for approximately 20 % of the familial ALS cases. ALS-causing SOD1 mutants display a gain-of-toxicity phenotype, but the nature of this toxicity is still not fully understood. The Ras GTPase-activating protein-binding protein G3BP1 plays a critical role in stress granule dynamics. Alterations in the dynamics of stress granules have been reported in several other forms of ALS unrelated to SOD1. To our surprise, the mutant G93A SOD1 transgenic mice exhibited pathological cytoplasmic inclusions that co-localized with G3BP1-positive granules in spinal cord motor neurons. The co-localization was also observed in fibroblast cells derived from familial ALS patient carrying SOD1 mutation L144F. Mutant SOD1, unlike wild-type SOD1, interacted with G3BP1 in an RNA-independent manner. Moreover, the interaction is specific for G3BP1 since mutant SOD1 showed little interaction with four other RNA-binding proteins implicated in ALS. The RNA-binding RRM domain of G3BP1 and two particular phenylalanine residues (F380 and F382) are critical for this interaction. Mutant SOD1 delayed the formation of G3BP1- and TIA1-positive stress granules in response to hyperosmolar shock and arsenite treatment in N2A cells. In summary, the aberrant mutant SOD1-G3BP1 interaction affects stress granule dynamics, suggesting a potential link between pathogenic SOD1 mutations and RNA metabolism alterations in ALS.

  7. Imaging of glial cell morphology, SOD1 distribution and elemental composition in the brainstem and hippocampus of the ALS hSOD1G93A rat.

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    Stamenković, Stefan; Dučić, Tanja; Stamenković, Vera; Kranz, Alexander; Andjus, Pavle R

    2017-08-15

    Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disorder affecting motor and cognitive domains of the CNS. Mutations in the Cu,Zn-superoxide dismutase (SOD1) cause 20% of familial ALS and provoke formation of intracellular aggregates and copper and zinc unbinding, leading to glial activation and neurodegeneration. Therefore, we investigated glial cell morphology, intracellular SOD1 distribution, and elemental composition in the brainstem and hippocampus of the hSOD1 G93A transgenic rat model of ALS. Immunostaining for astrocytes, microglia and SOD1 revealed glial proliferation and progressive tissue accumulation of SOD1 in both brain regions of ALS rats starting already at the presymptomatic stage. Glial cell morphology analysis in the brainstem of ALS rats revealed astrocyte activation occurring before disease symptoms onset, followed by activation of microglia. Hippocampal ALS astrocytes exhibited an identical reactive profile, while microglial morphology was unchanged. Additionally, ALS brainstem astrocytes demonstrated progressive SOD1 accumulation in the cell body and processes, while microglial SOD1 levels were reduced and its distribution limited to distal cell processes. In the hippocampus both glial cell types exhibited SOD1 accumulation in the cell body. X-ray fluorescence imaging revealed decreased P and increased Ca, Cl, K, Ni, Cu and Zn in the brainstem, and higher levels of Cl, Ni and Cu, but lower levels of Zn in the hippocampus of symptomatic ALS rats. These results bring new insights into the glial response during disease development and progression in motor as well as in non-motor CNS structures, and indicate disturbed tissue elemental homeostasis as a prominent hallmark of disease pathology. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.

  8. A molecular chaperone activity of CCS restores the maturation of SOD1 fALS mutants.

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    Luchinat, Enrico; Barbieri, Letizia; Banci, Lucia

    2017-12-12

    Superoxide dismutase 1 (SOD1) is an important metalloprotein for cellular oxidative stress defence, that is mutated in familiar variants of Amyotrophic Lateral Sclerosis (fALS). Some mutations destabilize the apo protein, leading to the formation of misfolded, toxic species. The Copper Chaperone for SOD1 (CCS) transiently interacts with SOD1 and promotes its correct maturation by transferring copper and catalyzing disulfide bond formation. By in vitro and in-cell NMR, we investigated the role of the SOD-like domain of CCS (CCS-D2). We showed that CCS-D2 forms a stable complex with zinc-bound SOD1 in human cells, that has a twofold stabilizing effect: it both prevents the accumulation of unstructured mutant SOD1 and promotes zinc binding. We further showed that CCS-D2 interacts with apo-SOD1 in vitro, suggesting that in cells CCS stabilizes mutant apo-SOD1 prior to zinc binding. Such molecular chaperone function of CCS-D2 is novel and its implications in SOD-linked fALS deserve further investigation.

  9. Spinal cord homogenates from SOD1 familial amyotrophic lateral sclerosis induce SOD1 aggregation in living cells.

    Directory of Open Access Journals (Sweden)

    Edward Pokrishevsky

    Full Text Available Mutant Cu/Zn superoxide dismutase (SOD1 can confer its misfolding on wild-type SOD1 in living cells; the propagation of misfolding can also be transmitted between cells in vitro. Recent studies identified fluorescently-tagged SOD1G85R as a promiscuous substrate that is highly prone to aggregate by a variety of templates, in vitro and in vivo. Here, we utilized several SOD1-GFP reporter proteins with G37R, G85R, or G93A mutations in SOD1. We observed that human spinal cord homogenates prepared from SOD1 familial ALS (FALS can induce significantly more intracellular reporter protein aggregation than spinal cord homogenates from sporadic ALS, Alzheimer's disease, multiple system atrophy or healthy control individuals. We also determined that the induction of reporter protein aggregation by SOD1-FALS tissue homogenates can be attenuated by incubating the cells with the SOD1 misfolding-specific antibody 3H1, or the small molecule 5-fluorouridine. Our study further implicates SOD1 as the seeding particle responsible for the spread of SOD1-FALS neurodegeneration from its initial onset site(s, and demonstrates two potential therapeutic strategies for SOD1-mediated disease. This work also comprises a medium-throughput cell-based platform of screening potential therapeutics to attenuate propagated aggregation of SOD1.

  10. Step growth of an AB2 monomer, with cycle formation

    DEFF Research Database (Denmark)

    Cameron, Colin; Fawcett, Allan H.; Hetherington, Cecil R.

    1998-01-01

    A computer-based lattice model of the step growth reaction of an AB2 monomer, the next elaborate system after an AB monomer, has been devised that allows the simultaneous and explicit occurrence of inter- and intramolecular reactions of A and B groups of the flexible and moving molecules according...... with fractal characteristics. Growth stops when each molecule contains a cycle. For the model explored, in which six lattice sites are used for each monomer, the limiting value of the number average degree of polymerization, 〈x〉n,∞, is 14.6(±0.3) (after infinite time). The occurrence within the system of rings...... of m residues (m=1,2,3,...) is found to depend upon m and the extent of reaction of the A groups, pa, according to Rm=C0pm am-2.71, the constant C0 reflecting the structure of the lattice and the monomer, and being shown to determine the final degree of polymerization. The exponent of the integers m...

  11. Effect of CCS on the accumulation of FALS SOD1 mutant-containing aggregates and on mitochondrial translocation of SOD1 mutants: implication of a free radical hypothesis.

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    Kim, Ha Kun; Chung, Youn Wook; Chock, P Boon; Yim, Moon B

    2011-05-15

    Missense mutations of SOD1 are linked to familial amyotrophic lateral sclerosis (FALS) through a yet-to-be identified toxic-gain-of-function. One of the proposed mechanisms involves enhanced aggregate formation. However, a recent study showed that dual transgenic mice overexpressing both G93A and CCS copper chaperone (G93A/CCS) exhibit no SOD1-positive aggregates yet show accelerated FALS symptoms with enhanced mitochondrial pathology compared to G93A mice. Using a dicistronic mRNA to simultaneously generate hSOD1 mutants, G93A, A4V and G85R, and hCCS in AAV293 cells, we revealed: (i) CCS is degraded primarily via a macroautophagy pathway. It forms a stable heterodimer with inactive G85R, and via its novel copper chaperone-independent molecular chaperone activity facilitates G85R degradation via a macroautophagy-mediated pathway. For active G93A and A4V, CCS catalyzes their maturation to form active and soluble homodimers. (ii) CCS reduces, under non-oxidative conditions, yet facilitates in the presence of H(2)O(2), mitochondrial translocation of inactive SOD1 mutants. These results, together with previous reports showing FALS SOD1 mutants enhanced free radical-generating activity, provide a mechanistic explanation for the observations with G93A/CCS dual transgenic mice and suggest that free radical generation by FALS SOD1, enhanced by CCS, may, in part, be responsible for the FALS SOD1 mutant-linked aggregation, mitochondrial translocation, and degradation. Published by Elsevier Inc.

  12. Import, maturation, and function of SOD1 and its copper chaperone CCS in the mitochondrial intermembrane space.

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    Kawamata, Hibiki; Manfredi, Giovanni

    2010-11-01

    Cu, Zn, superoxide dismutase (SOD1) is a ubiquitous enzyme localized in multiple cellular compartments, including mitochondria, where it concentrates in the intermembrane space (IMS). Similar to other small IMS proteins, the import and retention of SOD1 in the IMS is linked to its folding and maturation, involving the formation of critical intra- and intermolecular disulfide bonds. Therefore, the cysteine residues of SOD1 play a fundamental role in its IMS localization. IMS import of SOD1 involves its copper chaperone, CCS, whose mitochondrial distribution is regulated by the Mia40/Erv1 disulfide relay system in a redox-dependent manner: CCS promotes SOD1 maturation and retention in the IMS. The function of SOD1 in the IMS is still unknown, but it is plausible that it serves to remove superoxide released from the mitochondrial respiratory chain. Mutations in SOD1 cause familial amyotrophic lateral sclerosis (ALS), whose pathologic features include mitochondrial bioenergetic dysfunction. Mutant SOD1 localization in the IMS is not dictated by oxygen concentration and the Mia40/Erv1 system, but is primarily dependent on aberrant protein folding and aggregation. Mutant SOD1 localization and aggregation in the IMS might cause the mitochondrial abnormalities observed in familial ALS and could play a significant role in disease pathogenesis.

  13. Oxidized SOD1 alters proteasome activities in vitro and in the cortex of SOD1 overexpressing mice.

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    Le Pecheur, Marie; Bourdon, Emmanuel; Paly, Evelyne; Farout, Luc; Friguet, Bertrand; London, Jacqueline

    2005-07-04

    Premature ageing, one of the characteristics of Down syndrome (DS), may involve oxidative stress and impairment of proteasome activity. Transgenic mice overexpressing the human copper/zinc superoxide dismutase (SOD1) gene are one of the first murine models for DS and it has been shown that SOD1 overexpression might be either deleterious or beneficial. Here, we show a reduction in proteasome activities in the cortex of SOD1 transgenic mice and an associated increase in the content of oxidized SOD1 protein. As we demonstrate that in vitro oxidized SOD can inhibit purified proteasome peptidase activities, modified SOD1 might be partially responsible for proteasome inhibition shown in SOD1 transgenic mice.

  14. Radioimmunoassay of serum SOD-1 in the elderly

    International Nuclear Information System (INIS)

    Ren Yu'an; Lin Baoyuan

    1995-01-01

    A RIA for serum SOD-1 was performed in 168 aged subjects including 47 aged healthy subjects and 121 aged patients as well as in 35 healthy young and adult cases serving as control. The measuring results are as follows: serum SOD-1 value of 47 aged healthy subjects are 279.42 +- 89.38 μg/l, 121 aged patients are 405.10 +- 181.29 μg/l, and 35 young and adult cases are 185.80 +- 56.44 μg/l. It shows the obvious difference between the aged group and control group. It also shows the obvious difference between the aged healthy subjects and aged patients. In addition, the clinical evaluation is also discussed

  15. Defining SOD1 ALS natural history to guide therapeutic clinical trial design.

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    Bali, Taha; Self, Wade; Liu, Jingxia; Siddique, Teepu; Wang, Leo H; Bird, Thomas D; Ratti, Elena; Atassi, Nazem; Boylan, Kevin B; Glass, Jonathan D; Maragakis, Nicholas J; Caress, James B; McCluskey, Leo F; Appel, Stanley H; Wymer, James P; Gibson, Summer; Zinman, Lorne; Mozaffar, Tahseen; Callaghan, Brian; McVey, April L; Jockel-Balsarotti, Jennifer; Allred, Peggy; Fisher, Elena R; Lopate, Glenn; Pestronk, Alan; Cudkowicz, Merit E; Miller, Timothy M

    2017-02-01

    Understanding the natural history of familial amyotrophic lateral sclerosis (ALS) caused by SOD1 mutations (ALS SOD1 ) will provide key information for optimising clinical trials in this patient population. To establish an updated natural history of ALS SOD1 . Retrospective cohort study from 15 medical centres in North America evaluated records from 175 patients with ALS with genetically confirmed SOD1 mutations, cared for after the year 2000. Age of onset, survival, ALS Functional Rating Scale (ALS-FRS) scores and respiratory function were analysed. Patients with the A4V (Ala-Val) SOD1 mutation (SOD1 A4V ), the largest mutation population in North America with an aggressive disease progression, were distinguished from other SOD1 mutation patients (SOD1 non-A4V ) for analysis. Mean age of disease onset was 49.7±12.3 years (mean±SD) for all SOD1 patients, with no statistical significance between SOD1 A4V and SOD1 non-A4V (p=0.72, Kruskal-Wallis). Total SOD1 patient median survival was 2.7 years. Mean disease duration for all SOD1 was 4.6±6.0 and 1.4±0.7 years for SOD1 A4V . SOD1 A4V survival probability (median survival 1.2 years) was significantly decreased compared with SOD1 non-A4V (median survival 6.8 years; p<0.0001, log-rank). A statistically significant increase in ALS-FRS decline in SOD1 A4V compared with SOD1 non-A4V participants (p=0.02) was observed, as well as a statistically significant increase in ALS-forced vital capacity decline in SOD1 A4V compared with SOD1 non-A4V (p=0.02). SOD1 A4V is an aggressive, but relatively homogeneous form of ALS. These SOD1-specific ALS natural history data will be important for the design and implementation of clinical trials in the ALS SOD1 patient population. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

  16. APP/SOD1 overexpressing mice present reduced neuropathic pain sensitivity.

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    Kotulska, Katarzyna; Larysz-Brysz, Magdalena; LePecheur, Marie; Marcol, Wiesław; Olakowska, Edyta; Lewin-Kowalik, Joanna; London, Jacqueline

    2011-07-15

    There are controversies regarding pain expression in mentally disabled people, including Down syndrome patients. The aim of this study was to examine neuropathic pain-related behavior and peripheral nerve regeneration in mouse model of Down syndrome. Sciatic nerves of double transgenic mice, overexpressing both amyloid precursor protein (APP) and Cu/Zn superoxide dismutase (SOD1) genes, and FVB/N wild type mice were transected and immediately resutured. Evaluation of autotomy and functional recovery was carried out during 4-week follow-up. We found markedly less severe autotomy in transgenic animals, although the onset of autotomy was significantly delayed in control mice. Interestingly, neuroma formation at the injury site was significantly more prominent in transgenic animals. Sciatic function index outcome was better in transgenic mice than in wild-type group. Histological evaluation revealed no statistically significant differences in the number of GAP-43-positive growth cones and macrophages in the distal stump of the transected nerve between groups. However, in transgenic animals, the regenerating axons were arranged more chaotically. The number of Schwann cells in the distal stump of the transected nerves was significantly lower in transgenic mice. The number of surviving motoneurons was markedly decreased in transgenic group. We measured also the atrophy of denervated muscles and found it decreased in APP/SOD1 overexpressing mice. Taken together, in this model of Down syndrome, we observed increased neuroma formation and decreased autotomy after peripheral nerve injury. Our findings suggest that APP/SOD1 overexpressing mice are less sensitive for neuropathic pain associated with neuroma. Copyright © 2011 Elsevier Inc. All rights reserved.

  17. Isolated cytochrome c oxidase deficiency in G93A SOD1 mice overexpressing CCS protein.

    Science.gov (United States)

    Son, Marjatta; Leary, Scot C; Romain, Nadine; Pierrel, Fabien; Winge, Dennis R; Haller, Ronald G; Elliott, Jeffrey L

    2008-05-02

    G93A SOD1 transgenic mice overexpressing CCS protein develop an accelerated disease course that is associated with enhanced mitochondrial pathology and increased mitochondrial localization of mutant SOD1. Because these results suggest an effect of mutant SOD1 on mitochondrial function, we assessed the enzymatic activities of mitochondrial respiratory chain complexes in the spinal cords of CCS/G93A SOD1 and control mice. CCS/G93A SOD1 mouse spinal cord demonstrates a 55% loss of complex IV (cytochrome c oxidase) activity compared with spinal cord from age-matched non-transgenic or G93A SOD1 mice. In contrast, CCS/G93A SOD1 spinal cord shows no reduction in the activities of complex I, II, or III. Blue native gel analysis further demonstrates a marked reduction in the levels of complex IV but not of complex I, II, III, or V in spinal cords of CCS/G93A SOD1 mice compared with non-transgenic, G93A SOD1, or CCS/WT SOD1 controls. With SDS-PAGE analysis, spinal cords from CCS/G93A SOD1 mice showed significant decreases in the levels of two structural subunits of cytochrome c oxidase, COX1 and COX5b, relative to controls. In contrast, CCS/G93A SOD1 mouse spinal cord showed no reduction in levels of selected subunits from complexes I, II, III, or V. Heme A analyses of spinal cord further support the existence of cytochrome c oxidase deficiency in CCS/G93A SOD1 mice. Collectively, these results establish that CCS/G93A SOD1 mice manifest an isolated complex IV deficiency which may underlie a substantial part of mutant SOD1-induced mitochondrial cytopathy.

  18. Dimer monomer transition and dimer re-formation play important role for ATM cellular function during DNA repair

    International Nuclear Information System (INIS)

    Du, Fengxia; Zhang, Minjie; Li, Xiaohua; Yang, Caiyun; Meng, Hao; Wang, Dong; Chang, Shuang; Xu, Ye; Price, Brendan; Sun, Yingli

    2014-01-01

    Highlights: • ATM phosphorylates the opposite strand of the dimer in response to DNA damage. • The PETPVFRLT box of ATM plays a key role in its dimer dissociation in DNA repair. • The dephosphorylation of ATM is critical for dimer re-formation after DNA repair. - Abstract: The ATM protein kinase, is a serine/threonine protein kinase that is recruited and activated by DNA double-strand breaks, mediates responses to ionizing radiation in mammalian cells. Here we show that ATM is held inactive in unirradiated cells as a dimer and phosphorylates the opposite strand of the dimer in response to DNA damage. Cellular irradiation induces rapid intermolecular autophosphorylation of serine 1981 that causes dimer dissociation and initiates cellular ATM kinase activity. ATM cannot phosphorylate the substrates when it could not undergo dimer monomer transition. After DNA repair, the active monomer will undergo dephosphorylation to form dimer again and dephosphorylation is critical for dimer re-formation. Our work reveals novel function of ATM dimer monomer transition and explains why ATM dimer monomer transition plays such important role for ATM cellular activity during DNA repair

  19. SOD1 Transcriptional and Posttranscriptional Regulation and Its Potential Implications in ALS

    Directory of Open Access Journals (Sweden)

    Pamela Milani

    2011-01-01

    Full Text Available Copper-zinc superoxide dismutase (SOD1 is a detoxifying enzyme localized in the cytosol, nucleus, peroxisomes, and mitochondria. The discovery that mutations in SOD1 gene cause a subset of familial amyotrophic lateral sclerosis (FALS has attracted great attention, and studies to date have been mainly focused on discovering mutations in the coding region and investigation at protein level. Considering that changes in SOD1 mRNA levels have been associated with sporadic ALS (SALS, a molecular understanding of the processes involved in the regulation of SOD1 gene expression could not only unravel novel regulatory pathways that may govern cellular phenotypes and changes in diseases but also might reveal therapeutic targets and treatments. This review seeks to provide an overview of SOD1 gene structure and of the processes through which SOD1 transcription is controlled. Furthermore, we emphasize the importance to focus future researches on investigating posttranscriptional mechanisms and their relevance to ALS.

  20. Structures of the G85R Variant of SOD1 in Familial Amyotrophic Lateral Sclerosis

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xiaohang; Antonyuk, Svetlana V.; Seetharaman, Sai V.; Whitson, Lisa J.; Taylor, Alexander B.; Holloway, Stephen P.; Strange, Richard W.; Doucette, Peter A.; Valentine, Joan Selverstone; Tiwari, Ashutosh; Hayward, Lawrence J.; Padua, Shelby; Cohlberg, Jeffrey A.; Hasnain, S. Samar; Hart, P. John (Texas-HSC); (Cal. State); (UMASS, MED); (UCLA); (Daresbury)

    2008-07-21

    Mutations in the gene encoding human copper-zinc superoxide dismutase (SOD1) cause a dominant form of the progressive neurodegenerative disease amyotrophic lateral sclerosis. Transgenic mice expressing the human G85R SOD1 variant develop paralytic symptoms concomitant with the appearance of SOD1-enriched proteinaceous inclusions in their neural tissues. The process(es) through which misfolding or aggregation of G85R SOD1 induces motor neuron toxicity is not understood. Here we present structures of the human G85R SOD1 variant determined by single crystal x-ray diffraction. Alterations in structure of the metal-binding loop elements relative to the wild type enzyme suggest a molecular basis for the metal ion deficiency of the G85R SOD1 protein observed in the central nervous system of transgenic mice and in purified recombinant G85R SOD1. These findings support the notion that metal-deficient and/or disulfide-reduced mutant SOD1 species contribute to toxicity in SOD1-linked amyotrophic lateral sclerosis.

  1. TFE-induced local unfolding and fibrillation of SOD1: bridging the experiment and simulation studies.

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    Kumar, Vijay; Prakash, Amresh; Pandey, Preeti; Lynn, Andrew M; Hassan, Md Imtaiyaz

    2018-05-18

    Misfolding and aggregation of Cu, Zn Superoxide dismutase (SOD1) is involved in the neurodegenerative disease, amyotrophic lateral sclerosis. Many studies have shown that metal-depleted, monomeric form of SOD1 displays substantial local unfolding dynamics and is the precursor for aggregation. Here, we have studied the structure and dynamics of different apo monomeric SOD1 variants associated with unfolding and aggregation in aqueous trifluoroethanol (TFE) through experiments and simulation. TFE induces partially unfolded β-sheet-rich extended conformations in these SOD1 variants, which subsequently develops aggregates with fibril-like characteristics. Fibrillation was achieved more easily in disulfide-reduced monomeric SOD1 when compared with wild-type and mutant monomeric SOD1. At higher concentrations of TFE, a native-like structure with the increase in α-helical content was observed. The molecular dynamics simulation results illustrate distinct structural dynamics for different regions of SOD1 variants and show uniform local unfolding of β-strands. The strands protected by the zinc-binding and electrostatic loops were found to unfold first in 20% (v/v) TFE, leading to a partial unfolding of β-strands 4, 5, and 6 which are prone to aggregation. Our results thus shed light on the role of local unfolding and conformational dynamics in SOD1 misfolding and aggregation. © 2018 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

  2. An emerging role for misfolded wild-type SOD1 in sporadic ALS pathogenesis

    Directory of Open Access Journals (Sweden)

    Melissa S Rotunno

    2013-12-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is a fatal neurodegenerative disorder that targets motor neurons, leading to paralysis and death within a few years of disease onset. While several genes have been linked to the inheritable, or familial, form of ALS, much less is known about the cause(s of sporadic ALS, which accounts for approximately 90% of ALS cases. Due to the clinical similarities between familial and sporadic ALS, it is plausible that both forms of the disease converge on a common pathway and, therefore, involve common factors. Recent evidence suggests the Cu,Zn-superoxide dismutase (SOD1 protein to be one such factor that is common to both sporadic and familial ALS. In 1993, mutations were uncovered in SOD1 that represent the first known genetic cause of familial ALS. While the exact mechanism of mutant-SOD1 toxicity is still not known today, most evidence points to a gain of toxic function that stems, at least in part, from the propensity of this protein to misfold. In the wild-type SOD1 protein, non-genetic perturbations such as metal depletion, disruption of the quaternary structure, and oxidation, can also induce SOD1 to misfold. In fact, these aforementioned post-translational modifications cause wild-type SOD1 to adopt a toxic conformation that is similar to familial ALS-linked SOD1 variants. These observations, together with the detection of misfolded wild-type SOD1 within human post-mortem sporadic ALS samples, have been used to support the controversial hypothesis that misfolded forms of wild-type SOD1 contribute to sporadic ALS pathogenesis. In this review, we present data from the literature that both support and contradict this hypothesis. We also discuss SOD1 as a potential therapeutic target for both familial and sporadic ALS.

  3. Comprehensive analysis to explain reduced or increased SOD1 enzymatic activity in ALS patients and their relatives.

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    Keskin, Isil; Birve, Anna; Berdynski, Mariusz; Hjertkvist, Karin; Rofougaran, Reza; Nilsson, Torbjörn K; Glass, Jonathan D; Marklund, Stefan L; Andersen, Peter M

    2017-08-01

    To characterise stabilities in erythrocytes of mutant SOD1 proteins, compare SOD1 enzymatic activities between patients with different genetic causes of ALS and search for underlying causes of deviant SOD1 activities in individuals lacking SOD1 mutations. Blood samples from 4072 individuals, ALS patients with or without a SOD1 mutation, family members and controls were studied. Erythrocyte SOD1 enzymatic activities normalised to haemoglobin content were determined, and effects of haemoglobin disorders on dismutation assessed. Coding SOD1 sequences were analysed by Sanger sequencing, exon copy number variations by fragment length analysis and by TaqMan Assay. Of the 44 SOD1 mutations found, 75% caused severe destabilisation of the mutant protein but in 25% it was physically stable. Mutations producing structural changes caused halved erythrocyte SOD1 activities. There were no differences in SOD1 activities between patients without a SOD1 mutation and control individuals or carriers of TBK1 mutations and C9orf72 HRE . In the low and high SOD1 activity groups no deviations were found in exon copy numbers and intron gross structures. Thalassemias and iron deficiency were associated with increased SOD1 activity/haemoglobin ratios. Adjunct erythrocyte SOD1 activity analysis reliably signals destabilising SOD1 mutations including intronic mutations that are missed by exon sequencing.

  4. Overexpression of CCS in G93A-SOD1 mice leads to accelerated neurological deficits with severe mitochondrial pathology.

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    Son, Marjatta; Puttaparthi, Krishna; Kawamata, Hibiki; Rajendran, Bhagya; Boyer, Philip J; Manfredi, Giovanni; Elliott, Jeffrey L

    2007-04-03

    Cu, Zn superoxide dismutase (SOD1) has been detected within spinal cord mitochondria of mutant SOD1 transgenic mice, a model of familial ALS. The copper chaperone for SOD1 (CCS) provides SOD1 with copper, facilitates the conversion of immature apo-SOD1 to a mature holoform, and influences in yeast the cytosolic/mitochondrial partitioning of SOD1. To determine how CCS affects G93A-SOD1-induced disease, we generated transgenic mice overexpressing CCS and crossed them to G93A-SOD1 or wild-type SOD1 transgenic mice. Both CCS transgenic mice and CCS/wild-type-SOD1 dual transgenic mice are neurologically normal. In contrast, CCS/G93A-SOD1 dual transgenic mice develop accelerated neurological deficits, with a mean survival of 36 days, compared with 242 days for G93A-SOD1 mice. Immuno-EM and subcellular fractionation studies on the spinal cord show that G93A-SOD1 is enriched within mitochondria in the presence of CCS overexpression. Our results indicate that CCS overexpression in G93A-SOD1 mice produces severe mitochondrial pathology and accelerates disease course.

  5. Inhibitors of SOD1 Interaction as an Approach to Slow the Progressive Spread of ALS Symptoms

    Science.gov (United States)

    2016-07-01

    the progression of ALS caused by mutations in this protein . To accomplish this goal, we developed an assay that is based on the observation that the...force. In our assay , this force is the normal interaction that occurs when 2 individual SOD1 proteins come together to form a normal active enzyme...Using recombinant DNA, we create fusion proteins of SOD1 and each half of the luciferase enzyme. In the past year, we have characterized and optimized

  6. Destabilizing protein polymorphisms in the genetic background direct phenotypic expression of mutant SOD1 toxicity.

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    Tali Gidalevitz

    2009-03-01

    Full Text Available Genetic background exerts a strong modulatory effect on the toxicity of aggregation-prone proteins in conformational diseases. In addition to influencing the misfolding and aggregation behavior of the mutant proteins, polymorphisms in putative modifier genes may affect the molecular processes leading to the disease phenotype. Mutations in SOD1 in a subset of familial amyotrophic lateral sclerosis (ALS cases confer dominant but clinically variable toxicity, thought to be mediated by misfolding and aggregation of mutant SOD1 protein. While the mechanism of toxicity remains unknown, both the nature of the SOD1 mutation and the genetic background in which it is expressed appear important. To address this, we established a Caenorhabditis elegans model to systematically examine the aggregation behavior and genetic interactions of mutant forms of SOD1. Expression of three structurally distinct SOD1 mutants in C. elegans muscle cells resulted in the appearance of heterogeneous populations of aggregates and was associated with only mild cellular dysfunction. However, introduction of destabilizing temperature-sensitive mutations into the genetic background strongly enhanced the toxicity of SOD1 mutants, resulting in exposure of several deleterious phenotypes at permissive conditions in a manner dependent on the specific SOD1 mutation. The nature of the observed phenotype was dependent on the temperature-sensitive mutation present, while its penetrance reflected the specific combination of temperature-sensitive and SOD1 mutations. Thus, the specific toxic phenotypes of conformational disease may not be simply due to misfolding/aggregation toxicity of the causative mutant proteins, but may be defined by their genetic interactions with cellular pathways harboring mildly destabilizing missense alleles.

  7. Genetic disruption of SOD1 gene causes glucose intolerance and impairs β-cell function.

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    Muscogiuri, Giovanna; Salmon, Adam B; Aguayo-Mazzucato, Cristina; Li, Mengyao; Balas, Bogdan; Guardado-Mendoza, Rodolfo; Giaccari, Andrea; Reddick, Robert L; Reyna, Sara M; Weir, Gordon; Defronzo, Ralph A; Van Remmen, Holly; Musi, Nicolas

    2013-12-01

    Oxidative stress has been associated with insulin resistance and type 2 diabetes. However, it is not clear whether oxidative damage is a cause or a consequence of the metabolic abnormalities present in diabetic subjects. The goal of this study was to determine whether inducing oxidative damage through genetic ablation of superoxide dismutase 1 (SOD1) leads to abnormalities in glucose homeostasis. We studied SOD1-null mice and wild-type (WT) littermates. Glucose tolerance was evaluated with intraperitoneal glucose tolerance tests. Peripheral and hepatic insulin sensitivity was quantitated with the euglycemic-hyperinsulinemic clamp. β-Cell function was determined with the hyperglycemic clamp and morphometric analysis of pancreatic islets. Genetic ablation of SOD1 caused glucose intolerance, which was associated with reduced in vivo β-cell insulin secretion and decreased β-cell volume. Peripheral and hepatic insulin sensitivity were not significantly altered in SOD1-null mice. High-fat diet caused glucose intolerance in WT mice but did not further worsen the glucose intolerance observed in standard chow-fed SOD1-null mice. Our findings suggest that oxidative stress per se does not play a major role in the pathogenesis of insulin resistance and demonstrate that oxidative stress caused by SOD1 ablation leads to glucose intolerance secondary to β-cell dysfunction.

  8. Sod1 deficiency reduces incubation time in mouse models of prion disease.

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    Shaheen Akhtar

    Full Text Available Prion infections, causing neurodegenerative conditions such as Creutzfeldt-Jakob disease and kuru in humans, scrapie in sheep and BSE in cattle are characterised by prolonged and variable incubation periods that are faithfully reproduced in mouse models. Incubation time is partly determined by genetic factors including polymorphisms in the prion protein gene. Quantitative trait loci studies in mice and human genome-wide association studies have confirmed that multiple genes are involved. Candidate gene approaches have also been used and identified App, Il1-r1 and Sod1 as affecting incubation times. In this study we looked for an association between App, Il1-r1 and Sod1 representative SNPs and prion disease incubation time in the Northport heterogeneous stock of mice inoculated with the Chandler/RML prion strain. No association was seen with App, however, significant associations were seen with Il1-r1 (P = 0.02 and Sod1 (P<0.0001 suggesting that polymorphisms at these loci contribute to the natural variation observed in incubation time. Furthermore, following challenge with Chandler/RML, ME7 and MRC2 prion strains, Sod1 deficient mice showed highly significant reductions in incubation time of 20, 13 and 24%, respectively. No differences were detected in Sod1 expression or activity. Our data confirm the protective role of endogenous Sod1 in prion disease.

  9. In yeast redistribution of Sod1 to the mitochondrial intermembrane space provides protection against respiration derived oxidative stress.

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    Klöppel, Christine; Michels, Christine; Zimmer, Julia; Herrmann, Johannes M; Riemer, Jan

    2010-12-03

    The antioxidative enzyme copper-zinc superoxide dismutase (Sod1) is an important cellular defence system against reactive oxygen species (ROS). While the majority of this enzyme is localized to the cytosol, about 1% of the cellular Sod1 is present in the intermembrane space (IMS) of mitochondria. These amounts of mitochondrial Sod1 are increased for certain Sod1 mutants that are linked to the neurodegenerative disease amyotrophic lateral sclerosis (ALS). To date, only little is known about the physiological function of mitochondrial Sod1. Here, we use the model system Saccharomyces cerevisiae to generate cells in which Sod1 is exclusively localized to the IMS. We find that IMS-localized Sod1 can functionally substitute wild type Sod1 and that it even exceeds the protective capacity of wild type Sod1 under conditions of mitochondrial ROS stress. Moreover, we demonstrate that upon expression in yeast cells the common ALS-linked mutant Sod1(G93A) becomes enriched in the mitochondrial fraction and provides an increased protection of cells from mitochondrial oxidative stress. Such an effect cannot be observed for the catalytically inactive mutant Sod1(G85R). Our observations suggest that the targeting of Sod1 to the mitochondrial IMS provides an increased protection against respiration-derived ROS. Copyright © 2010 Elsevier Inc. All rights reserved.

  10. Unraveling ALS due to SOD1 mutation through the combination of brain and cervical cord MRI.

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    Agosta, Federica; Spinelli, Edoardo Gioele; Marjanovic, Ivan V; Stevic, Zorica; Pagani, Elisabetta; Valsasina, Paola; Salak-Djokic, Biljana; Jankovic, Milena; Lavrnic, Dragana; Kostic, Vladimir S; Filippi, Massimo

    2018-02-20

    To explore structural and functional changes of the brain and cervical cord in patients with amyotrophic lateral sclerosis (ALS) due to mutation in the superoxide dismutase ( SOD1 ) gene compared with sporadic ALS. Twenty patients with SOD1 ALS, 11 with sporadic ALS, and 33 healthy controls underwent clinical evaluation and brain MRI. Cortical thickness analysis, diffusion tensor MRI of the corticospinal tracts (CST) and corpus callosum, and resting-state functional connectivity were performed. Patients with ALS also underwent cervical cord MRI to evaluate cord cross-sectional area and magnetization transfer ratio (MTR). Patients with SOD1 ALS showed longer disease duration and slower rate of functional decline relative to those with sporadic ALS. No cortical thickness abnormalities were found in patients with ALS compared with controls. Fractional anisotropy showed that sporadic ALS patients had significant CST damage relative to both healthy controls ( p = 0.001-0.02) and SOD1-related ALS ( p = 0.05), although the latter showed alterations that were intermediate between controls and sporadic ALS. Functional hyperconnectivity of the motor cortex in the sensorimotor network was observed in patients with sporadic ALS relative to controls. Conversely, patients with SOD1 ALS showed lower cord cross-sectional area along the whole cervical cord relative to those with sporadic ALS ( p ALS showed cervical cord atrophy relative to those with sporadic ALS and a relative preservation of brain motor structural and functional networks. Neurodegeneration in SOD1 ALS is likely to occur primarily in the spinal cord. An objective and accurate estimate of spinal cord damage has potential in the future assessment of preventive SOD1 ALS therapies. © 2018 American Academy of Neurology.

  11. ALS-associated mutation SOD1G93A leads to abnormal mitochondrial dynamics in osteocytes.

    Science.gov (United States)

    Wang, Huan; Yi, Jianxun; Li, Xuejun; Xiao, Yajuan; Dhakal, Kamal; Zhou, Jingsong

    2018-01-01

    While the death of motor neuron is a pathological hallmark of amyotrophic lateral sclerosis (ALS), defects in other cell types or organs may also actively contribute to ALS disease progression. ALS patients experience progressive skeletal muscle wasting that may not only exacerbate neuronal degeneration, but likely has a significant impact on bone function. In our previous published study, we have discovered severe bone loss in an ALS mouse model with overexpression of ALS-associated mutation SOD1 G93A (G93A). Here we further provide a mechanistic understanding of the bone loss in ALS animal and cellular models. Combining mitochondrial fluorescent indicators and confocal live cell imaging, we discovered abnormalities in mitochondrial network and dynamics in primary osteocytes derived from the same ALS mouse model G93A. Those mitochondrial defects occur in ALS mice after the onset of neuromuscular symptoms, indicating that mitochondria in bone cells respond to muscle atrophy during ALS disease progression. To examine whether ALS mutation has a direct contribution to mitochondrial dysfunction independent of muscle atrophy, we evaluated mitochondrial morphology and motility in cultured osteocytes (MLO-Y4) with overexpression of mitochondrial targeted SOD1 G93A . Compared with osteocytes overexpressing the wild type SOD1 as a control, the SOD1 G93A osteocytes showed similar defects in mitochondrial network and dynamic as that of the primary osteocytes derived from the ALS mouse model. In addition, we further discovered that overexpression of SOD1 G93A enhanced the expression level of dynamin-related protein 1 (Drp1), a key protein promoting mitochondrial fission activity, and reduced the expression level of optic atrophy protein 1 (OPA1), a key protein related to mitochondrial fusion. A specific mitochondrial fission inhibitor (Mdivi-1) partially reversed the effect of SOD1 G93A on mitochondrial network and dynamics, indicating that SOD1 G93A likely promotes

  12. The stability and formation of native proteins from unfolded monomers is increased through interactions with unrelated proteins.

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    Claudia Rodríguez-Almazán

    Full Text Available The intracellular concentration of protein may be as high as 400 mg per ml; thus it seems inevitable that within the cell, numerous protein-protein contacts are constantly occurring. A basic biochemical principle states that the equilibrium of an association reaction can be shifted by ligand binding. This indicates that if within the cell many protein-protein interactions are indeed taking place, some fundamental characteristics of proteins would necessarily differ from those observed in traditional biochemical systems. Accordingly, we measured the effect of eight different proteins on the formation of homodimeric triosephosphate isomerase from Trypanosoma brucei (TbTIM from guanidinium chloride unfolded monomers. The eight proteins at concentrations of micrograms per ml induced an important increase on active dimer formation. Studies on the mechanism of this phenomenon showed that the proteins stabilize the dimeric structure of TbTIM, and that this is the driving force that promotes the formation of active dimers. Similar data were obtained with TIM from three other species. The heat changes that occur when TbTIM is mixed with lysozyme were determined by isothermal titration calorimetry; the results provided direct evidence of the weak interaction between apparently unrelated proteins. The data, therefore, are strongly suggestive that the numerous protein-protein interactions that occur in the intracellular space are an additional control factor in the formation and stability of proteins.

  13. Neuroprotective Effect of Bexarotene in the SOD1G93A Mouse Model of Amyotrophic Lateral Sclerosis

    Science.gov (United States)

    Riancho, Javier; Ruiz-Soto, María; Berciano, María T.; Berciano, José; Lafarga, Miguel

    2015-01-01

    Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease characterized by progressive weakness and muscle atrophy related to the loss of upper and lower motor neurons (MNs) without a curative treatment. There is experimental evidence suggesting that retinoids may be involved in ALS pathogenesis. Bexarotene (Bxt) is a retinoid-X receptor agonist used in the treatment of cutaneous lymphoma with a favorable safety profile whose effects have been recently investigated in other neurodegenerative diseases. In this study, we analyze the potential therapeutic effect of Bxt in the SOD1G93A mouse model of ALS. Mice were treated with Bxt or vehicle five times per week from day 60 onward. Survival, weight, and neuromuscular function studies together with histological and biochemical analyses were performed. Bxt significantly delayed motor function deterioration, ameliorated the loss of body weight, and extended mice survival up to 30% of the symptomatic period. Histological analyses of the lumbosacral spinal cord revealed that Bxt markedly delayed the early motor-neuron degeneration occurring at presymptomatic stages in ALS-transgenic mice. Bxt treatment contributed to preserve the MN homeostasis in the SOD1G93A mice. Particularly, it reduced the neuronal loss and the chromatolytic response, induced nucleolar hypertrophy, decreased the formation of ubiquitylated inclusions, and modulated the lysosomal response. As an agonist of the retinoic-X receptor (RXR) pathway, Bxt notably increased the nuclear expression of the RXRα throughout transcriptionally active euchromatin domains. Bxt also contributed to protect the MN environment by reducing reactive astrogliosis and preserving perisomatic synapsis. Overall, these neuroprotective effects suggest that treatment with Bxt could be useful in ALS, particularly in those cases related to SOD1 mutations. PMID:26190974

  14. Determining the Effect of Catechins on SOD1 Conformation and Aggregation by Ion Mobility Mass Spectrometry Combined with Optical Spectroscopy

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    Zhao, Bing; Zhuang, Xiaoyu; Pi, Zifeng; Liu, Shu; Liu, Zhiqiang; Song, Fengrui

    2018-02-01

    The aggregation of Cu,Zn-superoxide dismutase (SOD1) plays an important role in the etiology of amyotrophic lateral sclerosis (ALS). For the disruption of ALS progression, discovering new drugs or compounds that can prevent SOD1 aggregation is important. In this study, ESI-MS was used to investigate the interaction of catechins and SOD1. The noncovalent complex of catechins that interact with SOD1 was found and retained in the gas phase under native ESI-MS condition. The conformation changes of SOD1 after binding with catechins were also explored via traveling wave ion mobility (IM) spectrometry. Epigallocatechin gallate (EGCG) can stabilize SOD1 conformation against unfolding in three catechins. To further evaluate the efficacy of EGCG, we monitored the fluorescence changes of dimer E2,E2,-SOD1(apo-SOD1, E:empty) with and without ligands under denaturation conditions, and found that EGCG can inhibit apo-SOD1 aggregation. In addition, the circular dichroism spectra of the samples showed that EGCG can decrease the β-sheet content of SOD1, which can produce aggregates. These results indicated that orthogonal separation dimension in the gas-phase IM coupled with ESI-MS (ESI-IM-MS) can potentially provide insight into the interaction between SOD1 and small molecules. The advantage is that it dramatically decreases the analysis time. Meantime, optical spectroscopy techniques can be used to confirm ESI-IM-MS results. [Figure not available: see fulltext.

  15. FUS and TARDBP but not SOD1 interact in genetic models of amyotrophic lateral sclerosis.

    Science.gov (United States)

    Kabashi, Edor; Bercier, Valérie; Lissouba, Alexandra; Liao, Meijiang; Brustein, Edna; Rouleau, Guy A; Drapeau, Pierre

    2011-08-01

    Mutations in the SOD1 and TARDBP genes have been commonly identified in Amyotrophic Lateral Sclerosis (ALS). Recently, mutations in the Fused in sarcoma gene (FUS) were identified in familial (FALS) ALS cases and sporadic (SALS) patients. Similarly to TDP-43 (coded by TARDBP gene), FUS is an RNA binding protein. Using the zebrafish (Danio rerio), we examined the consequences of expressing human wild-type (WT) FUS and three ALS-related mutations, as well as their interactions with TARDBP and SOD1. Knockdown of zebrafish Fus yielded a motor phenotype that could be rescued upon co-expression of wild-type human FUS. In contrast, the two most frequent ALS-related FUS mutations, R521H and R521C, unlike S57Δ, failed to rescue the knockdown phenotype, indicating loss of function. The R521H mutation caused a toxic gain of function when expressed alone, similar to the phenotype observed upon knockdown of zebrafish Fus. This phenotype was not aggravated by co-expression of both mutant human TARDBP (G348C) and FUS (R521H) or by knockdown of both zebrafish Tardbp and Fus, consistent with a common pathogenic mechanism. We also observed that WT FUS rescued the Tardbp knockdown phenotype, but not vice versa, suggesting that TARDBP acts upstream of FUS in this pathway. In addition we observed that WT SOD1 failed to rescue the phenotype observed upon overexpression of mutant TARDBP or FUS or upon knockdown of Tardbp or Fus; similarly, WT TARDBP or FUS also failed to rescue the phenotype induced by mutant SOD1 (G93A). Finally, overexpression of mutant SOD1 exacerbated the motor phenotype caused by overexpression of mutant FUS. Together our results indicate that TARDBP and FUS act in a pathogenic pathway that is independent of SOD1.

  16. FUS and TARDBP but not SOD1 interact in genetic models of amyotrophic lateral sclerosis.

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    Edor Kabashi

    2011-08-01

    Full Text Available Mutations in the SOD1 and TARDBP genes have been commonly identified in Amyotrophic Lateral Sclerosis (ALS. Recently, mutations in the Fused in sarcoma gene (FUS were identified in familial (FALS ALS cases and sporadic (SALS patients. Similarly to TDP-43 (coded by TARDBP gene, FUS is an RNA binding protein. Using the zebrafish (Danio rerio, we examined the consequences of expressing human wild-type (WT FUS and three ALS-related mutations, as well as their interactions with TARDBP and SOD1. Knockdown of zebrafish Fus yielded a motor phenotype that could be rescued upon co-expression of wild-type human FUS. In contrast, the two most frequent ALS-related FUS mutations, R521H and R521C, unlike S57Δ, failed to rescue the knockdown phenotype, indicating loss of function. The R521H mutation caused a toxic gain of function when expressed alone, similar to the phenotype observed upon knockdown of zebrafish Fus. This phenotype was not aggravated by co-expression of both mutant human TARDBP (G348C and FUS (R521H or by knockdown of both zebrafish Tardbp and Fus, consistent with a common pathogenic mechanism. We also observed that WT FUS rescued the Tardbp knockdown phenotype, but not vice versa, suggesting that TARDBP acts upstream of FUS in this pathway. In addition we observed that WT SOD1 failed to rescue the phenotype observed upon overexpression of mutant TARDBP or FUS or upon knockdown of Tardbp or Fus; similarly, WT TARDBP or FUS also failed to rescue the phenotype induced by mutant SOD1 (G93A. Finally, overexpression of mutant SOD1 exacerbated the motor phenotype caused by overexpression of mutant FUS. Together our results indicate that TARDBP and FUS act in a pathogenic pathway that is independent of SOD1.

  17. Transient β-hairpin formation in α-synuclein monomer revealed by coarse-grained molecular dynamics simulation

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    Yu, Hang; Ma, Wen [Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Center for Biophysics and Computational Biology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Han, Wei [Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Department of Physics, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Schulten, Klaus, E-mail: kschulte@ks.uiuc.edu [Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Center for Biophysics and Computational Biology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Department of Physics, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States)

    2015-12-28

    Parkinson’s disease, originating from the intrinsically disordered peptide α-synuclein, is a common neurodegenerative disorder that affects more than 5% of the population above age 85. It remains unclear how α-synuclein monomers undergo conformational changes leading to aggregation and formation of fibrils characteristic for the disease. In the present study, we perform molecular dynamics simulations (over 180 μs in aggregated time) using a hybrid-resolution model, Proteins with Atomic details in Coarse-grained Environment (PACE), to characterize in atomic detail structural ensembles of wild type and mutant monomeric α-synuclein in aqueous solution. The simulations reproduce structural properties of α-synuclein characterized in experiments, such as secondary structure content, long-range contacts, chemical shifts, and {sup 3}J(H{sub N}H{sub C{sub α}})-coupling constants. Most notably, the simulations reveal that a short fragment encompassing region 38-53, adjacent to the non-amyloid-β component region, exhibits a high probability of forming a β-hairpin; this fragment, when isolated from the remainder of α-synuclein, fluctuates frequently into its β-hairpin conformation. Two disease-prone mutations, namely, A30P and A53T, significantly accelerate the formation of a β-hairpin in the stated fragment. We conclude that the formation of a β-hairpin in region 38-53 is a key event during α-synuclein aggregation. We predict further that the G47V mutation impedes the formation of a turn in the β-hairpin and slows down β-hairpin formation, thereby retarding α-synuclein aggregation.

  18. Overexpression of human SOD1 improves survival of mice susceptible to endotoxic shock

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    Charchaflieh J

    2012-07-01

    Full Text Available Jean Charchaflieh,1,2 Georges I Labaze,1 Pulsar Li,1 Holly Van Remmen,3 Haekyung Lee,1 Helen Stutz,1 Arlan Richardson,3 Asher Emanuel,1 Ming Zhang1,41Department of Anesthesiology, State University of New York (SUNY Downstate Medical Center, New York, NY, USA; 2Department of Anesthesiology, Yale University School of Medicine, New Haven, CT, USA; 3Barshop Center for Longevity and Aging Studies, University of Texas Health Science Center at San Antonio, San Antonio, TX, USA; 4Department of Cell Biology, State University of New York (SUNY Downstate Medical Center, New York, NY, USABackground: Protective effects of the antioxidant enzyme Cu-Zn superoxide dismutase (SOD1 against endotoxic shock have not been demonstrated in animal models. We used a murine model to investigate whether overexpression of SOD1 protects against endotoxic shock, and whether the genetic background of SOD1 affects its effective protective effects and susceptibility to endotoxic shock.Methods: Transgenic (tg mice overexpressing human SOD1 and control mice were divided into four groups based on their genetic background: (1 tg mice with mixed genetic background (tg-JAX; (2 wild-type (WT littermates of tg-JAX strain (WT-JAX; (3 tg mice with C57BL/6J background (tg-TX; (4 WT littermates of tg-TX strain (WT-TX. Activity of SOD1 in the intestine, heart, and liver of tg and control mice was confirmed using a polyacrylamide activity gel. Endotoxic shock was induced by intraperitoneal injection of lipopolysaccharide. Survival rates over 120 hours (mean, 95% confidence interval were analyzed using Kaplan–Meier survival curves.Results: Human SOD1 enzymatic activities were significantly higher in the intestine, heart, and liver of both tg strains (tg-JAX and tg-TX compared with their WT littermates (WT-JAX and WT-TX, respectively. Interestingly, the endogenous SOD1 activities in tg-JAX mice were decreased compared with their WT littermates (WT-JAX, but such aberrant changes were not

  19. Quercetin Protects Primary Human Osteoblasts Exposed to Cigarette Smoke through Activation of the Antioxidative Enzymes HO-1 and SOD-1

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    Karl F. Braun

    2011-01-01

    Full Text Available Smokers frequently suffer from impaired fracture healing often due to poor bone quality and stability. Cigarette smoking harms bone cells and their homeostasis by increased formation of reactive oxygen species (ROS. The aim of this study was to investigate whether Quercetin, a naturally occurring antioxidant, can protect osteoblasts from the toxic effects of smoking. Human osteoblasts exposed to cigarette smoke medium (CSM rapidly produced ROS and their viability decreased concentration- and time-dependently. Co-, pre- and postincubation with Quercetin dose-dependently improved their viability. Quercetin increased the expression of the anti-oxidative enzymes heme-oxygenase- (HO- 1 and superoxide-dismutase- (SOD- 1. Inhibiting HO-1 activity abolished the protective effect of Quercetin. Our results demonstrate that CSM damages human osteoblasts by accumulation of ROS. Quercetin can diminish this damage by scavenging the radicals and by upregulating the expression of HO-1 and SOD-1. Thus, a dietary supplementation with Quercetin could improve bone matter, stability and even fracture healing in smokers.

  20. Resveratrol Derivative-Rich Melinjo Seed Extract Attenuates Skin Atrophy in Sod1-Deficient Mice

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    Kenji Watanabe

    2015-01-01

    Full Text Available The oxidative damages induced by a redox imbalance cause age-related changes in cells and tissues. Superoxide dismutase (SOD enzymes play a pivotal role in the antioxidant system and they also catalyze superoxide radicals. Since the loss of cytoplasmic SOD (SOD1 resulted in aging-like phenotypes in several types of murine tissue, SOD1 is essential for the maintenance of tissue homeostasis. Melinjo (Gnetum gnemon Linn seed extract (MSE contains trans-resveratrol (RSV and resveratrol derivatives, including gnetin C, gnemonoside A, and gnemonoside D. MSE intake also exerts no adverse events in human study. In the present studies, we investigated protective effects of MSE on age-related skin pathologies in mice. Orally MSE and RSV treatment reversed the skin thinning associated with increased oxidative damage in the Sod1−/− mice. Furthermore, MSE and RSV normalized gene expression of Col1a1 and p53 and upregulated gene expression of Sirt1 in skin tissues. In vitro experiments revealed that RSV significantly promoted the viability of Sod1−/− fibroblasts. These finding demonstrated that RSV in MSE stably suppressed an intrinsic superoxide generation in vivo and in vitro leading to protecting skin damages. RSV derivative-rich MSE may be a powerful food of treatment for age-related skin diseases caused by oxidative damages.

  1. Conformations of islet amyloid polypeptide monomers in a membrane environment: implications for fibril formation.

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    Mojie Duan

    Full Text Available The amyloid fibrils formed by islet amyloid polypeptide (IAPP are associated with type II diabetes. One of the proposed mechanisms of the toxicity of IAPP is that it causes membrane damage. The fatal mutation of S20G human IAPP was reported to lead to early onset of type II diabetes and high tendency of amyloid formation in vitro. Characterizing the structural features of the S20G mutant in its monomeric state is experimentally difficult because of its unusually fast aggregation rate. Computational work complements experimental studies. We performed a series of molecular dynamics simulations of the monomeric state of human variants in the membrane. Our simulations are validated by extensive comparisons with experimental data. We find that a helical disruption at His18 is common to both human variants. An L-shaped motif of S20G mutant is observed in one of the conformational families. This motif that bends at His18 resembles the overall topology of IAPP fibrils. The conformational preorganization into the fibril-like topology provides a possible explanation for the fast aggregation rate of S20G IAPP.

  2. Mice overexpressing both non-mutated human SOD1 and mutated SOD1G93A genes: a competent experimental model for studying iron metabolism in amyotrophic lateral sclerosis

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    Anna eGajowiak

    2016-01-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is a progressive neurodegenerative disease characterized by degeneration and loss of motor neurons in the spinal cord, brainstem and motor cortex. Up to 10% of ALS cases are inherited (familial, fALS and associated with mutations, frequently in the superoxide dismutase 1 (SOD1 gene. Rodent transgenic models of ALS are often used to elucidate a complex pathogenesis of this disease. Of importance, both ALS patients and animals carrying mutated human SOD1 gene show symptoms of oxidative stress and iron metabolism misregulation. The aim of our study was to characterize changes in iron metabolism in one of the most commonly used models of ALS – transgenic mice overexpressing human mutated SOD1G93A gene. We analyzed the expression of iron-related genes in asymptomatic, 2-month old and symptomatic, 4-month old SOD1G93A mice. In parallel, respective age-matched mice overexpressing human non-mutated SOD1 transgene and control mice were analyzed. We demonstrate that the overexpression of both SOD1 and SOD1G93A genes account for a substantial increase in SOD1 protein levels and activity in selected tissues and that not all the changes in iron metabolism genes expression are specific for the overexpression of the mutated form of SOD1.

  3. Oxidant production and SOD1 protein expression in single skeletal myofibers from Down syndrome mice

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    Patrick M. Cowley

    2017-10-01

    Full Text Available Down syndrome (DS is a genetic condition caused by the triplication of chromosome 21. Persons with DS exhibit pronounced muscle weakness, which also occurs in the Ts65Dn mouse model of DS. Oxidative stress is thought to be an underlying factor in the development of DS-related pathologies including muscle dysfunction. High-levels of oxidative stress have been attributed to triplication and elevated expression of superoxide dismutase 1 (SOD1; a gene located on chromosome 21. The elevated expression of SOD1 is postulated to increase production of hydrogen peroxide and cause oxidative injury and cell death. However, it is unknown whether SOD1 protein expression is associated with greater oxidant production in skeletal muscle from Ts65Dn mice. Thus, our objective was to assess levels of SOD1 expression and oxidant production in skeletal myofibers from the flexor digitorum brevis obtained from Ts65Dn and control mice. Measurements of oxidant production were obtained from myofibers loaded with 2′,7′-dichlorodihydrofluorescein diacetate (DCFH2-DA in the basal state and following 15 min of stimulated unloaded contraction. Ts65Dn myofibers exhibited a significant decrease in basal DCF emissions (p 0.05. Myofibers from Ts65Dn mice tended to be smaller and myonuclear domain was lower (p < 0.05. In summary, myofibers from Ts65Dn mice exhibited decreased basal DCF emissions that were coupled with elevated protein expression of SOD1. Stimulated contraction in isolated myofibers did not affect DCF emissions in either group. These findings suggest the skeletal muscle dysfunction in the adult Ts65Dn mouse is not associated with skeletal muscle oxidative stress.

  4. Misfolded SOD1 associated with motor neuron mitochondria alters mitochondrial shape and distribution prior to clinical onset.

    Directory of Open Access Journals (Sweden)

    Christine Vande Velde

    Full Text Available Mutations in superoxide dismutase (SOD1 are causative for inherited amyotrophic lateral sclerosis. A proportion of SOD1 mutant protein is misfolded onto the cytoplasmic face of mitochondria in one or more spinal cord cell types. By construction of mice in which mitochondrially targeted enhanced green fluorescent protein is selectively expressed in motor neurons, we demonstrate that axonal mitochondria of motor neurons are primary in vivo targets for misfolded SOD1. Mutant SOD1 alters axonal mitochondrial morphology and distribution, with dismutase active SOD1 causing mitochondrial clustering at the proximal side of Schmidt-Lanterman incisures within motor axons and dismutase inactive SOD1 producing aberrantly elongated axonal mitochondria beginning pre-symptomatically and increasing in severity as disease progresses. Somal mitochondria are altered by mutant SOD1, with loss of the characteristic cylindrical, networked morphology and its replacement by a less elongated, more spherical shape. These data indicate that mutant SOD1 binding to mitochondria disrupts normal mitochondrial distribution and size homeostasis as early pathogenic features of SOD1 mutant-mediated ALS.

  5. Acute intermittent hypoxia induced phrenic long-term facilitation despite increased SOD1 expression in a rat model of ALS.

    Science.gov (United States)

    Nichols, Nicole L; Satriotomo, Irawan; Harrigan, Daniel J; Mitchell, Gordon S

    2015-11-01

    Amyotrophic lateral sclerosis (ALS) is a progressive and fatal neurodegenerative disease characterized by motor neuron death. Since most ALS patients succumb to ventilatory failure from loss of respiratory motor neurons, any effective ALS treatment must preserve and/or restore breathing capacity. In rats over-expressing mutated super-oxide dismutase-1 (SOD1(G93A)), the capacity to increase phrenic motor output is decreased at disease end-stage, suggesting imminent ventilatory failure. Acute intermittent hypoxia (AIH) induces phrenic long-term facilitation (pLTF), a form of spinal respiratory motor plasticity with potential to restore phrenic motor output in clinical disorders that compromise breathing. Since pLTF requires NADPH oxidase activity and reactive oxygen species (ROS) formation, it is blocked by NADPH oxidase inhibition and SOD mimetics in normal rats. Thus, we hypothesized that SOD1(G93A) (mutant; MT) rats do not express AIH-induced pLTF due to over-expression of active mutant superoxide dismutase-1. AIH-induced pLTF and hypoglossal (XII) LTF were assessed in young, pre-symptomatic and end-stage anesthetized MT rats and age-matched wild-type littermates. Contrary to predictions, pLTF and XII LTF were observed in MT rats at all ages; at end-stage, pLTF was actually enhanced. SOD1 levels were elevated in young and pre-symptomatic MT rats, yet superoxide accumulation in putative phrenic motor neurons (assessed with dihydroethidium) was unchanged; however, superoxide accumulation significantly decreased at end-stage. Thus, compensatory mechanisms appear to maintain ROS homoeostasis until late in disease progression, preserving AIH-induced respiratory plasticity. Following intrathecal injections of an NADPH oxidase inhibitor (apocynin; 600 μM; 12 μL), pLTF was abolished in pre-symptomatic, but not end-stage MT rats, demonstrating that pLTF is NADPH oxidase dependent in pre-symptomatic, but NADPH oxidase independent in end-stage MT rats. Mechanisms

  6. Differential effects of phytotherapic preparations in the hSOD1 Drosophila melanogaster model of ALS

    Science.gov (United States)

    De Rose, Francescaelena; Marotta, Roberto; Talani, Giuseppe; Catelani, Tiziano; Solari, Paolo; Poddighe, Simone; Borghero, Giuseppe; Marrosu, Francesco; Sanna, Enrico; Kasture, Sanjay; Acquas, Elio; Liscia, Anna

    2017-01-01

    The present study was aimed at characterizing the effects of Withania somnifera (Wse) and Mucuna pruriens (Mpe) on a Drosophila melanogaster model for Amyotrophic Lateral Sclerosis (ALS). In particular, the effects of Wse and Mpe were assessed following feeding the flies selectively overexpressing the wild human copper, zinc-superoxide dismutase (hSOD1-gain-of-function) in Drosophila motoneurons. Although ALS-hSOD1 mutants showed no impairment in life span, with respect to GAL4 controls, the results revealed impairment of climbing behaviour, muscle electrophysiological parameters (latency and amplitude of ePSPs) as well as thoracic ganglia mitochondrial functions. Interestingly, Wse treatment significantly increased lifespan of hSDO1 while Mpe had not effect. Conversely, both Wse and Mpe significantly rescued climbing impairment, and also latency and amplitude of ePSPs as well as failure responses to high frequency DLM stimulation. Finally, mitochondrial alterations were any more present in Wse- but not in Mpe-treated hSOD1 mutants. Hence, given the role of inflammation in the development of ALS, the high translational impact of the model, the known anti-inflammatory properties of these extracts, and the viability of their clinical use, these results suggest that the application of Wse and Mpe might represent a valuable pharmacological strategy to counteract the progression of ALS and related symptoms. PMID:28102336

  7. SOD1 aggregation in ALS mice shows simplistic test tube behavior.

    Science.gov (United States)

    Lang, Lisa; Zetterström, Per; Brännström, Thomas; Marklund, Stefan L; Danielsson, Jens; Oliveberg, Mikael

    2015-08-11

    A longstanding challenge in studies of neurodegenerative disease has been that the pathologic protein aggregates in live tissue are not amenable to structural and kinetic analysis by conventional methods. The situation is put in focus by the current progress in demarcating protein aggregation in vitro, exposing new mechanistic details that are now calling for quantitative in vivo comparison. In this study, we bridge this gap by presenting a direct comparison of the aggregation kinetics of the ALS-associated protein superoxide dismutase 1 (SOD1) in vitro and in transgenic mice. The results based on tissue sampling by quantitative antibody assays show that the SOD1 fibrillation kinetics in vitro mirror with remarkable accuracy the spinal cord aggregate buildup and disease progression in transgenic mice. This similarity between in vitro and in vivo data suggests that, despite the complexity of live tissue, SOD1 aggregation follows robust and simplistic rules, providing new mechanistic insights into the ALS pathology and organism-level manifestation of protein aggregation phenomena in general.

  8. Single chain variable fragment antibodies block aggregation and toxicity induced by familial ALS-linked mutant forms of SOD1.

    Science.gov (United States)

    Ghadge, Ghanashyam D; Pavlovic, John D; Koduvayur, Sujatha P; Kay, Brian K; Roos, Raymond P

    2013-08-01

    Approximately 10% of amyotrophic lateral sclerosis (ALS) cases are familial (known as FALS) with an autosomal dominant inheritance pattern, and ~25% of FALS cases are caused by mutations in Cu/Zn superoxide dismutase (SOD1). There is convincing evidence that mutant SOD1 (mtSOD1) kills motor neurons (MNs) because of a gain-of-function toxicity, most likely related to aggregation of mtSOD1. A number of recent reports have suggested that antibodies can be used to treat mtSOD1-induced FALS. To follow up on the use of antibodies as potential therapeutics, we generated single chain fragments of variable region antibodies (scFvs) against SOD1, and then expressed them as 'intrabodies' within a motor neuron cell line. In the present study, we describe isolation of human scFvs that interfere with mtSOD1 in vitro aggregation and toxicity. These scFvs may have therapeutic potential in sporadic ALS, as well as FALS, given that sporadic ALS may also involve abnormalities in the SOD1 protein or activity. Copyright © 2013 Elsevier Inc. All rights reserved.

  9. Pyrimethamine significantly lowers cerebrospinal fluid Cu/Zn superoxide dismutase in amyotrophic lateral sclerosis patients with SOD1 mutations.

    Science.gov (United States)

    Lange, Dale J; Shahbazi, Mona; Silani, Vincenzo; Ludolph, Albert C; Weishaupt, Jochen H; Ajroud-Driss, Senda; Fields, Kara G; Remanan, Rahul; Appel, Stanley H; Morelli, Claudia; Doretti, Alberto; Maderna, Luca; Messina, Stefano; Weiland, Ulrike; Marklund, Stefan L; Andersen, Peter M

    2017-06-01

    Cu/Zn superoxide dismutase (SOD1) reduction prolongs survival in SOD1-transgenic animal models. Pyrimethamine produces dose-dependent SOD1 reduction in cell culture systems. A previous phase 1 trial showed pyrimethamine lowers SOD1 levels in leukocytes in patients with SOD1 mutations. This study investigated whether pyrimethamine lowered SOD1 levels in the cerebrospinal fluid (CSF) in patients carrying SOD1 mutations linked to familial amyotrophic lateral sclerosis (fALS/SOD1). A multicenter (5 sites), open-label, 9-month-duration, dose-ranging study was undertaken to determine the safety and efficacy of pyrimethamine to lower SOD1 levels in the CSF in fALS/SOD1. All participants underwent 3 lumbar punctures, blood draw, clinical assessment of strength, motor function, quality of life, and adverse effect assessments. SOD1 levels were measured in erythrocytes and CSF. Pyrimethamine was measured in plasma and CSF. Appel ALS score, ALS Functional Rating Scale-Revised, and McGill Quality of Life Single-Item Scale were measured at screening, visit 6, and visit 9. We enrolled 32 patients; 24 completed 6 visits (18 weeks), and 21 completed all study visits. A linear mixed effects model showed a significant reduction in CSF SOD1 at visit 6 (p < 0.001) with a mean reduction of 13.5% (95% confidence interval [CI] = 8.4-18.5) and at visit 9 (p < 0.001) with a mean reduction of 10.5% (95% CI = 5.2-15.8). Pyrimethamine is safe and well tolerated in ALS. Pyrimethamine is capable of producing a significant reduction in total CSF SOD1 protein content in patients with ALS caused by different SOD1 mutations. Further long-term studies are warranted to assess clinical efficacy. Ann Neurol 2017;81:837-848. © 2017 The Authors. Annals of Neurology published by Wiley Periodicals, Inc. on behalf of American Neurological Association.

  10. Accumulation of Misfolded SOD1 in Dorsal Root Ganglion Degenerating Proprioceptive Sensory Neurons of Transgenic Mice with Amyotrophic Lateral Sclerosis

    Directory of Open Access Journals (Sweden)

    Javier Sábado

    2014-01-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is an adult-onset progressive neurodegenerative disease affecting upper and lower motoneurons (MNs. Although the motor phenotype is a hallmark for ALS, there is increasing evidence that systems other than the efferent MN system can be involved. Mutations of superoxide dismutase 1 (SOD1 gene cause a proportion of familial forms of this disease. Misfolding and aggregation of mutant SOD1 exert neurotoxicity in a noncell autonomous manner, as evidenced in studies using transgenic mouse models. Here, we used the SOD1G93A mouse model for ALS to detect, by means of conformational-specific anti-SOD1 antibodies, whether misfolded SOD1-mediated neurotoxicity extended to neuronal types other than MNs. We report that large dorsal root ganglion (DRG proprioceptive neurons accumulate misfolded SOD1 and suffer a degenerative process involving the inflammatory recruitment of macrophagic cells. Degenerating sensory axons were also detected in association with activated microglial cells in the spinal cord dorsal horn of diseased animals. As large proprioceptive DRG neurons project monosynaptically to ventral horn MNs, we hypothesise that a prion-like mechanism may be responsible for the transsynaptic propagation of SOD1 misfolding from ventral horn MNs to DRG sensory neurons.

  11. Enhanced tethered-flight duration and locomotor activity by overexpression of the human gene SOD1 in Drosophila motorneurons

    Directory of Open Access Journals (Sweden)

    Agavni Petrosyan

    2015-03-01

    Full Text Available Mutation of the human gene superoxide dismutase (hSOD1 is associated with the fatal neurodegenerative disease familial amyotrophic lateral sclerosis (Lou Gehrig’s disease. Selective overexpression of hSOD1 in Drosophila motorneurons increases lifespan to 140% of normal. The current study was designed to determine resistance to lifespan decline and failure of sensorimotor functions by overexpressing hSOD1 in Drosophila‘s motorneurons. First, we measured the ability to maintain continuous flight and wingbeat frequency (WBF as a function of age (5 to 50 days. Flies overexpressing hSOD1 under the D42-GAL4 activator were able to sustain flight significantly longer than controls, with the largest effect observed in the middle stages of life. The hSOD1-expressed line also had, on average, slower wingbeat frequencies in late, but not early life relative to age-matched controls. Second, we examined locomotor (exploratory walking behavior in late life when flies had lost the ability to fly (age ≥ 60 d. hSOD1-expressed flies showed significantly more robust walking activity relative to controls. Findings show patterns of functional decline dissimilar to those reported for other life-extended lines, and suggest that the hSOD1 gene not only delays death but enhances sensorimotor abilities critical to survival even in late life.

  12. Genetic biomarkers for ALS disease in transgenic SOD1(G93A mice.

    Directory of Open Access Journals (Sweden)

    Ana C Calvo

    Full Text Available The pathophysiological mechanisms of both familial and sporadic Amyotrophic Lateral Sclerosis (ALS are unknown, although growing evidence suggests that skeletal muscle tissue is a primary target of ALS toxicity. Skeletal muscle biopsies were performed on transgenic SOD1(G93A mice, a mouse model of ALS, to determine genetic biomarkers of disease longevity. Mice were anesthetized with isoflurane, and three biopsy samples were obtained per animal at the three main stages of the disease. Transcriptional expression levels of seventeen genes, Ankrd1, Calm1, Col19a1, Fbxo32, Gsr, Impa1, Mef2c, Mt2, Myf5, Myod1, Myog, Nnt, Nogo A, Pax7, Rrad, Sln and Snx10, were tested in each muscle biopsy sample. Total RNA was extracted using TRIzol Reagent according to the manufacturer's protocol, and variations in gene expression were assayed by real-time PCR for all of the samples. The Pearson correlation coefficient was used to determine the linear correlation between transcriptional expression levels throughout disease progression and longevity. Consistent with the results obtained from total skeletal muscle of transgenic SOD1(G93A mice and 74-day-old denervated mice, five genes (Mef2c, Gsr, Col19a1, Calm1 and Snx10 could be considered potential genetic biomarkers of longevity in transgenic SOD1(G93A mice. These results are important because they may lead to the exploration of previously unexamined tissues in the search for new disease biomarkers and even to the application of these findings in human studies.

  13. Oxidative Stress Induced Age Dependent Meibomian Gland Dysfunction in Cu, Zn-Superoxide Dismutase-1 (Sod1) Knockout Mice

    Science.gov (United States)

    Ibrahim, Osama M. A.; Dogru, Murat; Matsumoto, Yukihiro; Igarashi, Ayako; Kojima, Takashi; Wakamatsu, Tais Hitomi; Inaba, Takaaki; Shimizu, Takahiko; Shimazaki, Jun; Tsubota, Kazuo

    2014-01-01

    Purpose The purpose of our study was to investigate alterations in the meibomian gland (MG) in Cu, Zn-Superoxide Dismutase-1 knockout (Sod1 −/−) mouse. Methods Tear function tests [Break up time (BUT) and cotton thread] and ocular vital staining test were performed on Sod1 −/− male mice (n = 24) aged 10 and 50 weeks, and age and sex matched wild–type (+/+) mice (n = 25). Tear and serum samples were collected at sacrifice for inflammatory cytokine assays. MG specimens underwent Hematoxylin and Eosin staining, Mallory staining for fibrosis, Oil Red O lipid staining, TUNEL staining, immunohistochemistry stainings for 4HNE, 8-OHdG and CD45. Transmission electron microscopic examination (TEM) was also performed. Results Corneal vital staining scores in the Sod1 −/− mice were significantly higher compared with the wild type mice throughout the follow-up. Tear and serum IL-6 and TNF-α levels also showed significant elevations in the 10 to 50 week Sod1 −/− mice. Oil Red O staining showed an accumulation of large lipid droplets in the Sod1 −/− mice at 50 weeks. Immunohistochemistry revealed both increased TUNEL and oxidative stress marker stainings of the MG acinar epithelium in the Sod1 −/− mice compared to the wild type mice. Immunohistochemistry staining for CD45 showed increasing inflammatory cell infiltrates from 10 to 50 weeks in the Sod1 −/− mice compared to the wild type mice. TEM revealed prominent mitochondrial changes in 50 week Sod1 −/− mice. Conclusions Our results suggest that reactive oxygen species might play a vital role in the pathogensis of meibomian gland dysfunction. The Sod1 −/− mouse appears to be a promising model for the study of reactive oxygen species associated MG alterations. PMID:25036096

  14. A Model of Oxidative Stress Management: Moderation of Carbohydrate Metabolizing Enzymes in SOD1-Null Drosophila melanogaster

    Science.gov (United States)

    Bernard, Kristine E.; Parkes, Tony L.; Merritt, Thomas J. S.

    2011-01-01

    The response to oxidative stress involves numerous genes and mutations in these genes often manifest in pleiotropic ways that presumably reflect perturbations in ROS-mediated physiology. The Drosophila melanogaster SOD1-null allele (cSODn108) is proposed to result in oxidative stress by preventing superoxide breakdown. In SOD1-null flies, oxidative stress management is thought to be reliant on the glutathione-dependent antioxidants that utilize NADPH to cycle between reduced and oxidized form. Previous studies suggest that SOD1-null Drosophila rely on lipid catabolism for energy rather than carbohydrate metabolism. We tested these connections by comparing the activity of carbohydrate metabolizing enzymes, lipid and triglyceride concentration, and steady state NADPH:NADP+ in SOD1-null and control transgenic rescue flies. We find a negative shift in the activity of carbohydrate metabolizing enzymes in SOD1-nulls and the NADP+-reducing enzymes were found to have significantly lower activity than the other enzymes assayed. Little evidence for the catabolism of lipids as preferential energy source was found, as the concentration of lipids and triglycerides were not significantly lower in SOD1-nulls compared with controls. Using a starvation assay to impact lipids and triglycerides, we found that lipids were indeed depleted in both genotypes when under starvation stress, suggesting that oxidative damage was not preventing the catabolism of lipids in SOD1-null flies. Remarkably, SOD1-nulls were also found to be relatively resistant to starvation. Age profiles of enzyme activity, triglyceride and lipid concentration indicates that the trends observed are consistent over the average lifespan of the SOD1-nulls. Based on our results, we propose a model of physiological response in which organisms under oxidative stress limit the production of ROS through the down-regulation of carbohydrate metabolism in order to moderate the products exiting the electron transport chain. PMID

  15. Mechanisms of Enhanced Phrenic Long-Term Facilitation in SOD1G93A Rats

    Science.gov (United States)

    Satriotomo, Irawan; Grebe, Ashley M.

    2017-01-01

    Amyotrophic lateral sclerosis (ALS) is a degenerative motor neuron disease, causing muscle paralysis and death from respiratory failure. Effective means to preserve/restore ventilation are necessary to increase the quality and duration of life in ALS patients. At disease end-stage in a rat ALS model (SOD1G93A), acute intermittent hypoxia (AIH) restores phrenic nerve activity to normal levels via enhanced phrenic long-term facilitation (pLTF). Mechanisms enhancing pLTF in end-stage SOD1G93A rats are not known. Moderate AIH-induced pLTF is normally elicited via cellular mechanisms that require the following: Gq-protein-coupled 5-HT2 receptor activation, new BDNF synthesis, and MEK/ERK signaling (the Q pathway). In contrast, severe AIH elicits pLTF via a distinct mechanism that requires the following: Gs-protein-coupled adenosine 2A receptor activation, new TrkB synthesis, and PI3K/Akt signaling (the S pathway). In end-stage male SOD1G93A rats and wild-type littermates, we investigated relative Q versus S pathway contributions to enhanced pLTF via intrathecal (C4) delivery of small interfering RNAs targeting BDNF or TrkB mRNA, and MEK/ERK (U0126) or PI3 kinase/Akt (PI828) inhibitors. In anesthetized, paralyzed and ventilated rats, moderate AIH-induced pLTF was abolished by siBDNF and UO126, but not siTrkB or PI828, demonstrating that enhanced pLTF occurs via the Q pathway. Although phrenic motor neuron numbers were decreased in end-stage SOD1G93A rats (∼30% survival; p phrenic motor neurons (p phrenic motor plasticity results from amplification of normal cellular mechanisms versus addition/substitution of alternative mechanisms. Greater understanding of mechanisms underlying phrenic motor plasticity in ALS may guide development of new therapies to preserve and/or restore breathing in ALS patients. PMID:28500219

  16. Peripheral motor axons of SOD1(G127X) mutant mice are susceptible to activity-dependent degeneration

    DEFF Research Database (Denmark)

    Alvarez Herrero, Susana; Calin, A; Graffmo, K S

    2013-01-01

    -onset, fast-progression SOD1(G127X) mouse model of amyotrophic lateral sclerosis to long-lasting, high-frequency repetitive activity. Tibial nerves were stimulated at ankle in 7 to 8-month-old SOD1(G127X) mice when they were clinically indistinguishable from wild-type (WT) mice. The evoked compound muscle......-concentrations. It is possible that in SOD1(G127X) there is inadequate energy-dependent Na(+)/K(+) pumping, which may lead to a lethal Na(+) overload....

  17. Effect of functional monomers in all-in-one adhesive systems on formation of enamel/dentin acid-base resistant zone.

    Science.gov (United States)

    Nikaido, Toru; Ichikawa, Chiaki; Li, Na; Takagaki, Tomohiro; Sadr, Alireza; Yoshida, Yasuhiro; Suzuki, Kazuomi; Tagami, Junji

    2011-01-01

    This study aimed at evaluating the effect of functional monomers in all-in-one adhesive systems on formation of acid-base resistant zone (ABRZ) in enamel and dentin. Experimental adhesive systems containing one of three functional monomers; MDP, 3D-SR and 4-META were applied to enamel or dentin surface and light-cured. A universal resin composite was then placed. The specimens were subjected to a demineralizing solution (pH 4.5) and 5% NaClO for acid-base challenge and then observed by SEM. The ABRZ was clearly observed in both enamel and dentin interfaces. However, enamel ABRZ was thinner than dentin ABRZ in all adhesives. Morphology of the ABRZ was different between enamel and dentin, and also among the adhesives. Funnel-shaped erosion was observed only in the enamel specimen with the 4-META adhesive. The formation of enamel/dentin ABRZ was confirmed in all adhesives, but the morphology was influenced by the functional monomers.

  18. Novel biocompatible hydrogel nanoparticles: generation and size-tuning of nanoparticles by the formation of micelle templates obtained from thermo-responsive monomers mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Khandadash, Raz; Machtey, Victoria [Bar Ilan University, Department of Chemistry (Israel); Shainer, Inbal [Tel-Aviv University, Department of Neurobiology, The George S. Wise Faculty of Life Sciences (Israel); Gottlieb, Hugo E. [Bar Ilan University, Department of Chemistry (Israel); Gothilf, Yoav [Tel-Aviv University, Department of Neurobiology, The George S. Wise Faculty of Life Sciences, and Sagol School of Neuroscience (Israel); Ebenstein, Yuval [Tel Aviv University, Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry (Israel); Weiss, Aryeh [Bar Ilan University, School of Engineering (Israel); Byk, Gerardo, E-mail: gerardo.byk@biu.ac.il [Bar Ilan University, Department of Chemistry (Israel)

    2014-12-15

    Biocompatible hydrogel nanoparticles are prepared by polymerization and cross-linking of N-isopropyl acrylamide in a micelle template formed by block copolymers macro-monomers at high temperature. Different monomer ratios form, at high temperature, well-defined micelles of different sizes which are further polymerized leading to nanoparticles with varied sizes from 20 to 390 nm. Physico-chemical characterization of the nanoparticles demonstrates their composition and homogeneity. The NPs were tested in vitro and in vivo biocompatibility assays, and their lack of toxicity was proven. The NPs can be labeled with fluorescent probes, and their intracellular fate can be visualized and quantified using confocal microscopy. Their uptake by live stem cells and distribution in whole developing animals is reported. On the basis of our results, a mechanism of nanoparticle formation is suggested. The lack of toxicity makes these nanoparticles especially attractive for biological applications such as screening and bio-sensing.

  19. Biological effects of CCS in the absence of SOD1 enzyme activation: implications for disease in a mouse model for ALS.

    Science.gov (United States)

    Proescher, Jody B; Son, Marjatta; Elliott, Jeffrey L; Culotta, Valeria C

    2008-06-15

    The CCS copper chaperone is critical for maturation of Cu, Zn-superoxide dismutase (SOD1) through insertion of the copper co-factor and oxidization of an intra-subunit disulfide. The disulfide helps stabilize the SOD1 polypeptide, which can be particularly important in cases of amyotrophic lateral sclerosis (ALS) linked to misfolding of mutant SOD1. Surprisingly, however, over-expressed CCS was recently shown to greatly accelerate disease in a G93A SOD1 mouse model for ALS. Herein we show that disease in these G93A/CCS mice correlates with incomplete oxidation of the SOD1 disulfide. In the brain and spinal cord, CCS over-expression failed to enhance oxidation of the G93A SOD1 disulfide and if anything, effected some accumulation of disulfide-reduced SOD1. This effect was mirrored in culture with a C244,246S mutant of CCS that has the capacity to interact with SOD1 but can neither insert copper nor oxidize the disulfide. In spite of disulfide effects, there was no evidence for increased SOD1 aggregation. If anything, CCS over-expression prevented SOD1 misfolding in culture as monitored by detergent insolubility. This protection against SOD1 misfolding does not require SOD1 enzyme activation as the same effect was obtained with the C244,246S allele of CCS. In the G93A SOD1 mouse, CCS over-expression was likewise associated with a lack of obvious SOD1 misfolding marked by detergent insolubility. CCS over-expression accelerates SOD1-linked disease without the hallmarks of misfolding and aggregation seen in other mutant SOD1 models. These studies are the first to indicate biological effects of CCS in the absence of SOD1 enzymatic activation.

  20. Reactive oxygen species on bone mineral density and mechanics in Cu,Zn superoxide dismutase (Sod1) knockout mice

    International Nuclear Information System (INIS)

    Smietana, Michael J.; Arruda, Ellen M.; Faulkner, John A.; Brooks, Susan V.; Larkin, Lisa M.

    2010-01-01

    Research highlights: → Reactive oxygen species (ROS) are considered to be a factor in the onset of a number of age-associated conditions, including loss of BMD. → Cu,Zn-superoxide dismutase (Sod1) deficient mice have increased ROS, reduced bone mineral density, decreased bending stiffness, and decreased strength compared to WT controls. → Increased ROS caused by the deficiency of Sod1, may be responsible for the changes in BMD and bone mechanics and therefore represent an appropriate model for studying mechanisms of age-associated bone loss. -- Abstract: Reactive oxygen species (ROS) play a role in a number of degenerative conditions including osteoporosis. Mice deficient in Cu,Zn-superoxide dismutase (Sod1) (Sod1 -/- mice) have elevated oxidative stress and decreased muscle mass and strength compared to wild-type mice (WT) and appear to have an accelerated muscular aging phenotype. Thus, Sod1 -/- mice may be a good model for evaluating the effects of free radical generation on diseases associated with aging. In this experiment, we tested the hypothesis that the structural integrity of bone as measured by bending stiffness (EI; N/mm 2 ) and strength (MPa) is diminished in Sod1 -/- compared to WT mice. Femurs were obtained from male and female WT and Sod1 -/- mice at 8 months of age and three-point bending tests were used to determine bending stiffness and strength. Bones were also analyzed for bone mineral density (BMD; mg/cc) using micro-computed tomography. Femurs were approximately equal in length across all groups, and there were no significant differences in BMD or EI with respect to gender in either genotype. Although male and female mice demonstrated similar properties within each genotype, Sod1 -/- mice exhibited lower BMD and EI of femurs from both males and females compared with gender matched WT mice. Strength of femurs was also lower in Sod1 -/- mice compared to WT as well as between genders. These data indicate that increased oxidative stress

  1. Structural and biophysical properties of metal-free pathogenic SOD1 mutants A4V and G93A

    Energy Technology Data Exchange (ETDEWEB)

    Galaleldeen, Ahmad; Strange, Richard W.; Whitson, Lisa J.; Antonyuk, Svetlana V.; Narayana, Narendra; Taylor, Alexander B.; Schuermann, Jonathan P.; Holloway, Stephen P.; Hasnain, S.Samar; Hart, P. John; (Texas-HSC); (Liverpool)

    2010-07-19

    Amyotrophic lateral sclerosis (ALS) is a fatal, progressive neurodegenerative disease characterized by the destruction of motor neurons in the spinal cord and brain. A subset of ALS cases are linked to dominant mutations in copper-zinc superoxide dismutase (SOD1). The pathogenic SOD1 variants A4V and G93A have been the foci of multiple studies aimed at understanding the molecular basis for SOD1-linked ALS. The A4V variant is responsible for the majority of familial ALS cases in North America, causing rapidly progressing paralysis once symptoms begin and the G93A SOD1 variant is overexpressed in often studied murine models of the disease. Here we report the three-dimensional structures of metal-free A4V and of metal-bound and metal-free G93A SOD1. In the metal-free structures, the metal-binding loop elements are observed to be severely disordered, suggesting that these variants may share mechanisms of aggregation proposed previously for other pathogenic SOD1 proteins.

  2. Mechanisms of Enhanced Phrenic Long-Term Facilitation in SOD1G93A Rats.

    Science.gov (United States)

    Nichols, Nicole L; Satriotomo, Irawan; Allen, Latoya L; Grebe, Ashley M; Mitchell, Gordon S

    2017-06-14

    Amyotrophic lateral sclerosis (ALS) is a degenerative motor neuron disease, causing muscle paralysis and death from respiratory failure. Effective means to preserve/restore ventilation are necessary to increase the quality and duration of life in ALS patients. At disease end-stage in a rat ALS model ( SOD1 G93A ), acute intermittent hypoxia (AIH) restores phrenic nerve activity to normal levels via enhanced phrenic long-term facilitation (pLTF). Mechanisms enhancing pLTF in end-stage SOD1 G93A rats are not known. Moderate AIH-induced pLTF is normally elicited via cellular mechanisms that require the following: G q -protein-coupled 5-HT 2 receptor activation, new BDNF synthesis, and MEK/ERK signaling (the Q pathway). In contrast, severe AIH elicits pLTF via a distinct mechanism that requires the following: G s -protein-coupled adenosine 2A receptor activation, new TrkB synthesis, and PI3K/Akt signaling (the S pathway). In end-stage male S OD1 G93A rats and wild-type littermates, we investigated relative Q versus S pathway contributions to enhanced pLTF via intrathecal (C4) delivery of small interfering RNAs targeting BDNF or TrkB mRNA, and MEK/ERK (U0126) or PI3 kinase/Akt (PI828) inhibitors. In anesthetized, paralyzed and ventilated rats, moderate AIH-induced pLTF was abolished by siBDNF and UO126, but not siTrkB or PI828, demonstrating that enhanced pLTF occurs via the Q pathway. Although phrenic motor neuron numbers were decreased in end-stage SOD1 G93A rats (∼30% survival; p phrenic motor neurons ( p phrenic motor plasticity results from amplification of normal cellular mechanisms versus addition/substitution of alternative mechanisms. Greater understanding of mechanisms underlying phrenic motor plasticity in ALS may guide development of new therapies to preserve and/or restore breathing in ALS patients. Copyright © 2017 the authors 0270-6474/17/375834-12$15.00/0.

  3. Advanced age-related denervation and fiber-type grouping in skeletal muscle of SOD1 knockout mice.

    Science.gov (United States)

    Kostrominova, Tatiana Y

    2010-11-30

    In this study skeletal muscles from 1.5- and 10-month-old Cu/Zn superoxide dismutase (SOD1) homozygous knockout (JLSod1(-/-)) mice obtained from The Jackson Laboratory (C57Bl6/129SvEv background) were compared with muscles from age- and sex-matched heterozygous (JLSod1(+/-)) littermates. The results of this study were compared with previously published data on two different strains of Sod1(-/-) mice: one from Dr. Epstein's laboratory (ELSod1(-/-); C57Bl6 background) and the other from Cephalon, Inc. (CSod1(-/-); 129/CD-1 background). Grouping of succinate dehydrogenase-positive fibers characterized muscles of Sod1(-/-) mice from all three strains. The 10-month-old Sod1(-/-)C and JL mice displayed pronounced denervation of the gastrocnemius muscle, whereas the ELSod1(-/-) mice displayed a small degree of denervation at this age, but developed accelerated age-related denervation later on. Denervation markers were up-regulated in skeletal muscle of 10-month-old JLSod1(-/-) mice. This study is the first to show that metallothionein mRNA and protein expression was up-regulated in the skeletal muscle of 10-month-old JLSod1(-/-) mice and was mostly localized to the small atrophic muscle fibers. In conclusion, all three strains of Sod1(-/-) mice develop accelerated age-related muscle denervation, but the genetic background has significant influence on the progress of denervation. Copyright © 2010 Elsevier Inc. All rights reserved.

  4. Radio-sensitivity of the cells from amyotrophic lateral sclerosis model mice transfected with human mutant SOD1

    International Nuclear Information System (INIS)

    Wate, Reika; Ito, Hidefumi; Kusaka, Hirofumi; Takahashi, Sentaro; Kubota, Yoshihisa; Suetomi, Katsutoshi; Sato, Hiroshi; Okayasu, Ryuichi

    2005-01-01

    In order to clarify the possible involvement of oxidative damage induced by ionizing radiation in the onset and/or progression of familial amyotrophic lateral sclerosis (ALS), we studied radio-sensitivity in primary cells derived from ALS model mice expressing human mutant Cu/Zn superoxide dismutase (SOD1). The primary mouse cells expressed both mouse and the mutant human SOD1. The cell survival of the transgenic mice (with mutant SOD1), determined by counting cell numbers at a scheduled time after X-irradiation, is very similar to that of cells from wild type animals. The induction and repair of DNA damage in the transgenic cells, measured by single cell gel electrophoresis and pulsed field gel electrophoresis, are also similar to those of wild type cells. These results indicate that the human mutant SOD1 gene does not seem to contribute to the alteration of radio-sensitivity, at least in the fibroblastic cells used here. Although it is necessary to consider the difference in cell types between fibroblastic and neuronal cells, the present results may suggest that ionizing radiation is not primarily responsible for the onset of familial ALS with the SOD1 mutation, and that the excess risks are probably not a concern for radiation diagnosis and therapy in familial ALS patients. (author)

  5. Overexpression of survival motor neuron improves neuromuscular function and motor neuron survival in mutant SOD1 mice.

    Science.gov (United States)

    Turner, Bradley J; Alfazema, Neza; Sheean, Rebecca K; Sleigh, James N; Davies, Kay E; Horne, Malcolm K; Talbot, Kevin

    2014-04-01

    Spinal muscular atrophy results from diminished levels of survival motor neuron (SMN) protein in spinal motor neurons. Low levels of SMN also occur in models of amyotrophic lateral sclerosis (ALS) caused by mutant superoxide dismutase 1 (SOD1) and genetic reduction of SMN levels exacerbates the phenotype of transgenic SOD1(G93A) mice. Here, we demonstrate that SMN protein is significantly reduced in the spinal cords of patients with sporadic ALS. To test the potential of SMN as a modifier of ALS, we overexpressed SMN in 2 different strains of SOD1(G93A) mice. Neuronal overexpression of SMN significantly preserved locomotor function, rescued motor neurons, and attenuated astrogliosis in spinal cords of SOD1(G93A) mice. Despite this, survival was not prolonged, most likely resulting from SMN mislocalization and depletion of gems in motor neurons of symptomatic mice. Our results reveal that SMN upregulation slows locomotor deficit onset and motor neuron loss in this mouse model of ALS. However, disruption of SMN nuclear complexes by high levels of mutant SOD1, even in the presence of SMN overexpression, might limit its survival promoting effects in this specific mouse model. Studies in emerging mouse models of ALS are therefore warranted to further explore the potential of SMN as a modifier of ALS. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. ALS-linked mutant SOD1 proteins promote Aβ aggregates in ALS through direct interaction with Aβ.

    Science.gov (United States)

    Jang, Ja-Young; Cho, Hyungmin; Park, Hye-Yoon; Rhim, Hyangshuk; Kang, Seongman

    2017-11-04

    Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease characterized by progressive degeneration of motor neurons. Aggregation of ALS-linked mutant Cu/Zn superoxide dismutase (SOD1) is a hallmark of a subset of familial ALS (fALS). Recently, intracellular amyloid-β (Aβ) is detected in motor neurons of both sporadic and familial ALS. We have previously shown that intracellular Aβ specifically interacts with G93A, an ALS-linked SOD1 mutant. However, little is known about the pathological and biological effect of this interaction in neurons. In this study, we have demonstrated that the Aβ-binding region is exposed on the SOD1 surface through the conformational changes due to misfolding of SOD1. Interestingly, we found that the intracellular aggregation of Aβ is enhanced through the direct interaction of Aβ with the Aβ-binding region exposed to misfolded SOD1. Ultimately, increased Aβ aggregation by this interaction promotes neuronal cell death. Consistent with this result, Aβ aggregates was three-fold higher in the brains of G93A transgenic mice than those of non Tg. Our study provides the first direct evidence that Aβ, an AD-linked factor, is associated to the pathogenesis of ALS and provides molecular clues to understand common aggregation mechanisms in the pathogenesis of neurodegenerative diseases. Furthermore, it will provide new insights into the development of therapeutic approaches for ALS. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Delayed Disease Onset and Extended Survival in the SOD1G93A Rat Model of Amyotrophic Lateral Sclerosis after Suppression of Mutant SOD1 in the Motor Cortex

    Science.gov (United States)

    Thomsen, Gretchen M.; Gowing, Genevieve; Latter, Jessica; Chen, Maximus; Vit, Jean-Philippe; Staggenborg, Kevin; Avalos, Pablo; Alkaslasi, Mor; Ferraiuolo, Laura; Likhite, Shibi; Kaspar, Brian K.

    2014-01-01

    Sporadic amyotrophic lateral sclerosis (ALS) is a fatal disease with unknown etiology, characterized by a progressive loss of motor neurons leading to paralysis and death typically within 3–5 years of onset. Recently, there has been remarkable progress in understanding inherited forms of ALS in which well defined mutations are known to cause the disease. Rodent models in which the superoxide dismutase-1 (SOD1) mutation is overexpressed recapitulate hallmark signs of ALS in patients. Early anatomical changes in mouse models of fALS are seen in the neuromuscular junctions (NMJs) and lower motor neurons, and selective reduction of toxic mutant SOD1 in the spinal cord and muscle of these models has beneficial effects. Therefore, much of ALS research has focused on spinal motor neuron and NMJ aspects of the disease. Here we show that, in the SOD1G93A rat model of ALS, spinal motor neuron loss occurs presymptomatically and before degeneration of ventral root axons and denervation of NMJs. Although overt cell death of corticospinal motor neurons does not occur until disease endpoint, we wanted to establish whether the upper motor neuron might still play a critical role in disease progression. Surprisingly, the knockdown of mutant SOD1 in only the motor cortex of presymptomatic SOD1G93A rats through targeted delivery of AAV9–SOD1–shRNA resulted in a significant delay of disease onset, expansion of lifespan, enhanced survival of spinal motor neurons, and maintenance of NMJs. This datum suggests an early dysfunction and thus an important role of the upper motor neuron in this animal model of ALS and perhaps patients with the disease. PMID:25411487

  8. TDP-43 or FUS-induced misfolded human wild-type SOD1 can propagate intercellularly in a prion-like fashion.

    Science.gov (United States)

    Pokrishevsky, Edward; Grad, Leslie I; Cashman, Neil R

    2016-03-01

    Amyotrophic lateral sclerosis (ALS), which appears to spread through the neuroaxis in a spatiotemporally restricted manner, is linked to heritable mutations in genes encoding SOD1, TDP-43, FUS, C9ORF72, or can occur sporadically without recognized genetic mutations. Misfolded human wild-type (HuWt) SOD1 has been detected in both familial and sporadic ALS patients, despite mutations in SOD1 accounting for only 2% of total cases. We previously showed that accumulation of pathological TDP-43 or FUS coexist with misfolded HuWtSOD1 in patient motor neurons, and can trigger its misfolding in cultured cells. Here, we used immunocytochemistry and immunoprecipitation to demonstrate that TDP-43 or FUS-induced misfolded HuWtSOD1 can propagate from cell-to-cell via conditioned media, and seed cytotoxic misfolding of endogenous HuWtSOD1 in the recipient cells in a prion-like fashion. Knockdown of SOD1 using siRNA in recipient cells, or incubation of conditioned media with misfolded SOD1-specific antibodies, inhibits intercellular transmission, indicating that HuWtSOD1 is an obligate seed and substrate of propagated misfolding. In this system, intercellular spread of SOD1 misfolding is not accompanied by transmission of TDP-43 or FUS pathology. Our findings argue that pathological TDP-43 and FUS may exert motor neuron pathology in ALS through the initiation of propagated misfolding of SOD1.

  9. Differential survival among sSOD-1* genotypes in Chinook Salmon

    Science.gov (United States)

    Hayes, Michael C.; Reisenbichler, Reginald R.; Rubin, Stephen P.; Wetzel, Lisa A.; Marshall , Anne R.

    2011-01-01

    Differential survival and growth were tested in Chinook salmon Oncorhynchus tshawytscha expressing two common alleles, *–100 and *–260, at the superoxide dismutase locus (sSOD-1*). These tests were necessary to support separate studies in which the two alleles were used as genetic marks under the assumption of mark neutrality. Heterozygous adults were used to produce progeny with –100/–100, –100/–260, and –260/–260 genotypes that were reared in two natural streams and two hatcheries in the states of Washington and Oregon. The latter also were evaluated as returning adults. In general, the genotype ratios of juveniles reared at hatcheries were consistent with high survival and little or no differential survival in the hatchery. Adult returns at one hatchery were significantly different from the expected proportions, and the survival of the –260/–260 genotype was 0.56–0.89 times that of the –100/–100 genotype over four year-classes. Adult returns at a second hatchery (one year-class) were similar but not statistically significant: survival of the –260/–260genotype relative to the –100/–100 genotype was 0.76. The performance of the heterozygote group was intermediate at both hatcheries. Significant differences in growth were rarely observed among hatchery fish (one year-class of juveniles and one age-class of adult males) but were consistent with greater performance for the –100/–100 genotype. Results from two groups of juveniles reared in streams (one year-class from each stream) suggested few differences in growth, but the observed genotype ratios were significantly different from the expected ratios in one stream. Those differences were consistent with the adult data; survival for the –260/–260 genotype was 76% of that of the –100/–100 genotype. These results, which indicate nonneutrality among sSOD-1* genotypes, caused us to modify our related studies and suggest caution in the interpretation of results and analyses in

  10. Improving the Delivery of SOD1 Antisense Oligonucleotides to Motor Neurons Using Calcium Phosphate-Lipid Nanoparticles

    Directory of Open Access Journals (Sweden)

    Liyu Chen

    2017-08-01

    Full Text Available Amyotrophic Lateral Sclerosis (ALS is a fatal neurodegenerative disease affecting the upper and lower motor neurons in the motor cortex and spinal cord. Abnormal accumulation of mutant superoxide dismutase I (SOD1 in motor neurons is a pathological hallmark of some forms of the disease. We have shown that the orderly progression of the disease may be explained by misfolded SOD1 cell-to-cell propagation, which is reliant upon its active endogenous synthesis. Reducing the levels of SOD1 is therefore a promising therapeutic approach. Antisense oligonucleotides (ASOs can efficiently silence proteins with gain-of-function mutations. However, naked ASOs have a short circulation half-life and are unable to cross the blood brain barrier (BBB warranting the use of a drug carrier for effective delivery. In this study, calcium phosphate lipid coated nanoparticles (CaP-lipid NPs were developed for delivery of SOD1 ASO to motor neurons. The most promising nanoparticle formulation (Ca/P ratio of 100:1, had a uniform spherical core–shell morphology with an average size of 30 nm, and surface charge (ζ-potential of −4.86 mV. The encapsulation efficiency of ASO was 48% and stability studies found the particle to be stable over a period of 20 days. In vitro experiments demonstrated that the negatively charged ASO-loaded CaP-lipid NPs could effectively deliver SOD1-targeted ASO into a mouse motor neuron-like cell line (NSC-34 through endocytosis and significantly down-regulated SOD1 expression in HEK293 cells. The CaP-lipid NPs exhibited a pH-dependant dissociation, suggesting that that the acidification of lysosomes is the likely mechanism responsible for facilitating intracellular ASO release. To demonstrate tissue specific delivery and localization of these NPs we performed in vivo microinjections into zebrafish. Successful delivery of these NPs was confirmed for the zebrafish brain, the blood stream, and the spinal cord. These results suggest that Ca

  11. Higher levels of serum fibrin-monomer reflect hypercoagulable state and thrombus formation in the left atrial appendage in patients with acute ischemic stroke.

    Science.gov (United States)

    Okuyama, Hidenobu; Hirono, Osamu; Liu, Ling; Takeishi, Yasuchika; Kayama, Takamasa; Kubota, Isao

    2006-08-01

    It is sometimes difficult to make a diagnosis of cardioembolic stroke in the stroke care unit, because of the splashing and vanishing of the intracardiac source of the emboli on transesophageal echocardiography. Serum fibrin-monomer (FM) is a new marker for coagulation activity that is useful for identifying older individuals at increased risk of ischemic stroke. Two hundred and four patients with acute ischemic stroke were examined for serum coagulation and fibrinolytic activity on admission, and underwent transesophageal echocardiography within 7 days of onset. Serum levels of FM was significantly higher in patients with left atrial appendage (LAA) thrombus formation (n=24) than in those with no thrombus (88+/-52 vs 14+/-9 microg/ml, pvs 8+/-5 microg/ml, pstroke.

  12. Muscle Expression of SOD1G93A Triggers the Dismantlement of Neuromuscular Junction via PKC-Theta.

    Science.gov (United States)

    Dobrowolny, Gabriella; Martini, Martina; Scicchitano, Bianca Maria; Romanello, Vanina; Boncompagni, Simona; Nicoletti, Carmine; Pietrangelo, Laura; De Panfilis, Simone; Catizone, Angela; Bouchè, Marina; Sandri, Marco; Rudolf, Rüdiger; Protasi, Feliciano; Musarò, Antonio

    2018-04-20

    Neuromuscular junction (NMJ) represents the morphofunctional interface between muscle and nerve. Several chronic pathologies such as aging and neurodegenerative diseases, including muscular dystrophy and amyotrophic lateral sclerosis, display altered NMJ and functional denervation. However, the triggers and the molecular mechanisms underlying the dismantlement of NMJ remain unclear. Here we provide evidence that perturbation in redox signaling cascades, induced by muscle-specific accumulation of mutant SOD1 G93A in transgenic MLC/SOD1 G93A mice, is causally linked to morphological alterations of the neuromuscular presynaptic terminals, high turnover rate of acetylcholine receptor, and NMJ dismantlement. The analysis of potential molecular mechanisms that mediate the toxic activity of SOD1 G93A revealed a causal link between protein kinase Cθ (PKCθ) activation and NMJ disintegration. The study discloses the molecular mechanism that triggers functional denervation associated with the toxic activity of muscle SOD1 G93A expression and suggests the possibility of developing a new strategy to counteract age- and pathology-associated denervation based on pharmacological inhibition of PKCθ activity. Collectively, these data indicate that muscle-specific accumulation of oxidative damage can affect neuromuscular communication and induce NMJ dismantlement through a PKCθ-dependent mechanism. Antioxid. Redox Signal. 28, 1105-1119.

  13. An ALS-Associated Mutant SOD1 Rapidly Suppresses KCNT1 (Slack) Na+-Activated K+ Channels in Aplysia Neurons.

    Science.gov (United States)

    Zhang, Yalan; Ni, Weiming; Horwich, Arthur L; Kaczmarek, Leonard K

    2017-02-22

    Mutations that alter levels of Slack (KCNT1) Na + -activated K + current produce devastating effects on neuronal development and neuronal function. We now find that Slack currents are rapidly suppressed by oligomers of mutant human Cu/Zn superoxide dismutase 1 (SOD1), which are associated with motor neuron toxicity in an inherited form of amyotrophic lateral sclerosis (ALS). We recorded from bag cell neurons of Aplysia californica , a model system to study neuronal excitability. We found that injection of fluorescent wild-type SOD1 (wt SOD1YFP) or monomeric mutant G85R SOD1YFP had no effect on net ionic currents measured under voltage clamp. In contrast, outward potassium currents were significantly reduced by microinjection of mutant G85R SOD1YFP that had been preincubated at 37°C or of cross-linked dimers of G85R SOD1YFP. Reduction of potassium current was also seen with multimeric G85R SOD1YFP of ∼300 kDa or >300 kDa that had been cross-linked. In current clamp recordings, microinjection of cross-linked 300 kDa increased excitability by depolarizing the resting membrane potential, and decreasing the latency of action potentials triggered by depolarization. The effect of cross-linked 300 kDa on potassium current was reduced by removing Na + from the bath solution, or by knocking down levels of Slack using siRNA. It was also prevented by pharmacological inhibition of ASK1 (apoptosis signal-regulating kinase 1) or of c-Jun N-terminal kinase, but not by an inhibitor of p38 mitogen-activated protein kinase. These results suggest that soluble mutant SOD1 oligomers rapidly trigger a kinase pathway that regulates the activity of Na + -activated K + channels in neurons. SIGNIFICANCE STATEMENT Slack Na + -activated K + channels (KCNT1, K Na 1.1) regulate neuronal excitability but are also linked to cytoplasmic signaling pathways that control neuronal protein translation. Mutations that alter the amplitude of these currents have devastating effects on neuronal

  14. The effect of amyotrophic lateral sclerosis-linked exogenous SOD1-G93A on electrophysiological properties and intracellular calcium in cultured rat astrocytes.

    Science.gov (United States)

    Milošević, Milena; Bataveljić, Danijela; Nikolić, Ljiljana; Bijelić, Dunja; Andjus, Pavle

    2016-01-01

    Over 150 mutations in the SOD1 gene that encodes Cu/Zn superoxide dismutase (SOD1) cause 20-25% of familial ALS, albeit without a known gain-of-function mechanism. ALS is also non-cell-autonomous, the interactions between motor neurons and their glial neighbours being implicated in disease progression. The aim here was to investigate the biophysical effects of the exogenous human mutant SOD1-G93A on rat astrocytes in culture. Primary cortical astrocyte cultures were treated with recombinant human apo- mSOD1-G93A vs. wild-type control (wtSOD1) and recorded by patch-clamp and calcium imaging. Results showed that exogenous mSOD1 as well as wtSOD1 induced a decrease of membrane resistance, the effect being persistent (up to 13 min) only for the mutant form. Similarly, whole-cell inward currents in astrocytes were augmented by both wt and mSOD1, but the effect was twice larger and only progressed continuously for the latter. Both forms of SOD1 also induced a rise in intracellular Ca(2+) activity, the effect being dependent on external Ca(2+) and again only persisted with mSOD1, becoming significantly different from wtSOD1 only at longer times (14 min). In conclusion, this study points to membrane permeability and Ca(2+) signalling as processes affected by SOD1-G93A that presents the humoral factor triggering the role of astrocytes in ALS pathophysiology.

  15. Core sequence of PAPf39 amyloid fibrils and mechanism of pH-dependent fibril formation: the role of monomer conformation.

    Science.gov (United States)

    French, Kinsley C; Makhatadze, George I

    2012-12-21

    PAPf39, a 39-residue peptide fragment from human prostatic acidic phosphatase, has been shown to form amyloid fibrils in semen (SEVI), which increase HIV infectivity by up to 5 orders of magnitude. The sequence of the PAPf39 fibrillar core was identified using hydrogen-deuterium exchange (HDX) mass spectrometry and protease protection assays. The central and C-terminal regions are highly protected from HDX and proteolytic cleavage and, thus, are part of the fibrillar core. Conversely, the N-terminal region is unprotected from HDX and proteolytic cleavage, suggesting that it is exposed and not part of the fibrillar core. This finding was tested using two N-terminal truncated variants, PAPf39Δ1-8 and PAPf39Δ1-13. Both variants formed amyloid fibrils at neutral pH. However, these variants showed a markedly different pH dependence of fibril formation versus that of PAPf39. PAPf39 fibrils can form at pH 7.7, but not at pH 5.5 or 2.5, while both N-terminally truncated variants can form fibrils at these pH values. Thus, the N-terminal region is not necessary for fibril formation but modulates the pH dependence of PAPf39 fibril formation. PAPf39Δ1-8 and PAPf39Δ1-13 are capable of seeding PAPf39 fibril formation at neutral pH, suggesting that these variants are structurally compatible with PAPf39, yet no mixed fibril formation occurs between the truncated variants and PAPf39 at low pH. This suggests that pH affects the PAPf39 monomer conformational ensemble, which is supported by far-UV circular dichroism spectroscopy. A conceptual model describing the pH dependence of PAPf39 aggregation is proposed and provides potential biological implications.

  16. FUS-immunoreactive inclusions are a common feature in sporadic and non-SOD1 familial amyotrophic lateral sclerosis.

    Science.gov (United States)

    Deng, Han-Xiang; Zhai, Hong; Bigio, Eileen H; Yan, Jianhua; Fecto, Faisal; Ajroud, Kaouther; Mishra, Manjari; Ajroud-Driss, Senda; Heller, Scott; Sufit, Robert; Siddique, Nailah; Mugnaini, Enrico; Siddique, Teepu

    2010-06-01

    Amyotrophic lateral sclerosis (ALS) is a fatal disorder of motor neuron degeneration. Most cases of ALS are sporadic (SALS), but about 5 to 10% of ALS cases are familial (FALS). Recent studies have shown that mutations in FUS are causal in approximately 4 to 5% of FALS and some apparent SALS cases. The pathogenic mechanism of the mutant FUS-mediated ALS and potential roles of FUS in non-FUS ALS remain to be investigated. Immunostaining was performed on postmortem spinal cords from 78 ALS cases, including SALS (n = 52), ALS with dementia (ALS/dementia, n = 10), and FALS (n = 16). In addition, postmortem brains or spinal cords from 22 cases with or without frontotemporal lobar degeneration were also studied. In total, 100 cases were studied. FUS-immunoreactive inclusions were observed in spinal anterior horn neurons in all SALS and FALS cases, except for those with SOD1 mutations. The FUS-containing inclusions were also immunoreactive with antibodies to TDP43, p62, and ubiquitin. A fraction of tested FUS antibodies recognized FUS inclusions, and specific antigen retrieval protocol appeared to be important for detection of the skein-like FUS inclusions. Although mutations in FUS account for only a small fraction of FALS and SALS, our data suggest that FUS protein may be a common component of the cellular inclusions in non-SOD1 ALS and some other neurodegenerative conditions, implying a shared pathogenic pathway underlying SALS, non-SOD1 FALS, ALS/dementia, and related disorders. Our data also indicate that SOD1-linked ALS may have a pathogenic pathway distinct from SALS and other types of FALS.

  17. Step growth of two flexible ABf monomers

    DEFF Research Database (Denmark)

    Cameron, Colin; Fawcett, Allan H.; Hetherington, Cecil R.

    2000-01-01

    A three-dimensional lattice model was used to simulate the competition between the growth of hyperbranched structures and cycle formation that occurs when flexible ABf monomers undergo step growth. The monomers in the model are mapped onto several lattice sites. The effect of functionality...

  18. Analysis of Serum Cytokines and Single-Nucleotide Polymorphisms of SOD1, SOD2, and CAT in Erysipelas Patients

    Directory of Open Access Journals (Sweden)

    Charles C. Emene

    2017-01-01

    Full Text Available Increased free radical production had been documented in group A (β-hemolytic streptococcus infection cases. Comparing 71 erysipelas patients to 55 age-matched healthy individuals, we sought for CAT, SOD1, and SOD2 single polymorphism mutation (SNPs interactions with erysipelas’ predisposition and serum cytokine levels in the acute and recovery phases of erysipelas infection. Whereas female patients had a higher predisposition to erysipelas, male patients were prone to having a facial localization of the infection. The presence of SOD1 G7958, SOD2 T2734, and CAT C262 alleles was linked to erysipelas’ predisposition. T and C alleles of SOD2 T2734C individually were linked to patients with bullous and erythematous erysipelas, respectively. G and A alleles of SOD1 G7958A individually were associated with lower limbs and higher body part localizations of the infection, respectively. Serum levels of IL-1β, CCL11, IL-2Rα, CXCL9, TRAIL, PDGF-BB, and CCL4 were associated with symptoms accompanying the infection, while IL-6, IL-9, IL-10, IL-13, IL-15, IL-17, G-CSF, and VEGF were associated with predisposition and recurrence of erysipelas. While variations of IL-1β, IL-7, IL-8, IL-17, CCL5, and HGF were associated with the SOD2 T2734C SNP, variations of PDFG-BB and CCL2 were associated with the CAT C262T SNP.

  19. Measuring Neuromuscular Junction Functionality in the SOD1(G93A) Animal Model of Amyotrophic Lateral Sclerosis.

    Science.gov (United States)

    Rizzuto, Emanuele; Pisu, Simona; Musarò, Antonio; Del Prete, Zaccaria

    2015-09-01

    Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease that leads to motor neuron degeneration, alteration in neuromuscular junctions (NMJs), muscle atrophy, and paralysis. To investigate the NMJ functionality in ALS we tested, in vitro, two innervated muscle types excised from SOD1(G93A) transgenic mice at the end-stage of the disease: the Soleus, a postural muscle almost completely paralyzed at that stage, and the diaphragm, which, on the contrary, is functional until death. To this aim we employed an experimental protocol that combined two types of electrical stimulation: the direct stimulation and the stimulation through the nerve. The technique we applied allowed us to determine the relevance of NMJ functionality separately from muscle contractile properties in SOD1(G93A) animal model. Functional measurements revealed that the muscle contractility of transgenic diaphragms is almost unaltered in comparison to control muscles, while transgenic Soleus muscles were severely compromised. In contrast, when stimulated via the nerve, both transgenic muscle types showed a strong decrease of the contraction force, a slowing down of the kinetic parameters, as well as alterations in the neurotransmission failure parameter. All together, these results confirm a severely impaired functionality in the SOD1(G93A) neuromuscular junctions.

  20. Wildtype motoneurons, ALS-Linked SOD1 mutation and glutamate profoundly modify astrocyte metabolism and lactate shuttling.

    Science.gov (United States)

    Madji Hounoum, Blandine; Mavel, Sylvie; Coque, Emmanuelle; Patin, Franck; Vourc'h, Patrick; Marouillat, Sylviane; Nadal-Desbarats, Lydie; Emond, Patrick; Corcia, Philippe; Andres, Christian R; Raoul, Cédric; Blasco, Hélène

    2017-04-01

    The selective degeneration of motoneuron that typifies amyotrophic lateral sclerosis (ALS) implicates non-cell-autonomous effects of astrocytes. However, mechanisms underlying astrocyte-mediated neurotoxicity remain largely unknown. According to the determinant role of astrocyte metabolism in supporting neuronal function, we propose to explore the metabolic status of astrocytes exposed to ALS-associated conditions. We found a significant metabolic dysregulation including purine, pyrimidine, lysine, and glycerophospholipid metabolism pathways in astrocytes expressing an ALS-causing mutated superoxide dismutase-1 (SOD1) when co-cultured with motoneurons. SOD1 astrocytes exposed to glutamate revealed a significant modification of the astrocyte metabolic fingerprint. More importantly, we observed that SOD1 mutation and glutamate impact the cellular shuttling of lactate between astrocytes and motoneurons with a decreased in extra- and intra-cellular lactate levels in astrocytes. Based on the emergent strategy of metabolomics, this work provides novel insight for understanding metabolic dysfunction of astrocytes in ALS conditions and opens the perspective of therapeutics targets through focusing on these metabolic pathways. GLIA 2017 GLIA 2017;65:592-605. © 2017 Wiley Periodicals, Inc.

  1. A 50 bp deletion in the SOD1 promoter lowers enzyme expression but is not associated with ALS in Sweden.

    Science.gov (United States)

    Ingre, Caroline; Wuolikainen, Anna; Marklund, Stefan L; Birve, Anna; Press, Rayomand; Andersen, Peter M

    2016-01-01

    Mutations in the superoxide dismutase (SOD1) gene have been linked to amyotrophic lateral sclerosis (ALS). A 50 base pair (bp) deletion of SOD1 has been suggested to reduce transcription and to be associated with later disease onset in ALS. This study was aimed to reveal if the 50 bp deletion influenced SOD1 enzymatic activity, occurrence and phenotype of the disease in a Swedish ALS/control cohort. Blood samples from 512 Swedish ALS patients and 354 Swedish controls without coding SOD1 mutations were analysed for the 50 bp deletion allele. The enzymatic activity of SOD1 in erythrocytes was analysed and genotype-phenotype correlations were assessed. Results demonstrated that the genotype frequencies of the 50 bp deletion were all found to be in Hardy-Weinberg equilibrium. No significant differences were found for age of onset, disease duration or site of onset. SOD1 enzymatic activity showed a statistically significant decreasing trend in the control group, in which the allele was associated with a 5% reduction in SOD1 activity. The results suggest that the 50 bp deletion has a moderate reducing effect on SOD1 synthesis. No modulating effects, however, were found on ALS onset, phenotype and survival in the Swedish population.

  2. Fisetin Exerts Antioxidant and Neuroprotective Effects in Multiple Mutant hSOD1 Models of Amyotrophic Lateral Sclerosis by Activating ERK.

    Science.gov (United States)

    Wang, T H; Wang, S Y; Wang, X D; Jiang, H Q; Yang, Y Q; Wang, Y; Cheng, J L; Zhang, C T; Liang, W W; Feng, H L

    2018-05-21

    Oxidative stress exhibits a central role in the course of amyotrophic lateral sclerosis (ALS), a progressive neurodegenerative disease commonly found to include a copper/zinc superoxide dismutase (SOD1) gene mutation. Fisetin, a natural antioxidant, has shown benefits in varied neurodegenerative diseases. The possible effect of fisetin in ALS has not been clarified as of yet. We investigated whether fisetin affected mutant hSOD1 ALS models. Three different hSOD1-related mutant models were used: Drosophila expressing mutant hSOD1 G85R , hSOD1 G93A NSC34 cells, and transgenic mice. Fisetin treatment provided neuroprotection as demonstrated by an improved survival rate, attenuated motor impairment, reduced ROS damage and regulated redox homeostasis compared with those in controls. Furthermore, fisetin increased the expression of phosphorylated ERK and upregulated antioxidant factors, which were reversed by MEK/ERK inhibition. Finally, fisetin reduced the levels of both mutant and wild-type hSOD1 in vivo and in vitro, as well as the levels of detergent-insoluble hSOD1 proteins. The results indicate that fisetin protects cells from ROS damage and improves the pathological behaviors caused by oxidative stress in disease models related to SOD1 gene mutations probably by activating ERK, thereby providing a potential treatment for ALS. Copyright © 2018 IBRO. Published by Elsevier Ltd. All rights reserved.

  3. In-vivo effects of knocking-down metabotropic glutamate receptor 5 in the SOD1G93A mouse model of amyotrophic lateral sclerosis.

    Science.gov (United States)

    Bonifacino, Tiziana; Cattaneo, Luca; Gallia, Elena; Puliti, Aldamaria; Melone, Marcello; Provenzano, Francesca; Bossi, Simone; Musante, Ilaria; Usai, Cesare; Conti, Fiorenzo; Bonanno, Giambattista; Milanese, Marco

    2017-09-01

    Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disorder due to loss of upper and lower motor neurons (MNs). The mechanisms of neuronal death are largely unknown, thus prejudicing the successful pharmacological treatment. One major cause for MN degeneration in ALS is represented by glutamate(Glu)-mediated excitotoxicity. We have previously reported that activation of Group I metabotropic Glu receptors (mGluR1 and mGluR5) at glutamatergic spinal cord nerve terminals produces abnormal Glu release in the widely studied SOD1 G93A mouse model of ALS. We also demonstrated that halving mGluR1 expression in the SOD1 G93A mouse had a positive impact on survival, disease onset, disease progression, and on a number of cellular and biochemical readouts of ALS. We generated here SOD1 G93A mice with reduced expression of mGluR5 (SOD1 G93A Grm5 -/+ ) by crossing the SOD1 G93A mutant mouse with the mGluR5 heterozigous Grm5 -/+ mouse. SOD1 G93A Grm5 -/+ mice showed prolonged survival probability and delayed pathology onset. These effects were associated to enhanced number of preserved MNs, decreased astrocyte and microglia activation, reduced cytosolic free Ca 2+ concentration, and regularization of abnormal Glu release in the spinal cord of SOD1 G93A Grm5 -/+ mice. Unexpectedly, only male SOD1 G93A Grm5 -/+ mice showed improved motor skills during disease progression vs. SOD1 G93A mice, while SOD1 G93A Grm5 -/+ females did not. These results demonstrate that a lower constitutive level of mGluR5 has a significant positive impact in mice with ALS and support the idea that blocking Group I mGluRs may represent a potentially effective pharmacological approach to the disease. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Oral treatment with Cu(II)(atsm) increases mutant SOD1 in vivo but protects motor neurons and improves the phenotype of a transgenic mouse model of amyotrophic lateral sclerosis.

    Science.gov (United States)

    Roberts, Blaine R; Lim, Nastasia K H; McAllum, Erin J; Donnelly, Paul S; Hare, Dominic J; Doble, Philip A; Turner, Bradley J; Price, Katherine A; Lim, Sin Chun; Paterson, Brett M; Hickey, James L; Rhoads, Timothy W; Williams, Jared R; Kanninen, Katja M; Hung, Lin W; Liddell, Jeffrey R; Grubman, Alexandra; Monty, Jean-Francois; Llanos, Roxana M; Kramer, David R; Mercer, Julian F B; Bush, Ashley I; Masters, Colin L; Duce, James A; Li, Qiao-Xin; Beckman, Joseph S; Barnham, Kevin J; White, Anthony R; Crouch, Peter J

    2014-06-04

    Mutations in the metallo-protein Cu/Zn-superoxide dismutase (SOD1) cause amyotrophic lateral sclerosis (ALS) in humans and an expression level-dependent phenotype in transgenic rodents. We show that oral treatment with the therapeutic agent diacetyl-bis(4-methylthiosemicarbazonato)copper(II) [Cu(II)(atsm)] increased the concentration of mutant SOD1 (SOD1G37R) in ALS model mice, but paradoxically improved locomotor function and survival of the mice. To determine why the mice with increased levels of mutant SOD1 had an improved phenotype, we analyzed tissues by mass spectrometry. These analyses revealed most SOD1 in the spinal cord tissue of the SOD1G37R mice was Cu deficient. Treating with Cu(II)(atsm) decreased the pool of Cu-deficient SOD1 and increased the pool of fully metallated (holo) SOD1. Tracking isotopically enriched (65)Cu(II)(atsm) confirmed the increase in holo-SOD1 involved transfer of Cu from Cu(II)(atsm) to SOD1, suggesting the improved locomotor function and survival of the Cu(II)(atsm)-treated SOD1G37R mice involved, at least in part, the ability of the compound to improve the Cu content of the mutant SOD1. This was supported by improved survival of SOD1G37R mice that expressed the human gene for the Cu uptake protein CTR1. Improving the metal content of mutant SOD1 in vivo with Cu(II)(atsm) did not decrease levels of misfolded SOD1. These outcomes indicate the metal content of SOD1 may be a greater determinant of the toxicity of the protein in mutant SOD1-associated forms of ALS than the mutations themselves. Improving the metal content of SOD1 therefore represents a valid therapeutic strategy for treating ALS caused by SOD1. Copyright © 2014 the authors 0270-6474/14/348021-11$15.00/0.

  5. Un-catalyzed peptide bond formation between two monomers of glycine, alanine, serine, threonine, and aspartic acid in gas phase: a density functional theory study

    Science.gov (United States)

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K.

    2016-05-01

    In the present report, un-catalyzed peptide bond formation between two monomers of glycine (Gly), alanine (Ala), serine (Ser), threonine (Thr), and aspartic acid (Asp) has been investigated in gas phase via two steps reaction mechanism and concerted mechanism at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. The peptide bond is formed through a nucleophilic reaction via transition states, TS1 and TS2 in stepwise mechanism. The TS1 reveals formation of a new C-N bond while TS2 illustrate the formation of C=O bond. In case of concerted mechanism, C-N bond is formed by a single four-centre transition state (TS3). The energy barrier is used to explain the involvement of energy at each step of the reaction. The energy barrier (20-48 kcal/mol) is required for the transformation of reactant state R1 to TS1 state and intermediate state I1 to TS2 state. The large value of energy barrier is explained in terms of distortion and interaction energies for stepwise mechanism. The energy barrier of TS3 in concerted mechanism is very close to the energy barrier of the first transition state (TS1) of the stepwise mechanism for the formation of Gly-Gly and Ala-Ala di- peptide. However, in case of Ser-Ser, Thr-Thr and Asp-Asp di-peptide, the energy barrier of TS3 is relatively high than that of the energy barrier of TS1 calculated at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. In both the mechanisms, the value of energy barrier calculated at B3LYP/6-31G(d,p) level of theory is greater than that of the value calculated at M062X/6-31G(d,p) level of theory.

  6. Comparison of dendritic calcium transients in juvenile wild type and SOD1G93A mouse lumbar motoneurons

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    Katharina Ann Quinlan

    2015-04-01

    Full Text Available Previous studies of spinal motoneurons in the SOD1 mouse model of amyotrophic lateral sclerosis have shown alterations long before disease onset, including increased dendritic branching, increased persistent Na+ and Ca2+ currents, and impaired axonal transport. In this study dendritic Ca2+ entry was investigated using 2 photon excitation fluorescence microscopy and whole-cell patch-clamp of juvenile (P4-11 motoneurons. Neurons were filled with both Ca2+ Green-1 and Texas Red dextrans, and line scans performed throughout. Steps were taken to account for different sources of variability, including 1 dye filling and laser penetration, 2 dendritic anatomy, and 3 the time elapsed from the start of recording. First, Ca2+ Green-1 fluorescence was normalized by Texas Red; next, neurons were reconstructed so anatomy could be evaluated; finally, time was recorded. Customized software detected the largest Ca2+ transients (area under the curve from each line scan and matched it with parameters above. Overall, larger dendritic diameter and shorter path distance from the soma were significant predictors of larger transients, while time was not significant up to 2 hours (data thereafter was dropped. However, Ca2+ transients showed additional variability. Controlling for previous factors, significant variation was found between Ca2+ signals from different processes of the same neuron in 3/7 neurons. This could reflect differential expression of Ca2+ channels, local neuromodulation or other variations. Finally, Ca2+ transients in SOD1G93A motoneurons were significantly smaller than in non-transgenic motoneurons. In conclusion, motoneuron processes show highly variable Ca2+ transients, but these transients are smaller overall SOD1G93A motoneurons.

  7. Seeking homeostasis: Temporal trends in respiration, oxidation, and calcium in SOD1 G93A Amyotrophic Lateral Sclerosis mice

    Directory of Open Access Journals (Sweden)

    Cameron W Irvin

    2015-07-01

    Full Text Available Impairments in mitochondria, oxidative regulation, and calcium homeostasis have been well documented in numerous amyotrophic lateral sclerosis (ALS experimental models, especially in the superoxide dismutase 1 glycine 93 to alanine (SOD1 G93A transgenic mouse. However, the timing of these deficiencies has been debatable. In a systematic review of 45 articles, we examine experimental measurements of cellular respiration, mitochondrial mechanisms, oxidative markers, and calcium regulation. We evaluate the quantitative magnitude and statistical temporal trend of these aggregated assessments in high transgene copy SOD1 G93A mice compared to wild type mice. Analysis of overall trends reveals cellular respiration, intracellular ATP, and corresponding mitochondrial elements (Cox, cytochrome c, complex I, enzyme activity are depressed for the entire lifespan of the SOD1 G93A mouse. Oxidant markers (H2O2, 8OH2’dG, MDA are initially similar to wild type but are double that of wild type by the time of symptom onset despite early post-natal elevation of protective heat shock proteins. All aspects of calcium regulation show early disturbances, although a notable and likely compensatory convergence to near wild type levels appears to occur between 40-80 days (pre-onset, followed by a post-onset elevation in intracellular calcium. The identified temporal trends and compensatory fluctuations provide evidence that the cause of ALS may lay within failed homeostatic regulation, itself, rather than any one particular perturbing event or cellular mechanism. We discuss the vulnerabilities of motoneurons to regulatory instability and possible hypotheses regarding failed regulation and its potential treatment in ALS.

  8. PGC-1 silencing compounds the perturbation of mitochondrial function caused by mutant SOD1 in skeletal muscle of ALS mouse model

    Directory of Open Access Journals (Sweden)

    Yan eQi

    2015-10-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is a lethal neurodegenerative disease causing death of motor neurons. This study investigated the roles of energy metabolism in the pathogenesis of ALS in the SOD1(G93A transgenic mouse model. Control and SOD1(G93A mice were administered with shcontrol or shPGC-1α in combination with PBS or TZD for 8 weeks. Gene expression was analyzed by quantitative real-time PCR and western blot. ROS and fibrosis were assessed with a colorimetric kit and Sirius staining respectively. Inflammatory cytokines were measured using ELISA kits. The levels of tissue ROS and serum inflammatory cytokines were significantly higher in SOD1(G93A mice compared to control mice, and knocking down PGC-1α drastically increased cytokine levels in both control and SOD1(G93A mice. Muscle fibrosis was much severer in SOD1(G93A mice, and worsened by silencing PGC-1α and attenuate d by TZD. The expression levels of PGC-1α, SOD1, UCP2, and cytochrome C were substantially reduced by shPGC-1α and increased by TZD in muscle of both control and SOD1(G93A mice whereas the level of NF-B was significantly elevated in SOD1(G93A mice, which was further increased by PGC-1α silencing. These data indicated that disruption of energy homeostasis would exacerbate the pathological changes caused by SOD1 mutations to promote the pathogenesis of ALS.

  9. Human SOD1 ALS Mutations in a Drosophila Knock-In Model Cause Severe Phenotypes and Reveal Dosage-Sensitive Gain- and Loss-of-Function Components.

    Science.gov (United States)

    Şahin, Aslı; Held, Aaron; Bredvik, Kirsten; Major, Paxton; Achilli, Toni-Marie; Kerson, Abigail G; Wharton, Kristi; Stilwell, Geoff; Reenan, Robert

    2017-02-01

    Amyotrophic Lateral Sclerosis (ALS) is the most common adult-onset motor neuron disease and familial forms can be caused by numerous dominant mutations of the copper-zinc superoxide dismutase 1 (SOD1) gene. Substantial efforts have been invested in studying SOD1-ALS transgenic animal models; yet, the molecular mechanisms by which ALS-mutant SOD1 protein acquires toxicity are not well understood. ALS-like phenotypes in animal models are highly dependent on transgene dosage. Thus, issues of whether the ALS-like phenotypes of these models stem from overexpression of mutant alleles or from aspects of the SOD1 mutation itself are not easily deconvolved. To address concerns about levels of mutant SOD1 in disease pathogenesis, we have genetically engineered four human ALS-causing SOD1 point mutations (G37R, H48R, H71Y, and G85R) into the endogenous locus of Drosophila SOD1 (dsod) via ends-out homologous recombination and analyzed the resulting molecular, biochemical, and behavioral phenotypes. Contrary to previous transgenic models, we have recapitulated ALS-like phenotypes without overexpression of the mutant protein. Drosophila carrying homozygous mutations rendering SOD1 protein enzymatically inactive (G85R, H48R, and H71Y) exhibited neurodegeneration, locomotor deficits, and shortened life span. The mutation retaining enzymatic activity (G37R) was phenotypically indistinguishable from controls. While the observed mutant dsod phenotypes were recessive, a gain-of-function component was uncovered through dosage studies and comparisons with age-matched dsod null animals, which failed to show severe locomotor defects or nerve degeneration. We conclude that the Drosophila knock-in model captures important aspects of human SOD1-based ALS and provides a powerful and useful tool for further genetic studies. Copyright © 2017 by the Genetics Society of America.

  10. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation

    Science.gov (United States)

    Li, Hongliang; Wang, Liangbing; Dai, Yizhou; Pu, Zhengtian; Lao, Zhuohan; Chen, Yawei; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Si, Rui; Ma, Chao; Zeng, Jie

    2018-05-01

    Exploring the interaction between two neighbouring monomers has great potential to significantly raise the performance and deepen the mechanistic understanding of heterogeneous catalysis. Herein, we demonstrate that the synergetic interaction between neighbouring Pt monomers on MoS2 greatly enhanced the CO2 hydrogenation catalytic activity and reduced the activation energy relative to isolated monomers. Neighbouring Pt monomers were achieved by increasing the Pt mass loading up to 7.5% while maintaining the atomic dispersion of Pt. Mechanistic studies reveal that neighbouring Pt monomers not only worked in synergy to vary the reaction barrier, but also underwent distinct reaction paths compared with isolated monomers. Isolated Pt monomers favour the conversion of CO2 into methanol without the formation of formic acid, whereas CO2 is hydrogenated stepwise into formic acid and methanol for neighbouring Pt monomers. The discovery of the synergetic interaction between neighbouring monomers may create a new path for manipulating catalytic properties.

  11. A botanical containing freeze dried açai pulp promotes healthy aging and reduces oxidative damage in sod1 knockdown flies

    OpenAIRE

    Laslo, Mara; Sun, Xiaoping; Hsiao, Cheng-Te; Wu, Wells W.; Shen, Rong-Fong; Zou, Sige

    2012-01-01

    Superoxide dismutase 1 (SOD1), a critical enzyme against oxidative stress, is implicated in aging and degenerative diseases. We previously showed that a nutraceutical containing freeze-dried açai pulp promotes survival of flies fed a high-fat diet or sod1 knockdown flies fed a standard diet. Here, we investigated the effect of açai supplementation initiated at the early or late young adulthood on lifespan, physiological function, and oxidative damage in sod1 knockdown flies. We found that Aça...

  12. Differential Motor Neuron Impairment and Axonal Regeneration in Sporadic and Familiar Amyotrophic Lateral Sclerosis with SOD-1 Mutations: Lessons from Neurophysiology

    OpenAIRE

    Bocci, Tommaso; Pecori, Chiara; Giorli, Elisa; Briscese, Lucia; Tognazzi, Silvia; Caleo, Matteo; Sartucci, Ferdinando

    2011-01-01

    Amyotrophic Lateral Sclerosis (ALS) is a degenerative disorder of the motor system. About 10% of cases are familial and 20% of these families have point mutations in the Cu/Zn superoxide dismutase 1 (SOD-1) gene. SOD-1 catalyses the superoxide radical (O−2) into hydrogen peroxide and molecular oxygen. The clinical neurophysiology in ALS plays a fundamental role in differential diagnosis between the familial and sporadic forms and in the assessment of its severity and progression. Sixty ALS pa...

  13. Tempol moderately extends survival in a hSOD1(G93A ALS rat model by inhibiting neuronal cell loss, oxidative damage and levels of non-native hSOD1(G93A forms.

    Directory of Open Access Journals (Sweden)

    Edlaine Linares

    Full Text Available Amyotrophic lateral sclerosis (ALS is a fatal neurodegenerative disease characterized by the progressive dysfunction and death of motor neurons by mechanisms that remain unclear. Evidence indicates that oxidative mechanisms contribute to ALS pathology, but classical antioxidants have not performed well in clinical trials. Cyclic nitroxides are an alternative worth exploring because they are multifunctional antioxidants that display low toxicity in vivo. Here, we examine the effects of the cyclic nitroxide tempol (4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl on ALS onset and progression in transgenic female rats over-expressing the mutant hSOD1(G93A . Starting at 7 weeks of age, a high dose of tempol (155 mg/day/rat in the rat´s drinking water had marginal effects on the disease onset but decelerated disease progression and extended survival by 9 days. In addition, tempol protected spinal cord tissues as monitored by the number of neuronal cells, and the reducing capability and levels of carbonylated proteins and non-native hSOD1 forms in spinal cord homogenates. Intraperitoneal tempol (26 mg/rat, 3 times/week extended survival by 17 days. This group of rats, however, diverted to a decelerated disease progression. Therefore, it was inconclusive whether the higher protective effect of the lower i.p. dose was due to higher tempol bioavailability, decelerated disease development or both. Collectively, the results show that tempol moderately extends the survival of ALS rats while protecting their cellular and molecular structures against damage. Thus, the results provide proof that cyclic nitroxides are alternatives worth to be further tested in animal models of ALS.

  14. EGFR inhibitor erlotinib delays disease progression but does not extend survival in the SOD1 mouse model of ALS.

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    Claire E Le Pichon

    Full Text Available Amyotrophic lateral sclerosis (ALS is a fatal neurodegenerative disease that causes progressive paralysis due to motor neuron death. Several lines of published evidence suggested that inhibition of epidermal growth factor receptor (EGFR signaling might protect neurons from degeneration. To test this hypothesis in vivo, we treated the SOD1 transgenic mouse model of ALS with erlotinib, an EGFR inhibitor clinically approved for oncology indications. Although erlotinib failed to extend ALS mouse survival it did provide a modest but significant delay in the onset of multiple behavioral measures of disease progression. However, given the lack of protection of motor neuron synapses and the lack of survival extension, the small benefits observed after erlotinib treatment appear purely symptomatic, with no modification of disease course.

  15. Primary glia expressing the G93A-SOD1 mutation present a neuroinflammatory phenotype and provide a cellular system for studies of glial inflammation

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    Qi Min

    2006-01-01

    Full Text Available Abstract Detailed study of glial inflammation has been hindered by lack of cell culture systems that spontaneously demonstrate the "neuroinflammatory phenotype". Mice expressing a glycine → alanine substitution in cytosolic Cu, Zn-superoxide dismutase (G93A-SOD1 associated with familial amyotrophic lateral sclerosis (ALS demonstrate age-dependent neuroinflammation associated with broad-spectrum cytokine, eicosanoid and oxidant production. In order to more precisely study the cellular mechanisms underlying glial activation in the G93A-SOD1 mouse, primary astrocytes were cultured from 7 day mouse neonates. At this age, G93A-SOD1 mice demonstrated no in vivo hallmarks of neuroinflammation. Nonetheless astrocytes cultured from G93A-SOD1 (but not wild-type human SOD1-expressing transgenic mouse pups demonstrated a significant elevation in either the basal or the tumor necrosis alpha (TNFα-stimulated levels of proinflammatory eicosanoids prostaglandin E2 (PGE2 and leukotriene B4 (LTB4; inducible nitric oxide synthase (iNOS and •NO (indexed by nitrite release into the culture medium; and protein carbonyl products. Specific cytokine- and TNFα death-receptor-associated components were similarly upregulated in cultured G93A-SOD1 cells as assessed by multiprobe ribonuclease protection assays (RPAs for their mRNA transcripts. Thus, endogenous glial expression of G93A-SOD1 produces a metastable condition in which glia are more prone to enter an activated neuroinflammatory state associated with broad-spectrum increased production of paracrine-acting substances. These findings support a role for active glial involvement in ALS and may provide a useful cell culture tool for the study of glial inflammation.

  16. Enhancing mitochondrial calcium buffering capacity reduces aggregation of misfolded SOD1 and motor neuron cell death without extending survival in mouse models of inherited amyotrophic lateral sclerosis.

    Science.gov (United States)

    Parone, Philippe A; Da Cruz, Sandrine; Han, Joo Seok; McAlonis-Downes, Melissa; Vetto, Anne P; Lee, Sandra K; Tseng, Eva; Cleveland, Don W

    2013-03-13

    Mitochondria have been proposed as targets for toxicity in amyotrophic lateral sclerosis (ALS), a progressive, fatal adult-onset neurodegenerative disorder characterized by the selective loss of motor neurons. A decrease in the capacity of spinal cord mitochondria to buffer calcium (Ca(2+)) has been observed in mice expressing ALS-linked mutants of SOD1 that develop motor neuron disease with many of the key pathological hallmarks seen in ALS patients. In mice expressing three different ALS-causing SOD1 mutants, we now test the contribution of the loss of mitochondrial Ca(2+)-buffering capacity to disease mechanism(s) by eliminating ubiquitous expression of cyclophilin D, a critical regulator of Ca(2+)-mediated opening of the mitochondrial permeability transition pore that determines mitochondrial Ca(2+) content. A chronic increase in mitochondrial buffering of Ca(2+) in the absence of cyclophilin D was maintained throughout disease course and was associated with improved mitochondrial ATP synthesis, reduced mitochondrial swelling, and retention of normal morphology. This was accompanied by an attenuation of glial activation, reduction in levels of misfolded SOD1 aggregates in the spinal cord, and a significant suppression of motor neuron death throughout disease. Despite this, muscle denervation, motor axon degeneration, and disease progression and survival were unaffected, thereby eliminating mutant SOD1-mediated loss of mitochondrial Ca(2+) buffering capacity, altered mitochondrial morphology, motor neuron death, and misfolded SOD1 aggregates, as primary contributors to disease mechanism for fatal paralysis in these models of familial ALS.

  17. Differential motor neuron impairment and axonal regeneration in sporadic and familiar amyotrophic lateral sclerosis with SOD-1 mutations: lessons from neurophysiology.

    Science.gov (United States)

    Bocci, Tommaso; Pecori, Chiara; Giorli, Elisa; Briscese, Lucia; Tognazzi, Silvia; Caleo, Matteo; Sartucci, Ferdinando

    2011-01-01

    Amyotrophic Lateral Sclerosis (ALS) is a degenerative disorder of the motor system. About 10% of cases are familial and 20% of these families have point mutations in the Cu/Zn superoxide dismutase 1 (SOD-1) gene. SOD-1 catalyses the superoxide radical (O(-2)) into hydrogen peroxide and molecular oxygen. The clinical neurophysiology in ALS plays a fundamental role in differential diagnosis between the familial and sporadic forms and in the assessment of its severity and progression. Sixty ALS patients (34 males; 26 females) were enrolled in the study and examined basally (T0) and every 4 months (T1, T2, and T3). Fifteen of these patients are SOD-1 symptomatic mutation carriers (nine males, six females). We used Macro-EMG and Motor Unit Number Estimation (MUNE) in order to evaluate the neuronal loss and the re-innervation process at the onset of disease and during follow-up period. SOD-1 mutation carriers have a higher number of motor units at the moment of diagnosis when compared with the sporadic form, despite a more dramatic drop in later stages. Moreover, in familiar SOD-1 ALS there is not a specific time interval in which the axonal regeneration can balance the neuronal damage. Taken together, these results strengthen the idea of a different pathogenetic mechanism at the base of sALS and fALS.

  18. Differential Motor Neuron Impairment and Axonal Regeneration in Sporadic and Familiar Amyotrophic Lateral Sclerosis with SOD-1 Mutations: Lessons from Neurophysiology

    Directory of Open Access Journals (Sweden)

    Tommaso Bocci

    2011-12-01

    Full Text Available Amyotrophic Lateral Sclerosis (ALS is a degenerative disorder of the motor system. About 10% of cases are familial and 20% of these families have point mutations in the Cu/Zn superoxide dismutase 1 (SOD-1 gene. SOD-1 catalyses the superoxide radical (O−2 into hydrogen peroxide and molecular oxygen. The clinical neurophysiology in ALS plays a fundamental role in differential diagnosis between the familial and sporadic forms and in the assessment of its severity and progression. Sixty ALS patients (34 males; 26 females were enrolled in the study and examined basally (T0 and every 4 months (T1, T2, and T3. Fifteen of these patients are SOD-1 symptomatic mutation carriers (nine males, six females. We used Macro-EMG and Motor Unit Number Estimation (MUNE in order to evaluate the neuronal loss and the re-innervation process at the onset of disease and during follow-up period. Results and Discussion: SOD-1 mutation carriers have a higher number of motor units at the moment of diagnosis when compared with the sporadic form, despite a more dramatic drop in later stages. Moreover, in familiar SOD-1 ALS there is not a specific time interval in which the axonal regeneration can balance the neuronal damage. Taken together, these results strengthen the idea of a different pathogenetic mechanism at the base of sALS and fALS.

  19. Impairment of mitochondrial calcium handling in a mtSOD1 cell culture model of motoneuron disease

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    Zippelius Annette

    2009-06-01

    Full Text Available Abstract Background Amyotrophic lateral sclerosis (ALS is a fatal neurodegenerative disorder characterized by the selective loss of motor neurons (MN in the brain stem and spinal cord. Intracellular disruptions of cytosolic and mitochondrial calcium have been associated with selective MN degeneration, but the underlying mechanisms are not well understood. The present evidence supports a hypothesis that mitochondria are a target of mutant SOD1-mediated toxicity in familial amyotrophic lateral sclerosis (fALS and intracellular alterations of cytosolic and mitochondrial calcium might aggravate the course of this neurodegenerative disease. In this study, we used a fluorescence charged cool device (CCD imaging system to separate and simultaneously monitor cytosolic and mitochondrial calcium concentrations in individual cells in an established cellular model of ALS. Results To gain insights into the molecular mechanisms of SOD1G93A associated motor neuron disease, we simultaneously monitored cytosolic and mitochondrial calcium concentrations in individual cells. Voltage – dependent cytosolic Ca2+ elevations and mitochondria – controlled calcium release mechanisms were monitored after loading cells with fluorescent dyes fura-2 and rhod-2. Interestingly, comparable voltage-dependent cytosolic Ca2+ elevations in WT (SH-SY5YWT and G93A (SH-SY5YG93A expressing cells were observed. In contrast, mitochondrial intracellular Ca2+ release responses evoked by bath application of the mitochondrial toxin FCCP were significantly smaller in G93A expressing cells, suggesting impaired calcium stores. Pharmacological experiments further supported the concept that the presence of G93A severely disrupts mitochondrial Ca2+ regulation. Conclusion In this study, by fluorescence measurement of cytosolic calcium and using simultaneous [Ca2+]i and [Ca2+]mito measurements, we are able to separate and simultaneously monitor cytosolic and mitochondrial calcium concentrations

  20. Influence of genetic variations in the SOD1 gene on the development of ascites and spontaneous bacterial peritonitis in decompensated liver cirrhosis

    DEFF Research Database (Denmark)

    Schwab, Sebastian; Lehmann, Jennifer; Lutz, Philipp

    2017-01-01

    BACKGROUND: The balance between generation and elimination of reactive oxygen species by superoxide dismutase (SOD) is crucially involved in the pathophysiology of liver cirrhosis. Reactive oxygen species damage cells and induce inflammation/fibrosis, but also play a critical role in immune defense...... in carriers of rs1041740. In this cohort, rs1041740 was not associated with survival. CONCLUSION: These data suggest a complex role of SOD1 in different processes leading to complications of liver cirrhosis. rs1041740 might be associated with the development of ascites and possibly plays a role in SBP once...... from pathogens. As both processes are involved in the development of liver cirrhosis and its complications, genetic variation of the SOD1 gene was investigated. PATIENTS AND METHODS: Two SOD1 single nucleotide polymorphisms (rs1041740 and rs3844942) were analyzed in 49 cirrhotic patients undergoing...

  1. Gene expression changes in spinal motoneurons of the SOD1G93A transgenic model for ALS after treatment with G-CSF

    Science.gov (United States)

    Henriques, Alexandre; Kastner, Stefan; Chatzikonstantinou, Eva; Pitzer, Claudia; Plaas, Christian; Kirsch, Friederike; Wafzig, Oliver; Krüger, Carola; Spoelgen, Robert; Gonzalez De Aguilar, Jose-Luis; Gretz, Norbert; Schneider, Armin

    2015-01-01

    Background: Amyotrophic lateral sclerosis (ALS) is an incurable fatal motoneuron disease with a lifetime risk of approximately 1:400. It is characterized by progressive weakness, muscle wasting, and death ensuing 3–5 years after diagnosis. Granulocyte-colony stimulating factor (G-CSF) is a drug candidate for ALS, with evidence for efficacy from animal studies and interesting data from pilot clinical trials. To gain insight into the disease mechanisms and mode of action of G-CSF, we performed gene expression profiling on isolated lumbar motoneurons from SOD1G93A mice, the most frequently studied animal model for ALS, with and without G-CSF treatment. Results: Motoneurons from SOD1G93A mice present a distinct gene expression profile in comparison to controls already at an early disease stage (11 weeks of age), when treatment was initiated. The degree of deregulation increases at a time where motor symptoms are obvious (15 weeks of age). Upon G-CSF treatment, transcriptomic deregulations of SOD1G93A motoneurons were notably restored. Discriminant analysis revealed that SOD1 mice treated with G-CSF has a transcriptom close to presymptomatic SOD1 mice or wild type mice. Some interesting genes modulated by G-CSF treatment relate to neuromuscular function such as CCR4-NOT or Prss12. Conclusions: Our data suggest that G-CSF is able to re-adjust gene expression in symptomatic SOD1G93A motoneurons. This provides further arguments for G-CSF as a promising drug candidate for ALS. PMID:25653590

  2. Gene expression changes in spinal motoneurons of the SOD1G93A transgenic model for ALS after treatment with G-CSF.

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    Alexandre eHenriques

    2015-01-01

    Full Text Available ABSTRACTBackgroundAmyotrophic lateral sclerosis (ALS is an incurable fatal motoneuron disease with a lifetime risk of approximately 1:400. It is characterized by progressive weakness, muscle wasting, and death ensuing 3-5 years after diagnosis. Granulocyte-colony stimulating factor (G-CSF is a drug candidate for ALS, with evidence for efficacy from animal studies and interesting data from pilot clinical trials. To gain insight into the disease mechanisms and mode of action of G-CSF, we performed gene expression profiling on isolated lumbar motoneurons from SOD1G93A mice, the most frequently studied animal model for ALS, with and without G-CSF treatment. ResultsMotoneurons from SOD1G93A mice present a distinct gene expression profile in comparison to controls already at an early disease stage (11 weeks of age, when treatment was initiated. The degree of deregulation increases at a time where motor symptoms are obvious (15 weeks of age. Upon G-CSF treatment, transcriptomic deregulations of SOD1G93A motoneurons were notably restored. Discriminant analysis revealed that SOD1 mice treated with G-CSF has a transcriptom close to presymptomatic SOD1 mice or wild type mice. Some interesting genes modulated by G-CSF treatment relate to neuromuscular function such as CCR4-NOT or Prss12.ConclusionsOur data suggest that G-CSF is able to re-adjust gene expression in symptomatic SOD1G93A motoneurons. This provides further arguments for G-CSF as a promising drug candidate for ALS.

  3. Gene expression changes in spinal motoneurons of the SOD1(G93A) transgenic model for ALS after treatment with G-CSF.

    Science.gov (United States)

    Henriques, Alexandre; Kastner, Stefan; Chatzikonstantinou, Eva; Pitzer, Claudia; Plaas, Christian; Kirsch, Friederike; Wafzig, Oliver; Krüger, Carola; Spoelgen, Robert; Gonzalez De Aguilar, Jose-Luis; Gretz, Norbert; Schneider, Armin

    2014-01-01

    Amyotrophic lateral sclerosis (ALS) is an incurable fatal motoneuron disease with a lifetime risk of approximately 1:400. It is characterized by progressive weakness, muscle wasting, and death ensuing 3-5 years after diagnosis. Granulocyte-colony stimulating factor (G-CSF) is a drug candidate for ALS, with evidence for efficacy from animal studies and interesting data from pilot clinical trials. To gain insight into the disease mechanisms and mode of action of G-CSF, we performed gene expression profiling on isolated lumbar motoneurons from SOD1(G93A) mice, the most frequently studied animal model for ALS, with and without G-CSF treatment. Motoneurons from SOD1(G93A) mice present a distinct gene expression profile in comparison to controls already at an early disease stage (11 weeks of age), when treatment was initiated. The degree of deregulation increases at a time where motor symptoms are obvious (15 weeks of age). Upon G-CSF treatment, transcriptomic deregulations of SOD1(G93A) motoneurons were notably restored. Discriminant analysis revealed that SOD1 mice treated with G-CSF has a transcriptom close to presymptomatic SOD1 mice or wild type mice. Some interesting genes modulated by G-CSF treatment relate to neuromuscular function such as CCR4-NOT or Prss12. Our data suggest that G-CSF is able to re-adjust gene expression in symptomatic SOD1(G93A) motoneurons. This provides further arguments for G-CSF as a promising drug candidate for ALS.

  4. Knocking down metabotropic glutamate receptor 1 improves survival and disease progression in the SOD1(G93A) mouse model of amyotrophic lateral sclerosis.

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    Milanese, Marco; Giribaldi, Francesco; Melone, Marcello; Bonifacino, Tiziana; Musante, Ilaria; Carminati, Enrico; Rossi, Pia I A; Vergani, Laura; Voci, Adriana; Conti, Fiorenzo; Puliti, Aldamaria; Bonanno, Giambattista

    2014-04-01

    Amyotrophic lateral sclerosis (ALS) is a late-onset fatal neurodegenerative disease reflecting degeneration of upper and lower motoneurons (MNs). The cause of ALS and the mechanisms of neuronal death are still largely obscure, thus impairing the establishment of efficacious therapies. Glutamate (Glu)-mediated excitotoxicity plays a major role in MN degeneration in ALS. We recently demonstrated that the activation of Group I metabotropic Glu autoreceptors, belonging to both type 1 and type 5 receptors (mGluR1 and mGluR5), at glutamatergic spinal cord nerve terminals, produces excessive Glu release in mice over-expressing human superoxide-dismutase carrying the G93A point mutation (SOD1(G93A)), a widely used animal model of human ALS. To establish whether these receptors are implicated in ALS, we generated mice expressing half dosage of mGluR1 in the SOD1(G93A) background (SOD1(G93A)Grm1(crv4/+)), by crossing the SOD1(G93A) mutant mouse with the Grm1(crv4/+) mouse, lacking mGluR1 because of a spontaneous recessive mutation. SOD1(G93A)Grm1(crv4/+) mice showed prolonged survival probability, delayed pathology onset, slower disease progression and improved motor performances compared to SOD1(G93A) mice. These effects were associated to reduction of mGluR5 expression, enhanced number of MNs, decreased astrocyte and microglia activation, normalization of metallothionein and catalase mRNA expression, reduced mitochondrial damage, and decrease of abnormal Glu release in spinal cord of SOD1(G93A)Grm1(crv4/+)compared to SOD1(G93A) mice. These results demonstrate that a lower constitutive level of mGluR1 has a significant positive impact on mice with experimental ALS, thus providing the rationale for future pharmacological approaches to ALS by selectively blocking Group I metabotropic Glu receptors. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

  5. Presymptomatic Treatment with Acetylcholinesterase Antisense Oligonucleotides Prolongs Survival in ALS (G93A-SOD1 Mice

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    Gotkine Marc

    2013-01-01

    Full Text Available Objective. Previous research suggests that acetylcholinesterase (AChE may be involved in ALS pathogenesis. AChE enzyme inhibitors can upregulate AChE transcription which in certain contexts can have deleterious (noncatalytic effects, making them theoretically harmful in ALS, whilst AChE antisense-oligonucleotides (mEN101, which downregulate AChE may be beneficial. Our aim was to investigate whether downregulation of AChE using mEN101 is beneficial in an ALS mouse model. Methods. ALS (G93A-SOD1 mice received saline, mEN101, inverse-EN101, or neostigmine. Treatments were administered from 5 weeks. Disease-onset and survival were recorded. Additional mice were sacrificed for pathological analysis at 15 weeks of age. In a follow-up experiment treatment was started at the symptomatic stage at a higher dose. Results. mEN101 given at the presymptomatic (but not symptomatic stage prolonged survival and attenuated motor-neuron loss in ALS mice. In contrast, neostigmine exacerbated the clinical parameters. Conclusions. These results suggest that AChE may be involved in ALS pathogenesis. The accelerated disease course with neostigmine suggests that any beneficial effects of mEN101 occur through a non-catalytic rather than cholinergic mechanism.

  6. Absence of Nrf2 or its selective overexpression in neurons and muscle does not affect survival in ALS-linked mutant hSOD1 mouse models.

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    Marcelo R Vargas

    Full Text Available The nuclear factor erythroid 2-related factor 2 (Nrf2 governs the expression of antioxidant and phase II detoxifying enzymes. Nrf2 activation can prevent or reduce cellular damage associated with several types of injury in many different tissues and organs. Dominant mutations in Cu/Zn-superoxide dismutase (SOD1 cause familial forms of amyotrophic lateral sclerosis (ALS, a fatal disorder characterized by the progressive loss of motor neurons and subsequent muscular atrophy. We have previously shown that Nrf2 activation in astrocytes delays neurodegeneration in ALS mouse models. To further investigate the role of Nrf2 in ALS we determined the effect of absence of Nrf2 or its restricted overexpression in neurons or type II skeletal muscle fibers on symptoms onset and survival in mutant hSOD1 expressing mice. We did not observe any detrimental effect associated with the lack of Nrf2 in two different mutant hSOD1 animal models of ALS. However, restricted Nrf2 overexpression in neurons or type II skeletal muscle fibers delayed disease onset but failed to extend survival in hSOD1(G93A mice. These results highlight the concept that not only the pharmacological target but also the cell type targeted may be relevant when considering a Nrf2-mediated therapeutic approach for ALS.

  7. Aberrant association of misfolded SOD1 with Na(+)/K(+)ATPase-α3 impairs its activity and contributes to motor neuron vulnerability in ALS

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    Ruegsegger, Céline; Maharjan, Niran; Goswami, Anand; Filézac de L'Etang, Audrey; Weis, Joachim; Troost, Dirk; Heller, Manfred; Gut, Heinz; Saxena, Smita

    2016-01-01

    Amyotrophic lateral sclerosis (ALS) is an adult onset progressive motor neuron disease with no cure. Transgenic mice overexpressing familial ALS associated human mutant SOD1 are a commonly used model for examining disease mechanisms. Presently, it is well accepted that alterations in motor neuron

  8. The Cu-Zn superoxide dismutase (SOD1) inhibits ERK phosphorylation by muscarinic receptor modulation in rat pituitary GH3 cells

    International Nuclear Information System (INIS)

    Secondo, Agnese; De Mizio, Mariarosaria; Zirpoli, Laura; Santillo, Mariarosaria; Mondola, Paolo

    2008-01-01

    The Cu-Zn superoxide dismutase (SOD1) belongs to a family of isoenzymes that are able to dismutate the oxygen superoxide in hydrogen peroxide and molecular oxygen. This enzyme is secreted by many cellular lines and it is also released trough a calcium-dependent depolarization mechanism involving SNARE protein SNAP 25. Using rat pituitary GH3 cells that express muscarinic receptors we found that SOD1 inhibits P-ERK1/2 pathway trough an interaction with muscarinic M1 receptor. This effect is strengthened by oxotremorine, a muscarinic M agonist and partially reverted by pyrenzepine, an antagonist of M1 receptor; moreover this effect is independent from increased intracellular calcium concentration induced by SOD1. Finally, P-ERK1/2 inhibition was accompanied by the reduction of GH3 cell proliferation. These data indicate that SOD1 beside the well studied antioxidant properties can be considered as a neuromodulator able to affect mitogen-activated protein kinase in rat pituitary cells trough a M1 muscarinic receptor

  9. The Effects of Bee Venom Acupuncture on the Central Nervous System and Muscle in an Animal hSOD1G93A Mutant

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    MuDan Cai

    2015-03-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is caused by the degeneration of lower and upper motor neurons, leading to muscle paralysis and respiratory failure. However, there is no effective drug or therapy to treat ALS. Complementary and alternative medicine (CAM, including acupuncture, pharmacopuncture, herbal medicine, and massage is popular due to the significant limitations of conventional therapy. Bee venom acupuncture (BVA, also known as one of pharmacopunctures, has been used in Oriental medicine to treat inflammatory diseases. The purpose of this study is to investigate the effect of BVA on the central nervous system (CNS and muscle in symptomatic hSOD1G93A transgenic mice, an animal model of ALS. Our findings show that BVA at ST36 enhanced motor function and decreased motor neuron death in the spinal cord compared to that observed in hSOD1G93A transgenic mice injected intraperitoneally (i.p. with BV. Furthermore, BV treatment at ST36 eliminated signaling downstream of inflammatory proteins such as TLR4 in the spinal cords of symptomatic hSOD1G93A transgenic mice. However, i.p. treatment with BV reduced the levels of TNF-α and Bcl-2 expression in the muscle hSOD1G93A transgenic mice. Taken together, our findings suggest that BV pharmacopuncture into certain acupoints may act as a chemical stimulant to activate those acupoints and subsequently engage the endogenous immune modulatory system in the CNS in an animal model of ALS.

  10. Evidence of compromised blood-spinal cord barrier in early and late symptomatic SOD1 mice modeling ALS.

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    Svitlana Garbuzova-Davis

    2007-11-01

    Full Text Available The blood-brain barrier (BBB, blood-spinal cord barrier (BSCB, and blood-cerebrospinal fluid barrier (BCSFB control cerebral/spinal cord homeostasis by selective transport of molecules and cells from the systemic compartment. In the spinal cord and brain of both ALS patients and animal models, infiltration of T-cell lymphocytes, monocyte-derived macrophages and dendritic cells, and IgG deposits have been observed that may have a critical role in motor neuron damage. Additionally, increased levels of albumin and IgG have been found in the cerebrospinal fluid in ALS patients. These findings suggest altered barrier permeability in ALS. Recently, we showed disruption of the BBB and BSCB in areas of motor neuron degeneration in the brain and spinal cord in G93A SOD1 mice modeling ALS at both early and late stages of disease using electron microscopy. Examination of capillary ultrastructure revealed endothelial cell degeneration, which, along with astrocyte alteration, compromised the BBB and BSCB. However, the effect of these alterations upon barrier function in ALS is still unclear. The aim of this study was to determine the functional competence of the BSCB in G93A mice at different stages of disease.Evans Blue (EB dye was intravenously injected into ALS mice at early or late stage disease. Vascular leakage and the condition of basement membranes, endothelial cells, and astrocytes were investigated in cervical and lumbar spinal cords using immunohistochemistry. Results showed EB leakage in spinal cord microvessels from all G93A mice, indicating dysfunction in endothelia and basement membranes and confirming our previous ultrastructural findings on BSCB disruption. Additionally, downregulation of Glut-1 and CD146 expressions in the endothelial cells of the BSCB were found which may relate to vascular leakage.Results suggest that the BSCB is compromised in areas of motor neuron degeneration in ALS mice at both early and late stages of the disease.

  11. Loss of metal ions, disulfide reduction and mutations related to familial ALS promote formation of amyloid-like aggregates from superoxide dismutase.

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    Zeynep A Oztug Durer

    Full Text Available Mutations in the gene encoding Cu-Zn superoxide dismutase (SOD1 are one of the causes of familial amyotrophic lateral sclerosis (FALS. Fibrillar inclusions containing SOD1 and SOD1 inclusions that bind the amyloid-specific dye thioflavin S have been found in neurons of transgenic mice expressing mutant SOD1. Therefore, the formation of amyloid fibrils from human SOD1 was investigated. When agitated at acidic pH in the presence of low concentrations of guanidine or acetonitrile, metalated SOD1 formed fibrillar material which bound both thioflavin T and Congo red and had circular dichroism and infrared spectra characteristic of amyloid. While metalated SOD1 did not form amyloid-like aggregates at neutral pH, either removing metals from SOD1 with its intramolecular disulfide bond intact or reducing the intramolecular disulfide bond of metalated SOD1 was sufficient to promote formation of these aggregates. SOD1 formed amyloid-like aggregates both with and without intermolecular disulfide bonds, depending on the incubation conditions, and a mutant SOD1 lacking free sulfhydryl groups (AS-SOD1 formed amyloid-like aggregates at neutral pH under reducing conditions. ALS mutations enhanced the ability of disulfide-reduced SOD1 to form amyloid-like aggregates, and apo-AS-SOD1 formed amyloid-like aggregates at pH 7 only when an ALS mutation was also present. These results indicate that some mutations related to ALS promote formation of amyloid-like aggregates by facilitating the loss of metals and/or by making the intramolecular disulfide bond more susceptible to reduction, thus allowing the conversion of SOD1 to a form that aggregates to form resembling amyloid. Furthermore, the occurrence of amyloid-like aggregates per se does not depend on forming intermolecular disulfide bonds, and multiple forms of such aggregates can be produced from SOD1.

  12. ApoSOD1 lacking dismutase activity neuroprotects motor neurons exposed to beta-methylamino-L-alanine through the Ca2+/Akt/ERK1/2 prosurvival pathway

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    Petrozziello, Tiziana; Secondo, Agnese; Tedeschi, Valentina; Esposito, Alba; Sisalli, MariaJosè; Scorziello, Antonella; Di Renzo, Gianfranco; Annunziato, Lucio

    2017-01-01

    Amyotrophic lateral sclerosis (ALS) is a severe human adult-onset neurodegenerative disease affecting lower and upper motor neurons. In >20% of cases, the familial form of ALS is caused by mutations in the gene encoding Cu,Zn-superoxide dismutase (SOD1). Interestingly, administration of wild-type SOD1 to SOD1G93A transgenic rats ameliorates motor symptoms through an unknown mechanism. Here we investigated whether the neuroprotective effects of SOD1 are due to the Ca2+-dependent activation of such prosurvival signaling pathway and not to its catalytic activity. To this aim, we also examined the mechanism of neuroprotective action of ApoSOD1, the metal-depleted state of SOD1 that lacks dismutase activity, in differentiated motor neuron-like NSC-34 cells and in primary motor neurons exposed to the cycad neurotoxin beta-methylamino-L-alanine (L-BMAA). Preincubation of ApoSOD1 and SOD1, but not of human recombinant SOD1G93A, prevented cell death in motor neurons exposed to L-BMAA. Moreover, ApoSOD1 elicited ERK1/2 and Akt phosphorylation in motor neurons through an early increase of intracellular Ca2+ concentration ([Ca2+]i). Accordingly, inhibition of ERK1/2 by siMEK1 and PD98059 counteracted ApoSOD1- and SOD1-induced neuroprotection. Similarly, transfection of the dominant-negative form of Akt in NSC-34 motor neurons and treatment with the selective PI3K inhibitor LY294002 prevented ApoSOD1- and SOD1-mediated neuroprotective effects in L-BMAA-treated motor neurons. Furthermore, ApoSOD1 and SOD1 prevented the expression of the two markers of L-BMAA-induced ER stress GRP78 and caspase-12. Collectively, our data indicate that ApoSOD1, which is devoid of any catalytic dismutase activity, exerts a neuroprotective effect through an early activation of Ca2+/Akt/ERK1/2 pro-survival pathway that, in turn, prevents ER stress in a neurotoxic model of ALS. PMID:28085149

  13. The effect of SOD1 mutation on cellular bioenergetic profile and viability in response to oxidative stress and influence of mutation-type.

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    Katie Richardson

    Full Text Available Amyotrophic Lateral Sclerosis (ALS is a fatal neurodegenerative disorder characterized by the progressive degeneration of motor neurons. Substantial evidence implicates oxidative stress and mitochondrial dysfunction as early events in disease progression. Our aim was to ascertain whether mutation of the SOD1 protein increases metabolic functional susceptibility to oxidative stress. Here we used a motor neuron-like cell line (NSC34 stably transfected with various human mutant SOD1 transgenes (G93A, G37R, H48Q to investigate the impact of oxidative stress on cell viability and metabolic function within intact cells. NSC34 cells expressing mutant SOD1 showed a dose dependent reduction in cell viability when exposed to oxidative stress induced by hydrogen peroxide, with variation between mutations. The G93A transfectants showed greater cell death and LDH release compared to cells transfected with the other SOD1 mutations, and H48Q showed an accelerated decline at later time points. Differences in mitochondrial bioenergetics, including mitochondrial respiration, coupling efficiency and proton leak, were identified between the mutations, consistent with the differences observed in viability. NSC34 cells expressing G93A SOD1 displayed reduced coupled respiration and mitochondrial membrane potential compared to controls. Furthermore, the G93A mutation had significantly increased metabolic susceptibility to oxidative stress, with hydrogen peroxide increasing ROS production, reducing both cellular oxygen consumption and glycolytic flux in the cell. This study highlights bioenergetic defects within a cellular model of ALS and suggests that oxidative stress is not only detrimental to oxygen consumption but also glycolytic flux, which could lead to an energy deficit in the cell.

  14. A mutation in the dynein heavy chain gene compensates for energy deficit of mutant SOD1 mice and increases potentially neuroprotective IGF-1

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    Larmet Yves

    2011-04-01

    Full Text Available Abstract Background Amyotrophic lateral sclerosis (ALS is a fatal neurodegenerative disease characterized by a progressive loss of motor neurons. ALS patients, as well as animal models such as mice overexpressing mutant SOD1s, are characterized by increased energy expenditure. In mice, this hypermetabolism leads to energy deficit and precipitates motor neuron degeneration. Recent studies have shown that mutations in the gene encoding the dynein heavy chain protein are able to extend lifespan of mutant SOD1 mice. It remains unknown whether the protection offered by these dynein mutations relies on a compensation of energy metabolism defects. Results SOD1(G93A mice were crossbred with mice harboring the dynein mutant Cramping allele (Cra/+ mice. Dynein mutation increased adipose stores in compound transgenic mice through increasing carbohydrate oxidation and sparing lipids. Metabolic changes that occurred in double transgenic mice were accompanied by the normalization of the expression of key mRNAs in the white adipose tissue and liver. Furthermore, Dynein Cra mutation rescued decreased post-prandial plasma triglycerides and decreased non esterified fatty acids upon fasting. In SOD1(G93A mice, the dynein Cra mutation led to increased expression of IGF-1 in the liver, increased systemic IGF-1 and, most importantly, to increased spinal IGF-1 levels that are potentially neuroprotective. Conclusions These findings suggest that the protection against SOD1(G93A offered by the Cramping mutation in the dynein gene is, at least partially, mediated by a reversal in energy deficit and increased IGF-1 availability to motor neurons.

  15. A Novel Iron Chelator-Radical Scavenger Ameliorates Motor Dysfunction and Improves Life Span and Mitochondrial Biogenesis in SOD1G93A ALS Mice.

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    Golko-Perez, Sagit; Amit, Tamar; Bar-Am, Orit; Youdim, Moussa B H; Weinreb, Orly

    2017-02-01

    The aim of the present study was to evaluate the therapeutic effect of the novel neuroprotective multitarget brain permeable monoamine oxidase inhibitor/iron chelating-radical scavenging drug, VAR10303 (VAR), co-administered with high-calorie/energy-supplemented diet (ced) in SOD1 G93A transgenic amyotrophic lateral sclerosis (ALS) mice. Administration of VAR-ced was initiated after the appearance of disease symptoms (at day 88), as this regimen is comparable with the earliest time at which drug therapy could start in ALS patients. Using this rescue protocol, we demonstrated in the current study that VAR-ced treatment provided several beneficial effects in SOD1 G93A mice, including improvement in motor performance, elevation of survival time, and attenuation of iron accumulation and motoneuron loss in the spinal cord. Moreover, VAR-ced treatment attenuated neuromuscular junction denervation and exerted a significant preservation of myofibril regular morphology, associated with a reduction in the expression levels of genes related to denervation and atrophy in the gastrocnemius (GNS) muscle in SOD1 G93A mice. These effects were accompanied by upregulation of mitochondrial DNA and elevated activities of complexes I and II in the GNS muscle. We have also demonstrated that VAR-ced treatment upregulated the mitochondrial biogenesis master regulator, peroxisome proliferator-activated receptor-γ co-activator 1α (PGC-1α) and increased PGC-1α-targeted metabolic genes and proteins, such as, PPARγ, UCP1/3, NRF1/2, Tfam, and ERRα in GNS muscle. These results provide evidence of therapeutic potential of VAR-ced in SOD1 G93A mice with underlying molecular mechanisms, further supporting the importance role of multitarget iron chelators in ALS treatment.

  16. An ALS-linked mutant SOD1 produces a locomotor defect associated with aggregation and synaptic dysfunction when expressed in neurons of Caenorhabditis elegans.

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    Jiou Wang

    2009-01-01

    Full Text Available The nature of toxic effects exerted on neurons by misfolded proteins, occurring in a number of neurodegenerative diseases, is poorly understood. One approach to this problem is to measure effects when such proteins are expressed in heterologous neurons. We report on effects of an ALS-associated, misfolding-prone mutant human SOD1, G85R, when expressed in the neurons of Caenorhabditis elegans. Stable mutant transgenic animals, but not wild-type human SOD1 transgenics, exhibited a strong locomotor defect associated with the presence, specifically in mutant animals, of both soluble oligomers and insoluble aggregates of G85R protein. A whole-genome RNAi screen identified chaperones and other components whose deficiency increased aggregation and further diminished locomotion. The nature of the locomotor defect was investigated. Mutant animals were resistant to paralysis by the cholinesterase inhibitor aldicarb, while exhibiting normal sensitivity to the cholinergic agonist levamisole and normal muscle morphology. When fluorescently labeled presynaptic components were examined in the dorsal nerve cord, decreased numbers of puncta corresponding to neuromuscular junctions were observed in mutant animals and brightness was also diminished. At the EM level, mutant animals exhibited a reduced number of synaptic vesicles. Neurotoxicity in this system thus appears to be mediated by misfolded SOD1 and is exerted on synaptic vesicle biogenesis and/or trafficking.

  17. Genetic Correction of SOD1 Mutant iPSCs Reveals ERK and JNK Activated AP1 as a Driver of Neurodegeneration in Amyotrophic Lateral Sclerosis

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    Akshay Bhinge

    2017-04-01

    Full Text Available Summary: Although mutations in several genes with diverse functions have been known to cause amyotrophic lateral sclerosis (ALS, it is unknown to what extent causal mutations impinge on common pathways that drive motor neuron (MN-specific neurodegeneration. In this study, we combined induced pluripotent stem cells-based disease modeling with genome engineering and deep RNA sequencing to identify pathways dysregulated by mutant SOD1 in human MNs. Gene expression profiling and pathway analysis followed by pharmacological screening identified activated ERK and JNK signaling as key drivers of neurodegeneration in mutant SOD1 MNs. The AP1 complex member JUN, an ERK/JNK downstream target, was observed to be highly expressed in MNs compared with non-MNs, providing a mechanistic insight into the specific degeneration of MNs. Importantly, investigations of mutant FUS MNs identified activated p38 and ERK, indicating that network perturbations induced by ALS-causing mutations converge partly on a few specific pathways that are drug responsive and provide immense therapeutic potential. : In this article, Bhinge, Stanton, and colleagues use genome editing of patient-derived iPSCs to model ALS phenotypic defects in vitro. Transcriptomic analysis of disease MNs reveals activation of MAPK, AP1, WNT, cell-cycle, and p53 signaling in ALS MNs. Pharmacological screening uncovers activated ERK and JNK signaling as therapeutic targets in ALS. Keywords: ALS, SOD1, FUS, CRISPR-Cas9, p38, ERK, JNK, WNT, TP53, JUN

  18. Bee Venom Acupuncture Augments Anti-Inflammation in the Peripheral Organs of hSOD1G93A Transgenic Mice.

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    Lee, Sun-Hwa; Choi, Sun-Mi; Yang, Eun Jin

    2015-07-29

    Amyotrophic lateral sclerosis (ALS) includes progressively degenerated motor neurons in the brainstem, motor cortex, and spinal cord. Recent reports demonstrate the dysfunction of multiple organs, including the lungs, spleen, and liver, in ALS animals and patients. Bee venom acupuncture (BVA) has been used for treating inflammatory diseases in Oriental Medicine. In a previous study, we demonstrated that BV prevented motor neuron death and increased anti-inflammation in the spinal cord of symptomatic hSOD1G93A transgenic mice. In this study, we examined whether BVA's effects depend on acupuncture point (ST36) in the organs, including the liver, spleen and kidney, of hSOD1G93A transgenic mice. We found that BV treatment at ST36 reduces inflammation in the liver, spleen, and kidney compared with saline-treatment at ST36 and BV injected intraperitoneally in symptomatic hSOD1G93A transgenic mice. Those findings suggest that BV treatment combined with acupuncture stimulation is more effective at reducing inflammation and increasing immune responses compared with only BV treatment, at least in an ALS animal model.

  19. A Quick Phenotypic Neurological Scoring System for Evaluating Disease Progression in the SOD1-G93A Mouse Model of ALS.

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    Hatzipetros, Theo; Kidd, Joshua D; Moreno, Andy J; Thompson, Kenneth; Gill, Alan; Vieira, Fernando G

    2015-10-06

    The SOD1-G93A transgenic mouse is the most widely used animal model of amyotrophic lateral sclerosis (ALS). At ALS TDI we developed a phenotypic screening protocol, demonstrated in video herein, which reliably assesses the neuromuscular function of SOD1-G93A mice in a quick manner. This protocol encompasses a simple neurological scoring system (NeuroScore) designed to assess hindlimb function. NeuroScore is focused on hindlimb function because hindlimb deficits are the earliest reported neurological sign of disease in SOD1-G93A mice. The protocol developed by ALS TDI provides an unbiased assessment of onset of paresis (slight or partial paralysis), progression and severity of paralysis and it is sensitive enough to identify drug-induced changes in disease progression. In this report, the combination of a detailed manuscript with video minimizes scoring ambiguities and inter-experimenter variability thus allowing for the protocol to be adopted by other laboratories and enabling comparisons between studies taking place at different settings. We believe that this video protocol can serve as an excellent training tool for present and future ALS researchers.

  20. Administration of 4-(α-L-Rhamnosyloxy-benzyl Isothiocyanate Delays Disease Phenotype in SOD1G93A Rats: A Transgenic Model of Amyotrophic Lateral Sclerosis

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    Maria Galuppo

    2015-01-01

    Full Text Available 4-(α-L-Rhamnosyloxy-benzyl glucosinolate (glucomoringin, GMG is a compound found in Moringa oleifera seeds. Myrosinase-catalyzed hydrolysis at neutral pH of GMG releases the biologically active compound 4-(α-L-rhamnosyloxy-benzyl isothiocyanate (GMG-ITC. The present study was designed to test the potential therapeutic effectiveness of GMG-ITC to counteract the amyotrophic lateral sclerosis (ALS using SOD1tg rats, which physiologically develops SOD1G93A at about 16 weeks of life, and can be considered a genetic model of disease. Rats were treated once a day with GMG (10 mg/Kg bioactivated with myrosinase (20 µL/rat via intraperitoneal (i.p. injection for two weeks before disease onset and the treatment was prolonged for further two weeks before the sacrifice. Immune-inflammatory markers as well as apoptotic pathway were investigated to establish whether GMG-ITC could represent a new promising tool in clinical practice to prevent ALS. Achieved data display clear differences in molecular and biological profiles between treated and untreated SOD1tg rats leading to guessing that GMG-ITC can interfere with the pathophysiological mechanisms at the basis of ALS development. Therefore, GMG-ITC produced from myrosinase-catalyzed hydrolysis of pure GMG could be a candidate for further studies aimed to assess its possible use in clinical practice for the prevention or to slow down this disease.

  1. Multiple intracerebroventricular injections of human umbilical cord mesenchymal stem cells delay motor neurons loss but not disease progression of SOD1G93A mice.

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    Sironi, Francesca; Vallarola, Antonio; Violatto, Martina Bruna; Talamini, Laura; Freschi, Mattia; De Gioia, Roberta; Capelli, Chiara; Agostini, Azzurra; Moscatelli, Davide; Tortarolo, Massimo; Bigini, Paolo; Introna, Martino; Bendotti, Caterina

    2017-12-01

    Stem cell therapy is considered a promising approach in the treatment of amyotrophic lateral sclerosis (ALS) and mesenchymal stem cells (MSCs) seem to be the most effective in ALS animal models. The umbilical cord (UC) is a source of highly proliferating fetal MSCs, more easily collectable than other MSCs. Recently we demonstrated that human (h) UC-MSCs, double labeled with fluorescent nanoparticles and Hoechst-33258 and transplanted intracerebroventricularly (ICV) into SOD1G93A transgenic mice, partially migrated into the spinal cord after a single injection. This prompted us to assess the effect of repeated ICV injections of hUC-MSCs on disease progression in SOD1G93A mice. Although no transplanted cells migrated to the spinal cord, a partial but significant protection of motor neurons (MNs) was found in the lumbar spinal cord of hUC-MSCs-treated SOD1G93A mice, accompanied by a shift from a pro-inflammatory (IL-6, IL-1β) to anti-inflammatory (IL-4, IL-10) and neuroprotective (IGF-1) environment in the lumbar spinal cord, probably linked to the activation of p-Akt survival pathway in both motor neurons and reactive astrocytes. However, this treatment neither prevented the muscle denervation nor delayed the disease progression of mice, emphasizing the growing evidence that protecting the motor neuron perikarya is not sufficient to delay the ALS progression. Copyright © 2017. Published by Elsevier B.V.

  2. Elevated mRNA-levels of distinct mitochondrial and plasma membrane Ca2+ transporters in individual hypoglossal motor neurons of endstage SOD1 transgenic mice.

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    Tobias eMühling

    2014-11-01

    Full Text Available Disturbances in Ca2+ homeostasis and mitochondrial dysfunction have emerged as major pathogenic features in familial and sporadic forms of Amyotrophic Lateral Sclerosis (ALS, a fatal degenerative motor neuron disease. However, the distinct molecular ALS-pathology remains unclear. Recently, an activity-dependent Ca2+ homeostasis deficit, selectively in highly vulnerable cholinergic motor neurons in the hypoglossal nucleus (hMNs from a common ALS mouse model, endstage superoxide dismutase SOD1G93A transgenic mice, was described. This functional deficit was defined by a reduced hMN mitochondrial Ca2+ uptake capacity and elevated Ca2+ extrusion across the plasma membrane. To address the underlying molecular mechanisms, here we quantified mRNA-levels of respective potential mitochondrial and plasma membrane Ca2+ transporters in individual, choline-acetyltransferase (ChAT positive hMNs from wildtype (WT and endstage SOD1G93A mice, by combining UV laser microdissection with RT-qPCR techniques, and specific data normalization. As ChAT cDNA levels as well as cDNA and genomic DNA levels of the mitochondrially encoded NADH dehydrogenase ND1 were not different between hMNs from WT and endstage SOD1G93A mice, these genes were used to normalize hMN-specific mRNA-levels of plasma membrane and mitochondrial Ca2+ transporters, respectively. We detected about 2-fold higher levels of the mitochondrial Ca2+ transporters MCU/MICU1, Letm1 and UCP2 in remaining hMNs from endstage SOD1G93A mice. These higher expression-levels of mitochondrial Ca2+ transporters in individual hMNs were not associated with a respective increase in number of mitochondrial genomes, as evident from hMN specific ND1 DNA quantification. Normalized mRNA-levels for the plasma membrane Na2+/Ca2+exchanger NCX1 was also about 2-fold higher in hMNs from SOD1G93A mice. Thus, pharmacological stimulation of Ca2+ transporters in highly vulnerable hMNs might offer a novel neuroprotective strategy for ALS.

  3. The effects of 3% diquafosol sodium eye drop application on meibomian gland and ocular surface alterations in the Cu, Zn-superoxide dismutase-1 (Sod1) knockout mice.

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    Ikeda, Keisuke; Simsek, Cem; Kojima, Takashi; Higa, Kazunari; Kawashima, Motoko; Dogru, Murat; Shimizu, Takahiko; Tsubota, Kazuo; Shimazaki, Jun

    2018-04-01

    The purpose of the study is to investigate the effect of 3% diquafosol sodium eye drops on meibomian gland and ocular surface alterations in the superoxide dismutase-1 (Sod1 -/- ) mice in comparison to the wild-type mouse. Three percent diquafosol sodium eye drop was instilled to 20 eyes of 10 50-week-old male Sod1 -/- mice and 22 eyes of 11 C57BL/6 strain 50-week-old wild-type (WT) male mice six times a day for 2 weeks. Aqueous tear secretion quantity was measured with phenol red-impregnated cotton threads without anesthesia. Tear film stability and corneal epithelial damage were assessed by fluorescein and lissamine green staining. We also performed oil red O (ORO) lipid staining to evaluate the lipid changes in the meibomian glands. Meibomian gland specimens underwent hematoxylin and eosin staining to examine histopathological changes and meibomian gland acinar unit density after sacrifice. Immunohistochemistry staining was performed using cytokeratin 4, cytokeratin 13, and transglutaminase-1 antibodies. Quantitative real-time polymerase chain reaction for cytokeratin 4, cytokeratin 13, and transglutaminase-1 mRNA expression was also performed. The aqueous tear quantity, the mean tear film breakup time, and the number of lipid droplets significantly improved in the Sod1 -/- mice with treatment. The mean meibomian acinar unit density did not change in the Sod1 -/- mice and WT mice after treatment. Application of 3% diquafosol sodium eye drop significantly decreased the corneal fluorescein and lissamine green staining scores in the Sod1 -/- mice after 2 weeks. We showed a notable increase in cytokeratin 4, cytokeratin 13 immunohistochemistry staining, and cytokeratin 4, cytokeratin 13 mRNA expressions with a marked decrease in immunohistochemistry staining and significant decline in mRNA expression of transglutaminase-1 after 3% diquafosol sodium treatment. Topical application of 3% diquafosol sodium eye drop improved the number of lipid droplets, tear stability

  4. Monomers and Monomer Mixtures Used in Impregnation of Fibrous Materials

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1968-10-15

    Some important properties of monomers and polymers in relation to their use for reinforcement of fibrous materials are listed. Some monomers and their properties important in impregnation of fibrous materials are also listed. In general it is not advantageous to use a pure monomer for impregnation but rather a mixture of monomers or a mixture of a monomer and a low molecular weight polymer such as unsaturated polyester. Some of these mixtures which have been well studied in connection with WPC are listed together with some of their properties when used in WPC. Other monomer mixtures may well come in question and other monomers can probably be used. For instance, it is reported from Japan that the cheap monomer ethyleneoxide, which cannot be polymerized by gamma radiation as such, can be polymerized (in bulk) as a mixture with methylmethacrylate. Good results with WPC have generally been obtained without swelling agents but more is grafted if some swelling agent is used, and it is possible that a swelling agent might be useful in the case of fibre-boards. Solvents, plasticizers, crosslinkable natural resins, aromatic chlorinated hydrocarbons, and retardants can be added, and with their use the properties of WPC can be widely modified. For example, a chlorinated wax can act as retardant, can reduce the total dose of radiation and can increase the flame resistance simultaneously.

  5. On the formation of polymer non-grafted onto the surface during radiation-induced polymerization of monomers adsorbed on mineral substrates

    International Nuclear Information System (INIS)

    Bruk, M.A.; Mund, S.L.; Aksman, I.B.; Abkin, A.D.

    1977-01-01

    It has been established that during radiation polymerization of vinylacetate and acrylonitrile, adsorbed on aerosil from the vapour phase, considerable amounts of the polymer are formed even at the initial stage of the process which is extracted by the organic solvents. It has been shown for polyvinylacetate as an example that probability of the polymer chain located on the surface to transfer into the solution depends not only on the ''quality'' of the solvent with respect to the given polymer but on the energy of solvent interaction with the surface adsorption centers as well. It has been observed that the molecular mass of PVA extracted from the aerosil surface by acetone is several times lower than that of PVA which remains on the surface after treating with acetone. Probable participation of low-molecular radicals in the formation of polymer chains not forming a chemical bond with the surface has been considered

  6. Histamine Regulates the Inflammatory Profile of SOD1-G93A Microglia and the Histaminergic System Is Dysregulated in Amyotrophic Lateral Sclerosis

    Directory of Open Access Journals (Sweden)

    Savina Apolloni

    2017-11-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is a late-onset motor neuron disease where activated glia release pro-inflammatory cytokines that trigger a vicious cycle of neurodegeneration in the absence of resolution of inflammation. Given the well-established role of histamine as a neuron-to-glia alarm signal implicated in brain disorders, the aim of this study was to investigate the expression and regulation of the histaminergic pathway in microglial activation in ALS mouse model and in humans. By examining the contribution of the histaminergic system to ALS, we found that particularly via H1 and H4 receptors, histamine promoted an anti-inflammatory profile in microglia from SOD1-G93A mice by modulating their activation state. A decrease in NF-κB and NADPH oxidase 2 with an increase in arginase 1 and P2Y12 receptor was induced by histamine only in the ALS inflammatory environment, but not in the healthy microglia, together with an increase in IL-6, IL-10, CD163, and CD206 phenotypic markers in SOD1-G93A cells. Moreover, histaminergic H1, H2, H3, and H4 receptors, and histamine metabolizing enzymes histidine decarboxylase, histamine N-methyltransferase, and diamine oxidase were found deregulated in spinal cord, cortex, and hypothalamus of SOD1-G93A mice during disease progression. Finally, by performing a meta-analysis study, we found a modulated expression of histamine-related genes in cortex and spinal cord from sporadic ALS patients. Our findings disclose that histamine acts as anti-inflammatory agent in ALS microglia and suggest a dysregulation of the histaminergic signaling in ALS.

  7. Optimised and rapid pre-clinical screening in the SOD1(G93A transgenic mouse model of amyotrophic lateral sclerosis (ALS.

    Directory of Open Access Journals (Sweden)

    Richard J Mead

    Full Text Available The human SOD1(G93A transgenic mouse has been used extensively since its development in 1994 as a model for amyotrophic lateral sclerosis (ALS. In that time, a great many insights into the toxicity of mutant SOD1 have been gained using this and other mutant SOD transgenic mouse models. They all demonstrate a selective toxicity towards motor neurons and in some cases features of the pathology seen in the human disease. These models have two major drawbacks. Firstly the generation of robust preclinical data in these models has been highlighted as an area for concern. Secondly, the amount of time required for a single preclinical experiment in these models (3-4 months is a hurdle to the development of new therapies. We have developed an inbred C57BL/6 mouse line from the original mixed background (SJLxC57BL/6 SOD1(G93A transgenic line and show here that the disease course is remarkably consistent and much less prone to background noise, enabling reduced numbers of mice for testing of therapeutics. Secondly we have identified very early readouts showing a large decline in motor function compared to normal mice. This loss of motor function has allowed us to develop an early, sensitive and rapid screening protocol for the initial phases of denervation of muscle fibers, observed in this model. We describe multiple, quantitative readouts of motor function that can be used to interrogate this early mechanism. Such an approach will increase throughput for reduced costs, whilst reducing the severity of the experimental procedures involved.

  8. Degenerative myelopathy in German Shepherd Dog: comparison of two molecular assays for the identification of the SOD1:c.118G>A mutation.

    Science.gov (United States)

    Capucchio, Maria Teresa; Spalenza, Veronica; Biasibetti, Elena; Bottero, Maria Teresa; Rasero, Roberto; Dalmasso, Alessandra; Sacchi, Paola

    2014-02-01

    Degenerative myelopathy (DM) is a late-onset, slowly progressive degeneration of spinal cord white matter which is reported primarily in large breed dogs. The missense mutation SOD1:c.118G>A is associated with this pathology in several dog breeds, including the German Shepherd Dog (GSD). The aims of the present study were to develop a tool for the rapid screening of the SOD1 mutation site in dogs and to evaluate the association of the polymorphism with DM in the German Shepherd breed. Two different techniques were compared: a minisequencing test and a real-time pcr allelic discrimination assay. Both approaches resulted effective and efficient. A sample of 47 dogs were examined. Ten subjects presented the symptoms of the illness; for one of them the diagnosis was confirmed by postmortem investigations and it resulted to be an A/A homozygote. In another clinically suspected dog, heterozygote A/G, the histopathological examination of the medulla showed moderate axon and myelin degenerative changes. GSD shows a frequency of the mutant allele equal to 0.17, quite high being a high-risk allele. Because canine DM has a late onset in adulthood and homozygous mutant dogs are likely as fertile as other genotypes, the natural selection is mild and the mutant allele may reach high frequencies. A diagnostic test, easy to implement, may contribute to control the gene diffusion in populations. The SOD1:c.118G>A mutation could be a useful marker for breeding strategies intending to reduce the incidence of DM.

  9. Optimised and rapid pre-clinical screening in the SOD1(G93A) transgenic mouse model of amyotrophic lateral sclerosis (ALS).

    Science.gov (United States)

    Mead, Richard J; Bennett, Ellen J; Kennerley, Aneurin J; Sharp, Paul; Sunyach, Claire; Kasher, Paul; Berwick, Jason; Pettmann, Brigitte; Battaglia, Guiseppe; Azzouz, Mimoun; Grierson, Andrew; Shaw, Pamela J

    2011-01-01

    The human SOD1(G93A) transgenic mouse has been used extensively since its development in 1994 as a model for amyotrophic lateral sclerosis (ALS). In that time, a great many insights into the toxicity of mutant SOD1 have been gained using this and other mutant SOD transgenic mouse models. They all demonstrate a selective toxicity towards motor neurons and in some cases features of the pathology seen in the human disease. These models have two major drawbacks. Firstly the generation of robust preclinical data in these models has been highlighted as an area for concern. Secondly, the amount of time required for a single preclinical experiment in these models (3-4 months) is a hurdle to the development of new therapies. We have developed an inbred C57BL/6 mouse line from the original mixed background (SJLxC57BL/6) SOD1(G93A) transgenic line and show here that the disease course is remarkably consistent and much less prone to background noise, enabling reduced numbers of mice for testing of therapeutics. Secondly we have identified very early readouts showing a large decline in motor function compared to normal mice. This loss of motor function has allowed us to develop an early, sensitive and rapid screening protocol for the initial phases of denervation of muscle fibers, observed in this model. We describe multiple, quantitative readouts of motor function that can be used to interrogate this early mechanism. Such an approach will increase throughput for reduced costs, whilst reducing the severity of the experimental procedures involved.

  10. CCS and SOD1 mRNA are reduced after copper supplementation in peripheral mononuclear cells of individuals with high serum ceruloplasmin concentration.

    Science.gov (United States)

    Suazo, Miriam; Olivares, Felipe; Mendez, Marco A; Pulgar, Rodrigo; Prohaska, Joseph R; Arredondo, Miguel; Pizarro, Fernando; Olivares, Manuel; Araya, Magdalena; González, Mauricio

    2008-04-01

    The limits of copper homeostatic regulation in humans are not known, making it difficult to define the milder effects of early copper excess. Furthermore, a robust assay to facilitate the detection of early stages of copper excess is needed. To address these issues, we assessed changes in relative mRNA abundance of methallothionein 2A (MT2A), prion (PrP), amyloid precursor-like protein 2 (APLP2), Cu/Zn superoxide dismutase (SOD1) and its copper chaperone (CCS) in peripheral mononuclear cells (PMNCs) from healthy adults representing the 5% highest and lowest extremes in the distribution curve of serum ceruloplasmin (Cp) concentrations of 800 individuals. The intracellular Cu content was also determined. PMNCs were isolated from individuals before and after exposure to a single daily dose of 10 mg Cu (as CuSO(4)) for 2 months. Results showed that although there were fluctuations in serum Cp values of the samples assessed before copper exposure, no significant differences were observed in cell copper content or in the relative abundance of MT2A, PrP and APLP2 transcripts in PMNCs. Also, these values were not modified after copper supplementation. However, CCS and SOD1 mRNA levels were reduced in PMNCs after copper supplementation in the individuals with the high Cp values, suggesting that they should be further explored as biomarkers of moderate copper overload in humans.

  11. Non-invasive assessment of animal exercise stress: real-time PCR of GLUT4, COX2, SOD1 and HSP70 in avalanche military dog saliva.

    Science.gov (United States)

    Diverio, S; Guelfi, G; Barbato, O; Di Mari, W; Egidi, M G; Santoro, M M

    2015-01-01

    Exercise has been shown to increase mRNA expression of a growing number of genes. The aim of this study was to assess if mRNA expression of the metabolism- and oxidative stress-related genes GLUT4 (glucose transporter 4), COX2 (cyclooxygenase 2), SOD1 (superoxide dismutase 1) and HSP70 (heat shock protein 70) in saliva changes following acute exercise stress in dogs. For this purpose, 12 avalanche dogs of the Italian Military Force Guardia di Finanza were monitored during simulation of a search for a buried person in an artificial avalanche area. Rectal temperature (RT) and saliva samples were collected the day before the trial (T0), immediately after the descent from a helicopter at the onset of a simulated avalanche search and rescue operation (T1), after the discovery of the buried person (T2) and 2 h later (T3). Expressions of GLUT4, SOD1, COX2 and HSP70 were measured by real-time PCR. The simulated avalanche search and rescue operation was shown to exert a significant effect on RT, as well as on the expression of all metabolism- and oxidative stress-related genes investigated, which peaked at T2. The observed expression patterns indicate an acute exercise stress-induced upregulation, as confirmed by the reductions in expression at T3. Moreover, our findings indicate that saliva is useful for assessing metabolism- and oxidative stress-related genes without the need for restraint, which could affect working dog performance.

  12. Ionic Liquid Epoxy Resin Monomers

    Science.gov (United States)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  13. Elution of Monomers from Provisional Composite Materials

    Directory of Open Access Journals (Sweden)

    Simon Daniel Schulz

    2015-01-01

    Full Text Available The aim of this study was to evaluate the elution of substances from different materials used for the manufacturing of temporary indirect restorations, after storage in saliva and ethanol 75%. 10 samples of three chemically cured materials (Protemp 3 Garant, Systemp.c&b, and Trim and one light-cured material (Clip F were stored in saliva and ethanol 75% for 24 h, 7, and days 28 days. From the storage media at each time period, samples were prepared and analysed by LC-MS/MS, in order to access the elution of monomers. The results differed among the materials (P ≤ 0.05. No monomers were detected in the samples of Protemp 3 Garant and Clip F. Substances were detected only in ethanol samples of Systemp.c&b and Trim. The amount of BisGMA, TEGDMA, and UDMA 2 released from Systemp.c&b was higher compared to Trim. Storage time affected the release of substances (P ≤ 0.05. The highest release was observed within the first 24 h. It can be concluded that provisional resin composite materials do not show high release of monomers and this release is material dependent. However, the detection of additional peaks during the analysis, suggesting the formation of by-products of the eluted substances, may not be in favour of these materials with respect to their toxicity.

  14. Exercise training improves relaxation response and SOD-1 expression in aortic and mesenteric rings from high caloric diet-fed rats

    Directory of Open Access Journals (Sweden)

    Antunes Edson

    2008-05-01

    Full Text Available Abstract Background Obesity has been associated with a variety of disease such as type II diabetes mellitus, arterial hypertension and atherosclerosis. Evidences have shown that exercise training promotes beneficial effects on these disorders, but the underlying mechanisms are not fully understood. The aim of this study was to investigate whether physical preconditioning prevents the deleterious effect of high caloric diet in vascular reactivity of rat aortic and mesenteric rings. Methods Male Wistar rats were divided into sedentary (SD; trained (TR; sedentary diet (SDD and trained diet (TRD groups. Run training (RT was performed in sessions of 60 min, 5 days/week for 12 weeks (70–80% VO2max. Triglycerides, glucose, insulin and nitrite/nitrate concentrations (NOx- were measured. Concentration-response curves to acetylcholine (ACh and sodium nitroprusside (SNP were obtained. Expression of Cu/Zn superoxide dismutase (SOD-1 was assessed by Western blotting. Results High caloric diet increased triglycerides concentration (SDD: 216 ± 25 mg/dl and exercise training restored to the baseline value (TRD: 89 ± 9 mg/dl. Physical preconditioning significantly reduced insulin levels in both groups (TR: 0.54 ± 0.1 and TRD: 1.24 ± 0.3 ng/ml as compared to sedentary animals (SD: 0.87 ± 0.1 and SDD: 2.57 ± 0.3 ng/ml. On the other hand, glucose concentration was slightly increased by high caloric diet, and RT did not modify this parameter (SD: 126 ± 6; TR: 140 ± 8; SDD: 156 ± 8 and TRD 153 ± 9 mg/dl. Neither high caloric diet nor RT modified NOx- levels (SD: 27 ± 4; TR: 28 ± 6; SDD: 27 ± 3 and TRD: 30 ± 2 μM. Functional assays showed that high caloric diet impaired the relaxing response to ACh in mesenteric (about 13%, but not in aortic rings. RT improved the relaxing responses to ACh either in aortic (28%, for TR and 16%, to TRD groups or mesenteric rings (10%, for TR and 17%, to TRD groups that was accompanied by up-regulation of SOD-1

  15. Acrolein-Induced Oxidative Stress and Cell Death Exhibiting Features of Apoptosis in the Yeast Saccharomyces cerevisiae Deficient in SOD1.

    Science.gov (United States)

    Kwolek-Mirek, Magdalena; Zadrąg-Tęcza, Renata; Bednarska, Sabina; Bartosz, Grzegorz

    2015-04-01

    The yeast Saccharomyces cerevisiae is a useful eukaryotic model to study the toxicity of acrolein, an important environmental toxin and endogenous product of lipid peroxidation. The study was aimed at elucidation of the cytotoxic effect of acrolein on the yeast deficient in SOD1, Cu, Zn-superoxide dismutase which is hypersensitive to aldehydes. Acrolein generated within the cell from its precursor allyl alcohol caused growth arrest and cell death of the yeast cells. The growth inhibition involved an increase in production of reactive oxygen species and high level of protein carbonylation. DNA condensation and fragmentation, exposition of phosphatidylserine at the cell surface as well as decreased dynamic of actin microfilaments and mitochondria disintegration point to the induction of apoptotic-type cell death besides necrotic cell death.

  16. [Lower urinary tract dysfunction and neuropathological findings of the neural circuits controlling micturition in familial amyotrophic lateral sclerosis with L106V mutation in the SOD1 gene].

    Science.gov (United States)

    Hineno, Akiyo; Oyanagi, Kiyomitsu; Nakamura, Akinori; Shimojima, Yoshio; Yoshida, Kunihiro; Ikeda, Shu-Ichi

    2016-01-01

    We report lower urinary tract dysfunction and neuropathological findings of the neural circuits controlling micturition in the patients with familial amyotrophic lateral sclerosis having L106V mutation in the SOD1 gene. Ten of 20 patients showed lower urinary tract dysfunction and 5 patients developed within 1 year after the onset of weakness. In 8 patients with an artificial respirator, 6 patients showed lower urinary tract dysfunction. Lower urinary tract dysfunction and respiratory failure requiring an artificial respirator occurred simultaneously in 3 patients. Neuronal loss and gliosis were observed in the neural circuits controlling micturition, such as frontal lobe, thalamus, hypothalamus, striatum, periaqueductal gray, ascending spinal tract, lateral corticospinal tract, intermediolateral nucleus and Onufrowicz' nucleus. Lower urinary tract dysfunction, especially storage symptoms, developed about 1 year after the onset of weakness, and the dysfunction occurred simultaneously with artificial respirator use in the patients.

  17. Unlike physical exercise, modified environment increases the lifespan of SOD1G93A mice however both conditions induce cellular changes.

    Directory of Open Access Journals (Sweden)

    Yannick N Gerber

    Full Text Available Amyotrophic lateral sclerosis (ALS is characterized by a gradual muscular paralysis resulting from progressive motoneurons death. ALS etiology remains unknown although it has been demonstrated to be a multifactorial disease involving several cellular partners. There is currently no effective treatment. Even if the effect of exercise is under investigation for many years, whether physical exercise is beneficial or harmful is still under debate.We investigated the effect of three different intensities of running exercises on the survival of SOD1(G93A mice. At the early-symptomatic stage (P60, males were isolated and randomly assigned to 5 conditions: 2 sedentary groups ("sedentary" and "sedentary treadmill" placed on the inert treadmill, and 3 different training intensity groups (5 cm/s, 10 cm/s and 21 cm/s; 15 min/day, 5days/week. We first demonstrated that an appropriate "control" of the environment is of the utmost importance since comparison of the two sedentary groups evidenced an 11.6% increase in survival in the "sedentary treadmill" group. Moreover, we showed by immunohistochemistry that this increased lifespan is accompanied with motoneurons survival and increased glial reactivity in the spinal cord. In a second step, we showed that when compared with the proper control, all three running-based training did not modify lifespan of the animals, but result in motoneurons preservation and changes in glial cells activation.We demonstrate that increase in survival induced by a slight daily modification of the environment is associated with motoneurons preservation and strong glial modifications in the lumbar spinal cord of SOD1(G93A. Using the appropriate control, we then demonstrate that all running intensities have no effect on the survival of ALS mice but induce cellular modifications. Our results highlight the critical importance of the control of the environment in ALS studies and may explain discrepancy in the literature regarding the

  18. A Cystine-Rich Whey Supplement (Immunocal® Delays Disease Onset and Prevents Spinal Cord Glutathione Depletion in the hSOD1G93A Mouse Model of Amyotrophic Lateral Sclerosis

    Directory of Open Access Journals (Sweden)

    Erika K. Ross

    2014-12-01

    Full Text Available Depletion of the endogenous antioxidant, glutathione (GSH, underlies progression of the devastating neurodegenerative disease, amyotrophic lateral sclerosis (ALS. Thus, strategies aimed at elevating GSH may yield new therapeutics for ALS. Here, we investigated the effects of a unique non-denatured whey protein supplement, Immunocal®, in the transgenic Gly position 93 to Ala (G93A mutant hSOD1 (hSOD1G93A mouse model of ALS. Immunocal® is rich in the GSH precursor, cystine, and is therefore capable of bolstering GSH content. Transgenic hSOD1G93A mice receiving Immunocal® displayed a significant delay in disease onset compared to untreated hSOD1G93A controls. Additionally, Immunocal® treatment significantly decreased the rate of decline in grip strength and prevented disease-associated reductions in whole blood and spinal cord tissue GSH levels in end-stage hSOD1G93A mice. However, Immunocal® did not extend survival, likely due to its inability to preserve the mitochondrial GSH pool in spinal cord. Combination treatment with Immunocal® and the anti-glutamatergic compound, riluzole, delayed disease onset and extended survival in hSOD1G93A mice. These findings demonstrate that sustaining tissue GSH with Immunocal® only modestly delays disease onset and slows the loss of skeletal muscle strength in hSOD1G93A mice. Moreover, the inability of Immunocal® to rescue mitochondrial GSH in spinal cord provides a possible mechanism for its lack of effect on survival and is a limiting factor in the potential utility of this supplement as a therapeutic for ALS.

  19. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran

    Directory of Open Access Journals (Sweden)

    Sari Fouad

    2012-12-01

    Full Text Available We reported in this work that the cationic copolymerization in one step takes place between carbon–carbon double-bond monomer styrene with cyclic monomer tetrahydrofuran. The comonomers studied belong to different families: vinylic and cyclic ether. The reaction is initiated with maghnite-H+ an acid exchanged montmorillonite as acid solid ecocatalyst. Maghnite-H+ is already used as catalyst for polymerization of many vinylic and heterocyclic monomers. The oxonium ion of tetrahydrofuran and carbonium ion of styrene propagated the reaction of copolymerization. The acetic anhydride is essential for the maintenance of the ring opening of tetrahydrofuran and the entry in copolymerization. The temperature was kept constant at 40°C in oil bath heating for 6 hours. A typical reaction product was analyzed by 1H-NMR, 13C-NMR and IR and the formation of the copolymer was confirmed. The reaction was proved by matched with analysis. The maghnite-H+ allowed us to obtain extremely pure copolymer in good yield by following a simples operational conditions. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 29th October 2012; Revised: 29th November 2012; Accepted: 29th November 2012[How to Cite: S. Fouad, M.I. Ferrahi, M. Belbachir. (2012. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 165-171. (doi:10.9767/bcrec.7.2.4074.165-171][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.4074.165-171 ] | View in 

  20. Comparative Analyses of Cu-Zn Superoxide Dismutase (SOD1) and Thioredoxin Reductase (TrxR) at the mRNA Level between Apis mellifera L. and Apis cerana F. (Hymenoptera: Apidae) Under Stress Conditions.

    Science.gov (United States)

    Koo, Hyun-Na; Lee, Soon-Gyu; Yun, Seung-Hwan; Kim, Hyun Kyung; Choi, Yong Soo; Kim, Gil-Hah

    2016-01-01

    This study compared stress-induced expression of Cu-Zn superoxide dismutase (SOD1) and thioredoxin reductase (TrxR) genes in the European honeybee Apis mellifera L. and Asian honeybee Apis cerana F. Expression of both SOD1 and TrxR rapidly increased up to 5 h after exposure to cold (4 °C) or heat (37 °C) treatment and then gradually decreased, with a stronger effect induced by cold stress in A. mellifera compared with A. cerana. Injection of stress-inducing substances (methyl viologen, [MV] and H2O2) also increased SOD1 and TrxR expression in both A. mellifera and A. cerana, and this effect was more pronounced with MV than H2O2. Additionally, we heterologously expressed the A. mellifera and A. cerana SOD1 and TrxR proteins in an Escherichia coli expression system, and detection by SDS-PAGE, confirmed by Western blotting using anti-His tag antibodies, revealed bands at 16 and 60 kDa, respectively. Our results show that the expression patterns of SOD1 and TrxR differ between A. mellifera and A. cerana under conditions of low or high temperature as well as oxidative stress. © The Author 2016. Published by Oxford University Press on behalf of the Entomological Society of America.

  1. In vivo EPR pharmacokinetic evaluation of the redox status and the blood brain barrier permeability in the SOD1G93A ALS rat model.

    Science.gov (United States)

    Stamenković, Stefan; Pavićević, Aleksandra; Mojović, Miloš; Popović-Bijelić, Ana; Selaković, Vesna; Andjus, Pavle; Bačić, Goran

    2017-07-01

    Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disorder affecting the motor pathways of the central nervous system. Although a number of pathophysiological mechanisms have been described in the disease, post mortem and animal model studies indicate blood-brain barrier (BBB) disruption and elevated production of reactive oxygen species as major contributors to disease pathology. In this study, the BBB permeability and the brain tissue redox status of the SOD1 G93A ALS rat model in the presymptomatic (preALS) and symptomatic (ALS) stages of the disease were investigated by in vivo EPR spectroscopy using three aminoxyl radicals with different cell membrane and BBB permeabilities, Tempol, 3-carbamoyl proxyl (3CP), and 3-carboxy proxyl (3CxP). Additionally, the redox status of the two brain regions previously implicated in disease pathology, brainstem and hippocampus, was investigated by spectrophotometric biochemical assays. The EPR results indicated that among the three spin probes, 3CP is the most suitable for reporting the intracellular redox status changes, as Tempol was reduced in vivo within minutes (t 1/2 =2.0±0.5min), thus preventing reliable kinetic modeling, whereas 3CxP reduction kinetics gave divergent conclusions, most probably due to its membrane impermeability. It was observed that the reduction kinetics of 3CP in vivo, in the head of preALS and ALS SOD1 G93A rats was altered compared to the controls. Pharmacokinetic modeling of 3CP reduction in vivo, revealed elevated tissue distribution and tissue reduction rate constants indicating an altered brain tissue redox status, and possibly BBB disruption in these animals. The preALS and ALS brain tissue homogenates also showed increased nitrilation, superoxide production, lipid peroxidation and manganese superoxide dismutase activity, and a decreased copper-zinc superoxide dismutase activity. The present study highlights in vivo EPR spectroscopy as a reliable tool for the investigation of

  2. Spinal cord pathology is ameliorated by P2X7 antagonism in a SOD1-mutant mouse model of amyotrophic lateral sclerosis

    Directory of Open Access Journals (Sweden)

    Savina Apolloni

    2014-09-01

    Full Text Available In recent years there has been an increasing awareness of the role of P2X7, a receptor for extracellular ATP, in modulating physiopathological mechanisms in the central nervous system. In particular, P2X7 has been shown to be implicated in neuropsychiatry, chronic pain, neurodegeneration and neuroinflammation. Remarkably, P2X7 has also been shown to be a ‘gene modifier’ in amyotrophic lateral sclerosis (ALS: the receptor is upregulated in spinal cord microglia in human and rat at advanced stages of the disease; in vitro, activation of P2X7 exacerbates pro-inflammatory responses in microglia that have an ALS phenotype, as well as toxicity towards neuronal cells. Despite this detrimental in vitro role of P2X7, in SOD1-G93A mice lacking P2X7, the clinical onset of ALS was significantly accelerated and disease progression worsened, thus indicating that the receptor might have some beneficial effects, at least at certain stages of disease. In order to clarify this dual action of P2X7 in ALS pathogenesis, in the present work we used the antagonist Brilliant Blue G (BBG, a blood-brain barrier permeable and safe drug that has already been proven to reduce neuroinflammation in traumatic brain injury, cerebral ischemia-reperfusion, neuropathic pain and experimental autoimmune encephalitis. We tested BBG in the SOD1-G93A ALS mouse model at asymptomatic, pre-symptomatic and late pre-symptomatic phases of disease. BBG at late pre-onset significantly enhanced motor neuron survival and reduced microgliosis in lumbar spinal cord, modulating inflammatory markers such as NF-κB, NADPH oxidase 2, interleukin-1β, interleukin-10 and brain-derived neurotrophic factor. This was accompanied by delayed onset and improved general conditions and motor performance, in both male and female mice, although survival appeared unaffected. Our results prove the twofold role of P2X7 in the course of ALS and establish that P2X7 modulation might represent a promising

  3. An inducer of VGF protects cells against ER stress-induced cell death and prolongs survival in the mutant SOD1 animal models of familial ALS.

    Directory of Open Access Journals (Sweden)

    Masamitsu Shimazawa

    2010-12-01

    Full Text Available Amyotrophic lateral sclerosis (ALS is the most frequent adult-onset motor neuron disease, and recent evidence has suggested that endoplasmic reticulum (ER stress signaling is involved in the pathogenesis of ALS. Here we identified a small molecule, SUN N8075, which has a marked protective effect on ER stress-induced cell death, in an in vitro cell-based screening, and its protective mechanism was mediated by an induction of VGF nerve growth factor inducible (VGF: VGF knockdown with siRNA completely abolished the protective effect of SUN N8075 against ER-induced cell death, and overexpression of VGF inhibited ER-stress-induced cell death. VGF level was lower in the spinal cords of sporadic ALS patients than in the control patients. Furthermore, SUN N8075 slowed disease progression and prolonged survival in mutant SOD1 transgenic mouse and rat models of ALS, preventing the decrease of VGF expression in the spinal cords of ALS mice. These data suggest that VGF plays a critical role in motor neuron survival and may be a potential new therapeutic target for ALS, and SUN N8075 may become a potential therapeutic candidate for treatment of ALS.

  4. Postactivation depression of the Ia EPSP in motoneurons is reduced in both the G127X SOD1 model of amyotrophic lateral sclerosis and in aged mice

    DEFF Research Database (Denmark)

    Hedegaard, Anne; Lehnhoff, Janna; Moldovan, Mihai

    2015-01-01

    Post Activation Depression (PActD) of Ia afferent EPSPs in spinal motoneurons results in a long lasting depression of the stretch reflex. PActD is of clinical interest as it has been shown to be reduced in a number of spastic disorders. Using in vivo intracellular recordings of Ia EPSPs in adult...... mice, we demonstrate that PActD in adult (100-220 days) C57BL/6J mice is both qualitatively and quantitatively similar to that which has been observed in larger animals with respect to both magnitude (approximately 20% depression of EPSPs at 0.5 ms after a stimuli train) and time course (returning...... Sclerosis (ALS). Using the G127X SOD1 mutant mouse, an ALS model with a prolonged asymptomatic phase and fulminant symptom onset, we observed that PActD is significantly reduced at both pre-symptomatic (16% depression) and symptomatic (17.3% depression) time points compared to aged-matched controls (22...

  5. Systemic injection of AAV9-GDNF provides modest functional improvements in the SOD1G93A ALS rat but has adverse side effects.

    Science.gov (United States)

    Thomsen, G M; Alkaslasi, M; Vit, J-P; Lawless, G; Godoy, M; Gowing, G; Shelest, O; Svendsen, C N

    2017-04-01

    Injecting proteins into the central nervous system that stimulate neuronal growth can lead to beneficial effects in animal models of disease. In particular, glial cell line-derived neurotrophic factor (GDNF) has shown promise in animal and cell models of Parkinson's disease, Huntington's disease and amyotrophic lateral sclerosis (ALS). Here, systemic AAV9-GDNF was delivered via tail vein injections to young rats to determine whether this could be a safe and functional strategy to treat the SOD1 G93A rat model of ALS and, therefore, translated to a therapy for ALS patients. We found that GDNF administration in this manner resulted in modest functional improvement, whereby grip strength was maintained for longer and the onset of forelimb paralysis was delayed compared to non-treated rats. This did not, however, translate into an extension in survival. In addition, ALS rats receiving GDNF exhibited slower weight gain, reduced activity levels and decreased working memory. Collectively, these results confirm that caution should be applied when applying growth factors such as GDNF systemically to multiple tissues.

  6. Dysregulated expression of death, stress and mitochondrion related genes in the sciatic nerve of presymptomatic SOD1G93A mouse model of Amyotrophic Lateral Sclerosis

    Directory of Open Access Journals (Sweden)

    Chrystian Junqueira Alves

    2015-09-01

    Full Text Available Schwann cells are the main source of paracrine support to motor neurons. Oxidative stress and mitochondrial dysfunction have been correlated to motor neuron death in Amyotrophic Lateral Sclerosis (ALS. Despite the involvement of Schwann cells in early neuromuscular disruption in ALS, detailed molecular events of a dying-back triggering are unknown. Sciatic nerves of presymptomatic (60-day-old SOD1G93A mice were submitted to a high-density oligonucleotide microarray analysis. DAVID demonstrated the deregulated genes related to death, stress and mitochondrion, which allowed the identification of Cell cycle, ErbB signaling, Tryptophan metabolism and Rig-I-like receptor signaling as the most representative KEGG pathways. The protein-protein interaction networks based upon deregulated genes have identified the top hubs (TRAF2, H2AFX, E2F1, FOXO3, MSH2, NGFR, TGFBR1 and bottlenecks (TRAF2, E2F1, CDKN1B, TWIST1, FOXO3. Schwann cells were enriched from the sciatic nerve of presymptomatic mice using flow cytometry cell sorting. qPCR showed the up regulated (Ngfr, Cdnkn1b, E2f1, Traf2 and Erbb3, H2afx, Cdkn1a, Hspa1, Prdx, Mapk10 and down-regulated (Foxo3, Mtor genes in the enriched Schwann cells. In conclusion, molecular analyses in the presymptomatic sciatic nerve demonstrated the involvement of death, oxidative stress, and mitochondrial pathways in the Schwann cell non-autonomous mechanisms in the early stages of ALS.

  7. Evaluation of level of impregnation monomers in hydrotalcite

    International Nuclear Information System (INIS)

    Carmo, Danieli M. do; Machado, Jacson S.C.; Oliveira, Marcelo F.L.; Oliveira, Marcia G.; Soares, Bluma G.

    2011-01-01

    To evaluate the impregnation degree of 1,6-hexamethylene diisocyanate and 1,4-butanediol monomers in hydrotalcite clays it was prepared dispersions with mixing ratio 1:100 (clay/monomer), using the Ultraturrax and Ultrasound. Subsequently the samples were characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction. Swelling tests and Tyndall effect were used to illustrate the different dispersions. The results indicated a strong interaction between the hydrotalcite with 1,6-hexamethylene diisocyanate, favoring the formation of intercalated structures. (author)

  8. Association between single nucleotide polymorphisms in the antioxidant genes CAT, GR and SOD1, erythrocyte enzyme activities, dietary and life style factors and breast cancer risk in a Danish, prospective cohort study

    DEFF Research Database (Denmark)

    Kopp, Tine Iskov; Vogel, Ulla; Dragsted, Lars Ove

    2017-01-01

    Exposure to estrogens and alcohol consumption - the two only well-established risk factors for breast cancer - are capable of causing oxidative stress, which has been linked to progression of breast cancer. Here, five functional polymorphisms in the antioxidant genes SOD1, CAT and GSR were...

  9. ATF3 expression precedes death of spinal motoneurons in amyotrophic lateral sclerosis-SOD1 transgenic mice and correlates with c-Jun phosphorylation, CHOP expression, somato-dendritic ubiquitination and Golgi fragmentation

    NARCIS (Netherlands)

    Vlug, Angela S; Teuling, Eva; Haasdijk, Elize D; French, Pim; Hoogenraad, Casper C; Jaarsma, Dick

    2005-01-01

    To obtain insight into the morphological and molecular correlates of motoneuron degeneration in amyotrophic lateral sclerosis (ALS) mice that express G93A mutant superoxide dismutase (SOD)1 (G93A mice), we have mapped and characterized 'sick' motoneurons labelled by the 'stress transcription

  10. Enhancing NAD+ Salvage Pathway Reverts the Toxicity of Primary Astrocytes Expressing Amyotrophic Lateral Sclerosis-linked Mutant Superoxide Dismutase 1 (SOD1).

    Science.gov (United States)

    Harlan, Benjamin A; Pehar, Mariana; Sharma, Deep R; Beeson, Gyda; Beeson, Craig C; Vargas, Marcelo R

    2016-05-13

    Nicotinamide adenine dinucleotide (NAD(+)) participates in redox reactions and NAD(+)-dependent signaling pathways. Although the redox reactions are critical for efficient mitochondrial metabolism, they are not accompanied by any net consumption of the nucleotide. On the contrary, NAD(+)-dependent signaling processes lead to its degradation. Three distinct families of enzymes consume NAD(+) as substrate: poly(ADP-ribose) polymerases, ADP-ribosyl cyclases (CD38 and CD157), and sirtuins (SIRT1-7). Because all of the above enzymes generate nicotinamide as a byproduct, mammalian cells have evolved an NAD(+) salvage pathway capable of resynthesizing NAD(+) from nicotinamide. Overexpression of the rate-limiting enzyme in this pathway, nicotinamide phosphoribosyltransferase, increases total and mitochondrial NAD(+) levels in astrocytes. Moreover, targeting nicotinamide phosphoribosyltransferase to the mitochondria also enhances NAD(+) salvage pathway in astrocytes. Supplementation with the NAD(+) precursors nicotinamide mononucleotide and nicotinamide riboside also increases NAD(+) levels in astrocytes. Amyotrophic lateral sclerosis (ALS) is caused by the progressive degeneration of motor neurons in the spinal cord, brain stem, and motor cortex. Superoxide dismutase 1 (SOD1) mutations account for up to 20% of familial ALS and 1-2% of apparently sporadic ALS cases. Primary astrocytes isolated from mutant human superoxide dismutase 1-overexpressing mice as well as human post-mortem ALS spinal cord-derived astrocytes induce motor neuron death in co-culture. Increasing total and mitochondrial NAD(+) content in ALS astrocytes increases oxidative stress resistance and reverts their toxicity toward co-cultured motor neurons. Taken together, our results suggest that enhancing the NAD(+) salvage pathway in astrocytes could be a potential therapeutic target to prevent astrocyte-mediated motor neuron death in ALS. © 2016 by The American Society for Biochemistry and Molecular

  11. Enhancing NAD+ Salvage Pathway Reverts the Toxicity of Primary Astrocytes Expressing Amyotrophic Lateral Sclerosis-linked Mutant Superoxide Dismutase 1 (SOD1)*

    Science.gov (United States)

    Harlan, Benjamin A.; Pehar, Mariana; Sharma, Deep R.; Beeson, Gyda; Beeson, Craig C.; Vargas, Marcelo R.

    2016-01-01

    Nicotinamide adenine dinucleotide (NAD+) participates in redox reactions and NAD+-dependent signaling pathways. Although the redox reactions are critical for efficient mitochondrial metabolism, they are not accompanied by any net consumption of the nucleotide. On the contrary, NAD+-dependent signaling processes lead to its degradation. Three distinct families of enzymes consume NAD+ as substrate: poly(ADP-ribose) polymerases, ADP-ribosyl cyclases (CD38 and CD157), and sirtuins (SIRT1–7). Because all of the above enzymes generate nicotinamide as a byproduct, mammalian cells have evolved an NAD+ salvage pathway capable of resynthesizing NAD+ from nicotinamide. Overexpression of the rate-limiting enzyme in this pathway, nicotinamide phosphoribosyltransferase, increases total and mitochondrial NAD+ levels in astrocytes. Moreover, targeting nicotinamide phosphoribosyltransferase to the mitochondria also enhances NAD+ salvage pathway in astrocytes. Supplementation with the NAD+ precursors nicotinamide mononucleotide and nicotinamide riboside also increases NAD+ levels in astrocytes. Amyotrophic lateral sclerosis (ALS) is caused by the progressive degeneration of motor neurons in the spinal cord, brain stem, and motor cortex. Superoxide dismutase 1 (SOD1) mutations account for up to 20% of familial ALS and 1–2% of apparently sporadic ALS cases. Primary astrocytes isolated from mutant human superoxide dismutase 1-overexpressing mice as well as human post-mortem ALS spinal cord-derived astrocytes induce motor neuron death in co-culture. Increasing total and mitochondrial NAD+ content in ALS astrocytes increases oxidative stress resistance and reverts their toxicity toward co-cultured motor neurons. Taken together, our results suggest that enhancing the NAD+ salvage pathway in astrocytes could be a potential therapeutic target to prevent astrocyte-mediated motor neuron death in ALS. PMID:27002158

  12. Compensatory Motor Neuron Response to Chromatolysis in the Murine hSOD1G93A Model of Amyotrophic Lateral Sclerosis

    Science.gov (United States)

    Riancho, Javier; Ruiz-Soto, Maria; Villagrá, Nuria T.; Berciano, Jose; Berciano, Maria T.; Lafarga, Miguel

    2014-01-01

    We investigated neuronal self-defense mechanisms in a murine model of amyotrophic lateral sclerosis (ALS), the transgenic hSOD1G93A, during both the asymptomatic and symptomatic stages. This is an experimental model of endoplasmic reticulum (ER) stress with severe chromatolysis. As a compensatory response to translation inhibition, chromatolytic neurons tended to reorganize the protein synthesis machinery at the perinuclear region, preferentially at nuclear infolding domains enriched in nuclear pores. This organization could facilitate nucleo-cytoplasmic traffic of RNAs and proteins at translation sites. By electron microscopy analysis, we observed that the active euchromatin pattern and the reticulated nucleolar configuration of control motor neurons were preserved in ALS chromatolytic neurons. Moreover the 5′-fluorouridine (5′-FU) transcription assay, at the ultrastructural level, revealed high incorporation of the RNA precursor 5′-FU into nascent RNA. Immunogold particles of 5′-FU incorporation were distributed throughout the euchromatin and on the dense fibrillar component of the nucleolus in both control and ALS motor neurons. The high rate of rRNA transcription in ALS motor neurons could maintain ribosome biogenesis under conditions of severe dysfunction of proteostasis. Collectively, the perinuclear reorganization of protein synthesis machinery, the predominant euchromatin architecture, and the active nucleolar transcription could represent compensatory mechanisms in ALS motor neurons in response to the disturbance of ER proteostasis. In this scenario, epigenetic activation of chromatin and nucleolar transcription could have important therapeutic implications for neuroprotection in ALS and other neurodegenerative diseases. Although histone deacetylase inhibitors are currently used as therapeutic agents, we raise the untapped potential of the nucleolar transcription of ribosomal genes as an exciting new target for the therapy of some neurodegenerative

  13. Surface active monomers synthesis, properties, and application

    CERN Document Server

    Borzenkov, Mykola

    2014-01-01

    This brief includes information on the background?of and development of synthesis of various types of surface active monomers. The authors explain the importance of utilization of surface active monomers for creation of surface active polymers? and the various biomedical applications of such compounds . This brief introduces techniques for the synthesis of novel types of surface active monomers, their colloidal and polymerizable properties and application for needs of medicine and biology.

  14. Monomers capable of forming four hydrogen bridges and supramolecular polymers formed by copolymerization of these monomers with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

  15. Perturbation of the Monomer-Monomer Interfaces of the Benzoylformate Decarboxylase Tetramer

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, Forest H.; Rogers, Megan P.; Paul, Lake N.; McLeish, Michael J. [IUPUI; (Purdue)

    2014-08-14

    The X-ray structure of benzoylformate decarboxylase (BFDC) from Pseudomonas putida ATCC 12633 shows it to be a tetramer. This was believed to be typical of all thiamin diphosphate-dependent decarboxylases until recently when the structure of KdcA, a branched-chain 2-keto acid decarboxylase from Lactococcus lactis, showed it to be a homodimer. This lent credence to earlier unfolding experiments on pyruvate decarboxylase from Saccharomyces cerevisiae that indicated that it might be active as a dimer. To investigate this possibility in BFDC, we sought to shift the equilibrium toward dimer formation. Point mutations were made in the noncatalytic monomer–monomer interfaces, but these had a minimal effect on both tetramer formation and catalytic activity. Subsequently, the R141E/Y288A/A306F variant was shown by analytical ultracentrifugation to be partially dimeric. It was also found to be catalytically inactive. Further experiments revealed that just two mutations, R141E and A306F, were sufficient to markedly alter the dimer–tetramer equilibrium and to provide an ~450-fold decrease in kcat. Equilibrium denaturation studies suggested that the residual activity was possibly due to the presence of residual tetramer. The structures of the R141E and A306F variants, determined to <1.5 Å resolution, hinted that disruption of the monomer interfaces will be accompanied by movement of a loop containing Leu109 and Leu110. As these residues contribute to the hydrophobicity of the active site and the correct positioning of the substrate, it seems that tetramer formation may well be critical to the catalytic activity of BFDC.

  16. Lack of TNF-alpha receptor type 2 protects motor neurons in a cellular model of amyotrophic lateral sclerosis and in mutant SOD1 mice but does not affect disease progression.

    Science.gov (United States)

    Tortarolo, Massimo; Vallarola, Antonio; Lidonnici, Dario; Battaglia, Elisa; Gensano, Francesco; Spaltro, Gabriella; Fiordaliso, Fabio; Corbelli, Alessandro; Garetto, Stefano; Martini, Elisa; Pasetto, Laura; Kallikourdis, Marinos; Bonetto, Valentina; Bendotti, Caterina

    2015-10-01

    Changes in the homeostasis of tumor necrosis factor α (TNFα) have been demonstrated in patients and experimental models of amyotrophic lateral sclerosis (ALS). However, the contribution of TNFα to the development of ALS is still debated. TNFα is expressed by glia and neurons and acts through the membrane receptors TNFR1 and TNFR2, which may have opposite effects in neurodegeneration. We investigated the role of TNFα and its receptors in the selective motor neuron death in ALS in vitro and in vivo. TNFR2 expressed by astrocytes and neurons, but not TNFR1, was implicated in motor neuron loss in primary SOD1-G93A co-cultures. Deleting TNFR2 from SOD1-G93A mice, there was partial but significant protection of spinal motor neurons, sciatic nerves, and tibialis muscles. However, no improvement of motor impairment or survival was observed. Since the sciatic nerves of SOD1-G93A/TNFR2-/- mice showed high phospho-TAR DNA-binding protein 43 (TDP-43) accumulation and low levels of acetyl-tubulin, two indices of axonal dysfunction, the lack of symptom improvement in these mice might be due to impaired function of rescued motor neurons. These results indicate the interaction between TNFR2 and membrane-bound TNFα as an innovative pathway involved in motor neuron death. Nevertheless, its inhibition is not sufficient to stop disease progression in ALS mice, underlining the complexity of this pathology. We show evidence of the involvement of neuronal and astroglial TNFR2 in the motor neuron degeneration in ALS. Both concur to cause motor neuron death in primary astrocyte/spinal neuron co-cultures. TNFR2 deletion partially protects motor neurons and sciatic nerves in SOD1-G93A mice but does not improve their symptoms and survival. However, TNFR2 could be a new target for multi-intervention therapies. © 2015 International Society for Neurochemistry.

  17. ZNStress: a high-throughput drug screening protocol for identification of compounds modulating neuronal stress in the transgenic mutant sod1G93R zebrafish model of amyotrophic lateral sclerosis

    OpenAIRE

    McGown, Alexander; Shaw, Dame Pamela J.; Ramesh, Tennore

    2016-01-01

    Background Amyotrophic lateral sclerosis (ALS) is a lethal neurodegenerative disease with death on average within 2?3 years of symptom onset. Mutations in superoxide dismutase 1 (SOD1) have been identified to cause ALS. Riluzole, the only neuroprotective drug for ALS provides life extension of only 3 months on average. Thishighlights the need for compound screening in disease models to identify new neuroprotective therapies for this disease. Zebrafish is an emerging model system that is well ...

  18. ZNStress: a high-throughput drug screening protocol for identification of compounds modulating neuronal stress in the transgenic mutant sod1G93R zebrafish model of amyotrophic lateral sclerosis.

    Science.gov (United States)

    McGown, Alexander; Shaw, Dame Pamela J; Ramesh, Tennore

    2016-07-26

    Amyotrophic lateral sclerosis (ALS) is a lethal neurodegenerative disease with death on average within 2-3 years of symptom onset. Mutations in superoxide dismutase 1 (SOD1) have been identified to cause ALS. Riluzole, the only neuroprotective drug for ALS provides life extension of only 3 months on average. Thishighlights the need for compound screening in disease models to identify new neuroprotective therapies for this disease. Zebrafish is an emerging model system that is well suited for the study of diseasepathophysiology and also for high throughput (HT) drug screening. The mutant sod1 zebrafish model of ALS mimics the hallmark features of ALS. Using a fluorescence based readout of neuronal stress, we developed a high throughput (HT) screen to identify neuroprotective compounds. Here we show that the zebrafish screen is a robust system that can be used to rapidly screen thousands ofcompounds and also demonstrate that riluzole is capable of reducing neuronal stress in this model system. The screen shows optimal quality control, maintaining a high sensitivity and specificity withoutcompromising throughput. Most importantly, we demonstrate that many compounds previously failed in human clinical trials, showed no stress reducing activity in the zebrafish assay. We conclude that HT drug screening using a mutant sod1 zebrafish is a reliable model system which supplemented with secondary assays would be useful in identifying drugs with potential for neuroprotective efficacy in ALS.

  19. Binding interactions between suberin monomer components and pesticides

    Energy Technology Data Exchange (ETDEWEB)

    Olivella, M.À., E-mail: angels.olivella@udg.edu [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain); Bazzicalupi, C.; Bianchi, A. [Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3, 50019 Sesto Fiorentino (Italy); Río, J.C. del [Instituto de Recursos Naturales y Agrobiología de Sevilla, Consejo Superior de Investigaciones Científicas, P.O. Box 1052, 41080 Seville (Spain); Fiol, N.; Villaescusa, I. [Department of Chemical Engineering, Escola Politècnica Superior, Universitat de Girona, Maria Aurèlia Capmany, 61, 17071 Girona (Spain)

    2015-09-15

    Understanding the role of biomacromolecules and their interactions with pollutants is a key for elucidating the sorption mechanisms and making an accurate assessment of the environmental fate of pollutants. The knowledge of the sorption properties of the different constituents of these biomacromolecules may furnish a significant contribution to this purpose. Suberin is a very abundant biopolymer in higher plants. In this study, suberin monomers isolated from cork were analyzed by thermally-assisted methylation with tetramethylammonium hydroxide (TMAH) in a pyrolysis unit coupled to gas chromatography–mass spectrometry (GC/MS). The isolated monomer mixture was used to study the sorption of three pesticides (isoproturon, methomyl and oxamyl). The modes of pesticide–sorbent interactions were analyzed by means of two modeling calculations, the first one representing only the mixture of suberin monomers used in the sorption study, and the second one including glycerol to the mixture of suberin monomers, as a building block of the suberin molecule. The results indicated that the highest sorption capacity exhibited by the sorbent was for isoproturon (33%) being methomyl and oxamyl sorbed by the main suberin components to a lesser extent (3% and < 1%, respectively). In addition to van der Waals interactions with the apolar region of sorbent and isoproturon, modeling calculations evidenced the formation of a hydrogen bond between the isoproturon NH group and a carboxylic oxygen atom of a suberin monomer. In the case of methomyl and oxamyl only weak van der Waals interactions stabilize the pesticide–sorbent adducts. The presence of glycerol in the model provoked significant changes in the interactions with isoproturon and methomyl. - Highlights: • Suberin has low affinity to retain pesticides of aliphatic character. • Suberin has a moderate affinity to adsorb isoproturon. • Modeling calculations show that apolar portion of suberin interacts with isoproturon.

  20. Binding interactions between suberin monomer components and pesticides

    International Nuclear Information System (INIS)

    Olivella, M.À.; Bazzicalupi, C.; Bianchi, A.; Río, J.C. del; Fiol, N.; Villaescusa, I.

    2015-01-01

    Understanding the role of biomacromolecules and their interactions with pollutants is a key for elucidating the sorption mechanisms and making an accurate assessment of the environmental fate of pollutants. The knowledge of the sorption properties of the different constituents of these biomacromolecules may furnish a significant contribution to this purpose. Suberin is a very abundant biopolymer in higher plants. In this study, suberin monomers isolated from cork were analyzed by thermally-assisted methylation with tetramethylammonium hydroxide (TMAH) in a pyrolysis unit coupled to gas chromatography–mass spectrometry (GC/MS). The isolated monomer mixture was used to study the sorption of three pesticides (isoproturon, methomyl and oxamyl). The modes of pesticide–sorbent interactions were analyzed by means of two modeling calculations, the first one representing only the mixture of suberin monomers used in the sorption study, and the second one including glycerol to the mixture of suberin monomers, as a building block of the suberin molecule. The results indicated that the highest sorption capacity exhibited by the sorbent was for isoproturon (33%) being methomyl and oxamyl sorbed by the main suberin components to a lesser extent (3% and < 1%, respectively). In addition to van der Waals interactions with the apolar region of sorbent and isoproturon, modeling calculations evidenced the formation of a hydrogen bond between the isoproturon NH group and a carboxylic oxygen atom of a suberin monomer. In the case of methomyl and oxamyl only weak van der Waals interactions stabilize the pesticide–sorbent adducts. The presence of glycerol in the model provoked significant changes in the interactions with isoproturon and methomyl. - Highlights: • Suberin has low affinity to retain pesticides of aliphatic character. • Suberin has a moderate affinity to adsorb isoproturon. • Modeling calculations show that apolar portion of suberin interacts with isoproturon.

  1. Evolution of magnetization due to asymmetric dimerization: theoretical considerations and application to aberrant oligomers formed by apoSOD1(2SH).

    Science.gov (United States)

    Sekhar, Ashok; Bain, Alex D; Rumfeldt, Jessica A O; Meiering, Elizabeth M; Kay, Lewis E

    2016-02-17

    A set of coupled differential equations is presented describing the evolution of magnetization due to an exchange reaction whereby a pair of identical monomers form an asymmetric dimer. In their most general form the equations describe a three-site exchange process that reduces to two-site exchange under certain limiting conditions that are discussed. An application to the study of sparsely populated, transiently formed sets of aberrant dimers, symmetric and asymmetric, of superoxide dismutase is presented. Fits of concentration dependent CPMG relaxation dispersion profiles provide measures of the dimer dissociation constants and both on- and off-rates. Dissociation constants on the order of 70 mM are extracted from fits of the data, with dimeric populations of ∼2% and lifetimes of ∼6 and ∼2 ms for the symmetric and asymmetric complexes, respectively. This work emphasizes the important role that NMR relaxation experiments can play in characterizing very weak molecular complexes that remain invisible to most biophysical approaches.

  2. Valve seat pores sealed with thermosetting monomer

    Science.gov (United States)

    Olmore, A. B.

    1966-01-01

    Hard anodic coating provides a smooth wear resistant value seating surface on a cast aluminum alloy valve body. Vacuum impregnation with a thermosetting monomer, diallyl phthalate, seals the pores on the coating to prevent galvanic corrosion.

  3. Photopolymerizable silicone monomers, oligomers, and resins

    International Nuclear Information System (INIS)

    Jacobine, A.F.; Nakos, S.T.

    1992-01-01

    The purpose of this chapter is to acquaint the general photopolymer researcher with the historical development of the chemistry and technology of photopolymerizable silicone monomers, fluids, and resins. The current status of research in these areas is assessed. The focus of this chapter is not only on the polymer chemistry and application of this technology, but also on important aspects of the synthetic chemistry involved in the preparation of UV-curable silicone monomers, oligomers, and resins. 236 refs., 6 tabs

  4. The Overexpression of TDP-43 Protein in the Neuron and Oligodendrocyte Cells Causes the Progressive Motor Neuron Degeneration in the SOD1 G93A Transgenic Mouse Model of Amyotrophic Lateral Sclerosis.

    Science.gov (United States)

    Lu, Yi; Tang, Chunyan; Zhu, Lei; Li, Jiao; Liang, Huiting; Zhang, Jie; Xu, Renshi

    2016-01-01

    The recent investigation suggested that the TDP-43 protein was closely related to the motor neuron degeneration in amyotrophic lateral sclerosis (ALS), but the pathogenesis contributed to motor neuron degeneration largely remained unknown. Therefore, we detected the alteration of TDP-43 expression and distribution in the adult spinal cord of the SOD1 G93A transgenic mouse model for searching the possible pathogenesis of ALS. We examined the TDP-43 expression and distribution in the different anatomic regions, segments and neural cells in the adult spinal cord at the different stages of the SOD1 wild-type and G93A transgenic model by the fluorescent immunohistochemical technology. We revealed that the amount of TDP-43 positive cell was cervical>lumbar>thoracic segment, that in the ventral horn was more than that in the dorsal horn, a few of TDP-43 protein sparsely expressed and distributed in the other regions, the TDP-43 protein weren't detected in the white matter and the central canal. The TDP-43 protein was mostly expressed and distributed in the nuclear of neuron cells and the cytoplasm of oligodendrocyte cells of the gray matter surrounding the central canal of spinal cord by the granular shape in the SOD1 wild-type and G93A transgenic mice. The amount of TDP-43 positive cell significantly increased at the onset and progression stages of ALS following with the increase of neuron death in spinal cord, particularly in the ventral horn of cervical segment at the progression stage. Our results suggested that the overexpression of TDP-43 protein in the neuron and oligodendrocyte cell causes the progressive motor neuron degeneration in the ALS-like mouse model.

  5. Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

    Science.gov (United States)

    Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

    2014-02-01

    One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

  6. Association between single nucleotide polymorphisms in the antioxidant genes CAT, GR and SOD1, erythrocyte enzyme activities, dietary and life style factors and breast cancer risk in a Danish, prospective cohort study

    DEFF Research Database (Denmark)

    Kopp, Tine Iskov; Vogel, Ulla; Dragsted, Lars Ove

    2017-01-01

    investigated in 703 breast cancer case-control pairs in the Danish, prospective "Diet, Cancer and Health" cohort together with gene-environment interactions between the polymorphisms, enzyme activities and intake of fruits and vegetables, alcohol and smoking in relation to breast cancer risk. Our results...... showed that genetically determined variations in the antioxidant enzyme activities of SOD1, CAT and GSR were not associated with risk of breast cancer per se. However, intake of alcohol, fruit and vegetables, and smoking status interacted with some of the polymorphisms in relation to breast cancer risk...

  7. Preparation of supramolecular polymers by copolymerization of monomers containing quadruple hydrogen bonding units with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

  8. Preparation of supramolecular polymers by copolymerization of monomers containing quadruple hydrogen bonding units with regular monomers

    NARCIS (Netherlands)

    2004-01-01

    The invention relates to the synthesis of polymers contg. self-complementary quadruple H groups by copolymg. monomers contg. a quadruple H bonding group with ³1 monomers of choice. The resulting polymers show unique new characteristics due to the presence of addnl. phys. interactions between the

  9. Thermodynamics of monomer partitioning in polymer latices: effect of molar volume of the monomers

    NARCIS (Netherlands)

    Schoonbrood, H.A.S.; German, A.L.

    1994-01-01

    A model of the thermodn. of partitioning of moderately water-sol. monomers in polymer latex systems is developed to show deviations that occur when the molar vols. of the monomers are not similar. The model, as well as expts. with Me acrylate and cyclohexyl methacrylate in polystyrene latex systems,

  10. Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

    International Nuclear Information System (INIS)

    Richter, Andrew; Dergunov, Sergey; Ganus, Bill; Thomas, Zachary; Pingali, Sai Venkatesh; Urban, Volker S.; Liu, Yun; Porcar, Lionel; Pinkhassik, Eugene

    2011-01-01

    Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.

  11. Radiation cured and monomer modified silicon elastomers

    International Nuclear Information System (INIS)

    Eldred, R.J.

    1979-01-01

    A method is described for the production of a tear resistant silicone elastomer, which has improved elongation properties. This elastomer is the radiation induced reaction product of a noncured methyl vinyl silicone resin (VMQ) and uniformly dispersed therein a blend of a polyfunctional acrylic crosslinking monomer and a filler

  12. New monomers for high performance polymers

    Science.gov (United States)

    Gratz, Roy F.

    1993-01-01

    This laboratory has been concerned with the development of new polymeric materials with high thermo-oxidative stability for use in the aerospace and electronics industries. Currently, there is special emphasis on developing matrix resins and composites for the high speed civil transport (HSCT) program. This application requires polymers that have service lifetimes of 60,000 hr at 350 F (177 C) and that are readily processible into void-free composites, preferably by melt-flow or powder techniques that avoid the use of high boiling solvents. Recent work has focused on copolymers which have thermally stable imide groups separated by flexible arylene ether linkages, some with trifluoromethyl groups attached to the aromatic rings. The presence of trifluoromethyl groups in monomers and polymers often improves their solubility and processibility. The goal of this research was to synthesize several new monomers containing pendant trifluoromethyl groups and to incorporate these monomers into new imide/arylene ether copolymers. Initially, work was begun on the synthesis of three target compounds. The first two, 3,5-dihydroxybenzo trifluoride and 3-amino 5-hydroxybenzo trifluoride, are intermediates in the synthesis of more complex monomers. The third, 3,5-bis (3-amino-phenoxy) benzotrifluoride, is an interesting diamine that could be incorporated into a polyimide directly.

  13. Softening and elution of monomers in ethanol

    DEFF Research Database (Denmark)

    Benetti, Ana Raquel; Asmussen, Erik; Munksgaard, E Christian

    2009-01-01

    The purpose of this study was to investigate the effect of light-curing protocol on softening and elution of monomers in ethanol as measured on a model polymer. It was a further aim to correlate the measured values with previously reported data on degree of conversion and glass transition...

  14. Improved thrombin binding aptamer by incorporation of a single unlocked nucleic acid monomer

    DEFF Research Database (Denmark)

    Pasternak, Anna; Hernandez, Frank J; Rasmussen, Lars Melholt

    2011-01-01

    A 15-mer DNA aptamer (named TBA) adopts a G-quadruplex structure that strongly inhibits fibrin-clot formation by binding to thrombin. We have performed thermodynamic analysis, binding affinity and biological activity studies of TBA variants modified by unlocked nucleic acid (UNA) monomers. UNA...... that a UNA monomer is allowed in many positions of the aptamer without significantly changing the thrombin-binding properties. The biological effect of a selection of the modified aptamers was tested by a thrombin time assay and showed that most of the UNA-modified TBAs possess anticoagulant properties......, and that the construct with a UNA-U monomer in position 7 is a highly potent inhibitor of fibrin-clot formation....

  15. Neuronal glucose metabolism is impaired while astrocytic TCA cycling is unaffected at symptomatic stages in the hSOD1G93A mouse model of amyotrophic lateral sclerosis.

    Science.gov (United States)

    Tefera, Tesfaye W; Borges, Karin

    2018-01-01

    Although alterations in energy metabolism are known in ALS, the specific mechanisms leading to energy deficit are not understood. We measured metabolite levels derived from injected [1- 13 C]glucose and [1,2- 13 C]acetate (i.p.) in cerebral cortex and spinal cord extracts of wild type and hSOD1 G93A mice at onset and mid disease stages using high-pressure liquid chromatography, 1 H and 13 C nuclear magnetic resonance spectroscopy. Levels of spinal and cortical CNS total lactate, [3- 13 C]lactate, total alanine and [3- 13 C]alanine, but not cortical glucose and [1- 13 C]glucose, were reduced mostly at mid stage indicating impaired glycolysis. The [1- 13 C]glucose-derived [4- 13 C]glutamate, [4- 13 C]glutamine and [2- 13 C]GABA amounts were diminished at mid stage in cortex and both time points in spinal cord, suggesting decreased [3- 13 C]pyruvate entry into the TCA cycle. Lack of changes in [1,2- 13 C]acetate-derived [4,5- 13 C]glutamate, [4,5- 13 C]glutamine and [1,2- 13 C]GABA levels indicate unchanged astrocytic 13 C-acetate metabolism. Reduced levels of leucine, isoleucine and valine in CNS suggest compensatory breakdown to refill TCA cycle intermediate levels. Unlabelled, [2- 13 C] and [4- 13 C]GABA concentrations were decreased in spinal cord indicating that impaired glucose metabolism contributes to hyperexcitability and supporting the use of treatments which increase GABA amounts. In conclusion, CNS glucose metabolism is compromised, while astrocytic TCA cycling appears to be normal in the hSOD1 G93A mouse model at symptomatic disease stages.

  16. Growth of monodisperse mesoscopic metal-oxide colloids under constant monomer supply

    Science.gov (United States)

    Nozawa, Koh; Delville, Marie-Hélène; Ushiki, Hideharu; Panizza, Pascal; Delville, Jean-Pierre

    2005-07-01

    In closed systems, control over the size of monodisperse metal-oxide colloids is generally limited to submicrometric dimensions. To overcome this difficulty, we explore the formation and growth of silica particles under constant monomer supply. The monomer source is externally driven by the progressive addition into the system of one of the precursors. Monodisperse spherical particles are produced up to a mesoscopic size. We analyze their growth versus the monomer addition rate at different temperatures. Our results show that in the presence of a continuous monomer addition, growth is limited by diffusion over the investigated temporal window. Using the temperature variation of the growth rate, we prove that rescaling leads to a data reduction onto a single master curve. Contrary to the growth process, the final particle’s size reached after the end of the reagent supply strongly depends on the addition rate. The variation of the final particle size versus addition rate can be deduced from an analogy with crystal formation in jet precipitation. Within this framework, and using the temperature dependences of both the particle growth law and the final size, we determine the value of the molecular heat of dissolution associated to the silica solubility. These observations support the fact that classical theories of phase-ordering dynamics can be extended to the synthesis of inorganic particles. The emergence of a master behavior in the presence of continuous monomer addition also suggests the extension of these theories to open systems.

  17. Photokopolimerisasi monomer akrilat degan kulit kras sapi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati

    1997-06-01

    Full Text Available The research on photocopolymerization of acrylate monomer with cow crust hide had object to observe the resulted copolymer onto cow crust hide. Crust hides, saturated with aqueous emulsions containing 25 wt % of n-butyl acrylate (n-BA or tripropylene glycol diacrylate (TPGDA were irradiated by cobalt – 60 gamma rays with doses ranges from 5 to 25 kGy. The irradiated hides were washed with water, dried in air and extracted in soxhlet apparatus for 48 hours to remove homopolymer. The highest yield of photocopolymerization of n – butyl acrylate monomer with crust hides was found 17,7878% at dose 25 kGy, and for photocopolymerization of tripropylene glycol diacrylate with crust hides was found 39,4245% at dose 20 kGy.

  18. Radiation crosslinking of PVC with polyfunctional monomers

    International Nuclear Information System (INIS)

    Dobo, J.; Takacs, E.; Csato, P.

    1984-01-01

    The radiation crosslinking of PVC in the presence of ethylene glycol dimethacrylate (EGDM) and of trimethylol propane trimethacrylate (TMPTM) was investigated. The effect of PVC powders of different types on the polymerization rate of these monomers was studied by a Calvet-type microcalorimeter. In the milled PVC sheets containing 50 part EGDM a high concentration of trapped free radicals was found by ESR after 16 months storage. (author)

  19. Shelf Life of PMR Polyimide Monomer Solutions and Prepregs Extended

    Science.gov (United States)

    Alston, William B.; Scheiman, Daniel A.

    2000-01-01

    PMR (Polymerization of Monomeric Reactants) technology was developed in the mid-1970's at the NASA Glenn Research Center at Lewis Field for fabricating high-temperature stable polyimide composites. This technology allowed a solution of polyimide monomers or prepreg (a fiber, such as glass or graphite, impregnated with PMR polyimide monomers) to be thermally cured without the release of volatiles that cause the formation of voids unlike the non-PMR technology used for polyimide condensation type resins. The initial PMR resin introduced as PMR 15 is still commercially available and is used worldwide by aerospace industries as the state-of-the-art resin for high-temperature polyimide composite applications. PMR 15 offers easy composite processing, excellent composite mechanical property retention, a long lifetime at use temperatures of 500 to 550 F, and relatively low cost. Later, second-generation PMR resin versions, such as PMR II 50 and VCAP 75, offer improvements in the upper-use temperature (to 700 F) and in the useful life at temperature without major compromises in processing and property retention but with significant increases in resin cost. Newer versions of nontoxic (non-methylene dianiline) PMR resins, such as BAX PMR 15, offer similar advantages as originally found for PMR 15 but also with significant increases in resin cost. Thus, the current scope of the entire PMR technology available meets a wide range of aeronautical requirements for polymer composite applications.

  20. 21 CFR 888.4220 - Cement monomer vapor evacuator.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Cement monomer vapor evacuator. 888.4220 Section... (CONTINUED) MEDICAL DEVICES ORTHOPEDIC DEVICES Surgical Devices § 888.4220 Cement monomer vapor evacuator. (a) Identification. A cement monomer vapor evacuator is a device intended for use during surgery to contain or remove...

  1. Thermodynamics of swelling of latex particles with two monomers

    NARCIS (Netherlands)

    Maxwell, I.A.; Kurja, J.; van Doremaele, G.H.J.; German, A.L.

    1992-01-01

    The partitioning of 2 monomers between the latex particle, monomer droplet, and aq. phases of an emulsion polymer latex are measured at satn. swelling of the latex particle phase (corresponding to intervals I and II of an emulsion polymn.). The monomer (Me acrylate, Bu acrylate, styrene) and polymer

  2. Photoligation of self-assembled DNA constructs containing anthracene-functionalized 2'-amino-LNA monomers

    DEFF Research Database (Denmark)

    Pasternak, Karol; Pasternak, Anna; Gupta, Pankaj

    2011-01-01

    Efficient synthesis of a novel anthracene-functionalized 2'-amino-LNA phosphoramidite derivative is described together with its incorporation into oligodeoxynucleotides. Two DNA strands with the novel 2'-N-anthracenylmethyl-2'-amino-LNA monomers can be effectively cross-linked by photoligation...... at 366nm in various types of DNA constructs. Successful application of three differently functionalized 2'-amino-LNA monomers in self-assembled higher ordered structures for simultaneous cross-linking and monitoring of assembly formation is furthermore demonstrated....

  3. Kinetics of monomer biodegradation in soil.

    Science.gov (United States)

    Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria

    2012-01-01

    In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Sustainable Poly(Ionic Liquids) for CO2 Capture Based on Deep Eutectic Monomers

    KAUST Repository

    Isik, Mehmet; Zulfiqar, Sonia; Edhaim, Fatimah; Ruiperez, Fernando; Rothenberger, Alexander; Mecerreyes, David

    2016-01-01

    The design of high performance solid sorbent materials for CO2 capture is a technology which has been employed to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multistep energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even though they possess good properties as CO2 sorbents. Here we show a new family of polymers which are based on amines, amidoximes, and natural carboxylic acids and can be obtained using sustainable low energy processes. Thus, deep eutectic monomers based on natural carboxylic acids, amidoximes, and amines have been prepared by just mixing with cholinium type methacrylic ammonium monomer. The formation of deep eutectic monomers was confirmed by differential scanning calorimetry measurements. In all cases, the monomers displayed glass transition temperatures well below room temperature. Computational studies revealed that the formation of eutectic complexes lengthens the distance between the cation and the anion causing charge delocalization. The liquid nature of the resulting deep eutectic monomers (DEMs) made it possible to conduct a fast photopolymerization process to obtain the corresponding poly(ionic liquids). Materials were characterized by means of nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction to evaluate the properties of the polymers. The polymers were then used as solid sorbents for CO2 capture. It has been shown that the polymers prepared with citric acid displayed better performance both experimentally and computationally. The current endeavor showed that sustainable poly(ionic liquids) based on deep eutectic monomers can be easily prepared to produce low-energy-cost alternatives to the materials currently being researched for CO2 capture. © 2016 American Chemical Society.

  5. Sustainable Poly(Ionic Liquids) for CO2 Capture Based on Deep Eutectic Monomers

    KAUST Repository

    Isik, Mehmet

    2016-10-05

    The design of high performance solid sorbent materials for CO2 capture is a technology which has been employed to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multistep energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even though they possess good properties as CO2 sorbents. Here we show a new family of polymers which are based on amines, amidoximes, and natural carboxylic acids and can be obtained using sustainable low energy processes. Thus, deep eutectic monomers based on natural carboxylic acids, amidoximes, and amines have been prepared by just mixing with cholinium type methacrylic ammonium monomer. The formation of deep eutectic monomers was confirmed by differential scanning calorimetry measurements. In all cases, the monomers displayed glass transition temperatures well below room temperature. Computational studies revealed that the formation of eutectic complexes lengthens the distance between the cation and the anion causing charge delocalization. The liquid nature of the resulting deep eutectic monomers (DEMs) made it possible to conduct a fast photopolymerization process to obtain the corresponding poly(ionic liquids). Materials were characterized by means of nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction to evaluate the properties of the polymers. The polymers were then used as solid sorbents for CO2 capture. It has been shown that the polymers prepared with citric acid displayed better performance both experimentally and computationally. The current endeavor showed that sustainable poly(ionic liquids) based on deep eutectic monomers can be easily prepared to produce low-energy-cost alternatives to the materials currently being researched for CO2 capture. © 2016 American Chemical Society.

  6. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser

    2016-10-11

    Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

  7. In vitro evidence for impaired neuroprotective capacities of adult mesenchymal stem cells derived from a rat model of familial amyotrophic lateral sclerosis (hSOD1(G93A)).

    Science.gov (United States)

    Boucherie, Cédric; Caumont, Anne-Sophie; Maloteaux, Jean-Marie; Hermans, Emmanuel

    2008-08-01

    Protection of neurons by stem cells is an attractive challenge in the development of efficient therapies of neurodegenerative diseases. When giving preference to autologous grafts, the bone marrow constitutes a valuable source of adult stem cells. Therefore, we herein studied the acquisition of neuroprotective functions by cultured mesenchymal stem cells (MSCs) exposed to growth factors known to promote the differentiation of neural stem cells into astrocytes. In these conditions, MSCs showed increased transcription and expression of the high-affinity glutamate transporter GLT-1 and functional studies revealed increased aspartate uptake activity. In addition, differentiation was shown to endow the cells with the capacity to respond to riluzole which triggers a robust up-regulation of the GDNF production. In parallel, MSCs derived from the bone marrow of a transgenic rat model of familial ALS (hSOD1(G93A)) were also characterised. Unexpectedly, cells from this rat strain submitted to the differentiation protocol showed modest capacity to take up aspartate and did not respond to the riluzole treatments. These data highlight the neuroprotective potential attributable to MSCs, supporting their use as valuable tools for the treatment of neurodegenerative disorders. However, the cells from the transgenic animal model of ALS appeared deficient in their capacity to gain the neuroprotective properties, raising questions regarding the suitability of autologous stem cell grafts in future therapies against familial forms of this disease.

  8. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    International Nuclear Information System (INIS)

    Melinte, Violeta; Buruiana, Tinca; Aldea, Horia; Matiut, Simona; Silion, Mihaela; Buruiana, Emil C.

    2014-01-01

    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s −1 ) were lower than those determined in the monomer combinations (0.116–0.158 s −1 ) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm 3 ) and water solubility (3.51–13.38 μg/mm 3 ), and the contact angle was dependent on the presence of CO-DAP (θ F1 : 66.67°), TMP-DAP (θ F2 : 55.05°) or AMP-P (θ F3 : 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ F4 : 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of photopolymerizable phosphate acrylate

  9. Photopolymerizable phosphate acrylates as comonomers in dental adhesives with or without triclosan monomer units

    Energy Technology Data Exchange (ETDEWEB)

    Melinte, Violeta [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Buruiana, Tinca, E-mail: tbur@icmpp.ro [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Aldea, Horia [Gr. T. Popa University of Medicine and Pharmacy, Faculty of Dentistry, Iasi (Romania); Matiut, Simona [Praxis Medical Investigations, 33 Independence, 700102 Iasi (Romania); Silion, Mihaela; Buruiana, Emil C. [Petru Poni Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania)

    2014-01-01

    Phosphate diacrylates (CO-DAP, TMP-DAP) based on castor oil or trimethylolpropane were synthesized and evaluated in dental adhesive formulations in comparison with 3-acryloyloxy-2-hydroxypropyl methacrylate phosphate (AMP-P). In an attempt to promote antibacterial activity, another photopolymerizable monomer (TCS-UMA) containing 5-chloro-2-(2,4-dichlorophenoxy)phenol moiety (triclosan) was prepared and incorporated in adhesive resins. Each of these monomers had a molecular structure confirmed by spectral methods. The photopolymerization rates for monomers (0.063–0.088 s{sup −1}) were lower than those determined in the monomer combinations (0.116–0.158 s{sup −1}) incorporating phosphate diacrylate (11 wt.%), BisGMA (33 wt.%), TEGDMA (10 wt.%), UDMA (10 wt.%) and HEMA (15 wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65–57.02 μg/mm{sup 3}) and water solubility (3.51–13.38 μg/mm{sup 3}), and the contact angle was dependent on the presence of CO-DAP (θ{sub F1}: 66.67°), TMP-DAP (θ{sub F2}: 55.05°) or AMP-P (θ{sub F3}: 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θ{sub F4}: 82.14°). The scanning electron microscopy image of the dentin–resin composite interface after applying our F1 formulation (pH: 4.1) and its light-curing for 20 s supports the evidence of the formation of the hybrid layer with the tooth structure created by self-etching approach, with no gaps or cracks in the adhesive. A comparative analysis of the adhesion achieved with commercial adhesive systems (Single Bond Universal, C-Bond) rather indicates similarities than differences between them. The addition of triclosan methacrylate (1 wt.%) into the formulation inhibited the bacterial growth of the Streptococcus mutans and Escherichia coli in the direct contact area due to the covalently linked antibacterial monomer. - Highlights: • Synthesis of

  10. Influence of Monomer Concentration on the Morphologies and Electrochemical Properties of PEDOT, PANI, and PPy Prepared from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Shalini Kulandaivalu

    2016-01-01

    Full Text Available Poly(3,4-ethylenedioxyhiophene (PEDOT, polyaniline (PANI, and polypyrrole (PPy were prepared on indium tin oxide (ITO substrate via potentiostatic from aqueous solutions containing monomer and lithium perchlorate. The concentration of monomers was varied between 1 and 10 mM. The effects of monomer concentration on the polymers formation were investigated and compared by using Fourier transform infrared spectroscopy (FTIR, Raman spectroscopy, scanning electron microscopy (SEM, cyclic voltammetry (CV, and electrochemical impedance spectroscopy (EIS measurements. FTIR and Raman spectra showed no changes in the peaks upon the increment of the concentration. Based on the SEM images, the increment in monomer concentration gives significant effect on morphologies and eventually affects the electrochemical properties. PEDOT electrodeposited from 10 mM solution showed excellent electrochemical properties with the highest specific capacitance value of 12.8 mF/cm2.

  11. High performance dental resin composites with hydrolytically stable monomers.

    Science.gov (United States)

    Wang, Xiaohong; Huyang, George; Palagummi, Sri Vikram; Liu, Xiaohui; Skrtic, Drago; Beauchamp, Carlos; Bowen, Rafael; Sun, Jirun

    2018-02-01

    The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications. New resins comprising hydrolytically stable, ether-based monomer, i.e., triethylene glycol divinylbenzyl ether (TEG-DVBE), and urethane dimethacrylate (UDMA) were produced via composition-controlled photo-polymerization. Their composites contained 67.5wt% of micro and 7.5wt% of nano-sized filler. The performances of both copolymers and composites were evaluated by a battery of clinically-relevant assessments: degree of vinyl conversion (DC: FTIR and NIR spectroscopy); refractive index (n: optical microscopy); elastic modulus (E), flexural strength (F) and fracture toughness (K IC ) (universal mechanical testing); Knoop hardness (HK; indentation); water sorption (W sp ) and solubility (W su ) (gravimetry); polymerization shrinkage (S v ; mercury dilatometry) and polymerization stress (tensometer). The experimental UDMA/TEG-DVBE composites were compared with the Bis-GMA/TEGDMA composites containing the identical filler contents, and with the commercial micro hybrid flowable composite. UDMA/TEG-DBVE composites exhibited n, E, W sp , W su and S v equivalent to the controls. They outperformed the controls with respect to F (up to 26.8% increase), K IC (up to 27.7% increase), modulus recovery upon water sorption (full recovery vs. 91.9% recovery), and stress formation (up to 52.7% reduction). In addition, new composites showed up to 27.7% increase in attainable DC compared to the traditional composites. Bis-GMA/TEGDMA controls exceeded the experimental composites with respect to only one property, the composite hardness. Significantly, up to 18.1% lower HK values in

  12. Interference of functional monomers with polymerization efficiency of adhesives.

    Science.gov (United States)

    Hanabusa, Masao; Yoshihara, Kumiko; Yoshida, Yasuhiro; Okihara, Takumi; Yamamoto, Takatsugu; Momoi, Yasuko; Van Meerbeek, Bart

    2016-04-01

    The degree of conversion (DC) of camphorquinone/amine-based adhesives is affected by acidic functional monomers as a result of inactivation of the amine co-initiator through an acid-base reaction. During bonding, functional monomers of self-etch adhesives chemically interact with hydroxyapatite (HAp). Here, we tested in how far the latter interaction of functional monomers with HAp counteracts the expected reduction in DC of camphorquinone/amine-based adhesives. The DC of three experimental adhesive formulations, containing either of the two functional monomers [10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) or 4-methacryloxyethyl trimellitic acid anhydride (4-META)] or no functional monomer (no-FM; control), was measured with and without HAp powder added to the adhesive formulations. Both the variables 'functional monomer' and 'HAp' were found to be significant, with the functional monomer reducing the DC and HAp counteracting this effect. It is concluded that the functional monomers 10-MDP and 4-META interfere with the polymerization efficiency of adhesives. This interference is less prominent in the presence of HAp, which would clinically correspond to when these two functional monomers of the adhesive simultaneously interact with HAp in tooth tissue. © 2016 Eur J Oral Sci.

  13. The effect of monomer molecular weight on grafting reaction

    International Nuclear Information System (INIS)

    Wu Minghong; Ding Zhongli; Ma Zueteh

    1995-01-01

    In this paper, some condensed ethylene glycol acrylate monomers with different molecular weight being grafted to the PE film by means of pre-irradiation is reported. The effect of molecular weight of monomer on grafting reaction and the hydrophilicity of grafting sample have been discussed. The experimental results show: molar degrees of grafting decreased non-linearly with the increasement of molecular weight of monomer, the grafting reaction of polymer is greater effected by the swelling degree of PE film, the greater the swelling degree of grafting material, the higher the grating degree grafting is, the initial rate of grafting reaction decreased with the increasement of molecular weight of monomer. (author)

  14. Preparation of unsaturated acrylic prepolymer and electron beam curing of its mixture with vinyl monomers

    International Nuclear Information System (INIS)

    Pyun, H.C.; Park, W.B.; Kim, K.Y.; Sung, K.Y.

    1980-01-01

    Electron beam curable prepolymers were prepared by the addition reaction of methyl methacrylate-glycidyl methacrylate copolymer with methacrylic acid, and electron beam curing was studied for the prepolymer and their mixtures of several kind of vinyl monomers. When the reaction was carried out in the presence of triethylbenzyl ammonium chloride in N,N-dimethyl formamide solution, the rate of addition reaction obeyed first-order kinetics. In the electron beam curing, the rate of gel formation of the prepolymer was slower than that of the mixtures of prepolymer and monomers. In the curing of mixtures of prepolymer with polyethyleneglycol dimethacrylates, the rate of gel formation increased with the increase in the degree of polymerization of polyethylene oxide fraction of polyethyleneglycol dimethacrylate, and decreased with the increase the polyethyleneglycol dimethacrylate content. The properties of cured coatings were also examined. (author)

  15. Partial swelling of latex particles by two monomers

    NARCIS (Netherlands)

    Noel, E.F.J.; Maxwell, I.A.; German, A.L.

    1993-01-01

    The swelling of polymeric latex particles with solvent and monomer is of great importance for the emulsion polymn. process in regard to compn. drift and rate of polymn. For the monomer combination, Me acrylate-vinyl acetate, both satn. and partial swelling were detd. exptl. Theories for satn.

  16. Oligonucleotides with 1,4-dioxane-based nucleotide monomers

    DEFF Research Database (Denmark)

    Madsen, Andreas S; Wengel, Jesper

    2012-01-01

    An epimeric mixture of H-phosphonates 5R and 5S has been synthesized in three steps from known secouridine 1. Separation of the epimers has been accomplished by RP-HPLC, allowing full characterization and incorporation of monomers X and Y into 9-mer oligonucleotides using H-phosphonates building...... blocks 5R and 5S, respectively. A single incorporation of either monomer X or monomer Y in the central position of a DNA 9-mer results in decreased thermal affinity toward both DNA and RNA complements (ΔT(m) = -3.5 °C/-3.5 °C for monomer X and ΔT(m) = -11.0 °C/-6.5 °C for monomer Y). CD measurements do...

  17. Pulse radiolysis study of monomer and dimer cations of styrene, 1-methylstyrene and 1,1'-diphenylethylene

    International Nuclear Information System (INIS)

    Mehnert, R.; Helmstreit, W.; Boes, J.; Brede, O.

    1977-01-01

    In pulse-irradiated solutions of styrene, 1-methylstyrene and 1,1'-diphenylethylene, the decay kinetics of the olefin monomer cations and the formation kinetics of the corresponding dimer cations have been studied at room temperature. The solutions were irradiated with 15-nsec 15-ampere pulses of 1-MeV electrons from an Elit-type accelerator. The total dose per pulse was approximately 10 krad. The monomer cations were generated with rate constants of about 10 11 M -1 sec -1 . From the time decay of the monomer light absorption and the growth in time of the dimer absorption rate constants for the dimer formation between 0.8x10 10 and 1.2x10 10 M -1 sec -1 have been determined. (T.I.)

  18. Quantitative analysis of detailed lignin monomer composition by pyrolysis-gas chromatography combined with preliminary acetylation of the samples.

    Science.gov (United States)

    Sonoda, T; Ona, T; Yokoi, H; Ishida, Y; Ohtani, H; Tsuge, S

    2001-11-15

    Detailed quantitative analysis of lignin monomer composition comprising p-coumaryl, coniferyl, and sinapyl alcohol and p-coumaraldehyde, coniferaldehyde, and sinapaldehyde in plant has not been studied from every point mainly because of artifact formation during the lignin isolation procedure, partial loss of the lignin components inherent in the chemical degradative methods, and difficulty in the explanation of the complex spectra generally observed for the lignin components. Here we propose a new method to quantify lignin monomer composition in detail by pyrolysis-gas chromatography (Py-GC) using acetylated lignin samples. The lignin acetylation procedure would contribute to prevent secondary formation of cinnamaldehydes from the corresponding alcohol forms during pyrolysis, which are otherwise unavoidable in conventional Py-GC process to some extent. On the basis of the characteristic peaks on the pyrograms of the acetylated sample, lignin monomer compositions in various dehydrogenative polymers (DHP) as lignin model compounds were determined, taking even minor components such as cinnamaldehydes into consideration. The observed compositions by Py-GC were in good agreement with the supplied lignin monomer contents on DHP synthesis. The new Py-GC method combined with sample preacetylation allowed us an accurate quantitative analysis of detailed lignin monomer composition using a microgram order of extractive-free plant samples.

  19. Highly Efficient Synthesis of Allopurinol Locked Nucleic Acid Monomer by C6 Deamination of 8-Aza-7-bromo-7-deazaadenine Locked Nucleic Acid Monomer

    DEFF Research Database (Denmark)

    Kosbar, Tamer Reda El-Saeed; Sofan, M.; Abou-Zeid, L.

    2013-01-01

    An allopurinol locked nucleic acid (LNA) monomer was prepared by a novel strategy through C6 deamination of the corresponding 8-aza-7-bromo-7-deazaadenine LNA monomer with aqueous sodium hydroxide. An 8-aza-7-deazaadenine LNA monomer was also synthesized by a modification of the new synthetic...... the required LNA monomers....

  20. Redesign of the monomer-monomer interface of Cre recombinase yields an obligate heterotetrameric complex.

    Science.gov (United States)

    Zhang, Chi; Myers, Connie A; Qi, Zongtai; Mitra, Robi D; Corbo, Joseph C; Havranek, James J

    2015-10-15

    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  1. Modeling the structure and vibrational spectra for oxouranium dichloride monomer and dimer

    Science.gov (United States)

    Umreiko, D. S.; Shundalau, M. B.; Trubina, O. V.

    2010-11-01

    Structural models are designed and spectral characteristics are computed for the monomer and dimer of the oxouranium dichloride (UOCl2) molecule based on ab initio calculations. The calculations were carried out in the LANL2DZ effective core potential approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). A close-to-planar Y-shaped equilibrium configuration with Cs symmetry is obtained for the UOCl2 monomer. The formation of the dimer is accompanied by both significant changes in the structure of the monomeric fragments and the actual loss of their identities. The obtained spectral characteristics are analyzed and compared with experimental data. The adequacy of the proposed models and qualitative agreement between calculation and experiment are demonstrated.

  2. Evaluation of level of impregnation monomers in hydrotalcite; Avaliacao do grau de impregnacao de monomeros em hidrotalcita

    Energy Technology Data Exchange (ETDEWEB)

    Carmo, Danieli M. do, E-mail: danielimcarmo@hotmail.com [Instituto de Macromoleculas Professora Eloisa Mano - IMA, Universidade Federal do Rio de Janeiro - UFRJ, RJ (Brazil); Machado, Jacson S.C.; Oliveira, Marcelo F.L.; Oliveira, Marcia G. [Instituto Nacional de Tecnologia - INT, Rio de Janeiro, RJ (Brazil); Soares, Bluma G. [Instituto de Macromoleculas Professora Eloisa Mano - IMA, Universidade Federal do Rio de Janeiro - UFRJ, RJ (Brazil)

    2011-07-01

    To evaluate the impregnation degree of 1,6-hexamethylene diisocyanate and 1,4-butanediol monomers in hydrotalcite clays it was prepared dispersions with mixing ratio 1:100 (clay/monomer), using the Ultraturrax and Ultrasound. Subsequently the samples were characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction. Swelling tests and Tyndall effect were used to illustrate the different dispersions. The results indicated a strong interaction between the hydrotalcite with 1,6-hexamethylene diisocyanate, favoring the formation of intercalated structures. (author)

  3. Synthesis of New Vinyl Monomers for Chemical Agent Sensing Applications

    National Research Council Canada - National Science Library

    Hogen-Esch, Thieo

    2001-01-01

    The synthesis of styrene momomer p-vinylbenzoylacetophenone (monomer i) has been carried by the acetylation of 2- chloroethylbenzene and base elimination of the resulting 4-acetyl-2-chloroethylbenzene to give 4-acetylstyrene...

  4. Polymerization of impregnated monomer in wood by microwave irradiation

    International Nuclear Information System (INIS)

    Kawase, Kaoru; Hayakawa, Kiyoshi

    1976-01-01

    The manufacturing of a wood-plastic combination (WPC) by irradiation of microwave (2,450 and 915 +- 50 MHz) or gamma-ray was carried out. After the impregnation of dry woods (Hinoki: Chamaecyparis obtusa Endl., Buna: Acer mono Maxim., and Kaede: Fagus crenata Blume) with the mixture of the vinyl monomers and chemical reagents, the monomer in wood was polymerized by irradiation. In case of polymerization with microwave (2,450 MHz) the effect of oxygen was not recognized, but in the case of gamma-ray the rate of polymerization remarkably decreased in the presence of oxygen. The polymerization of various monomers was carried out also in the air, and the conversions of styrene, methyl-, ethyl-, n-propyl-, and n-butyl-methacrylate were 51.8 -- 89.1%, but that of vinyl acetate was lower (4.3 -- 8.2%). The conversion of monomers with irradiation of 915 MHz microwave was very low (2.6 -- 33.5%). The conversion of monomers increased when toluylene diisocyanate was added in the monomers. The percentage of extraction with hot benzene of WPC (chip) decreased by the addition of toluylene diisocyanate. It was concluded from C.H.N. analyses that the reaction took place among the wood, toluylene diisocyanate and methyl methacrylate. (auth.)

  5. Low-temperature radiation-induced polymerization of vinyl monomers in the crystal matrix of polydimethyl siloxane

    International Nuclear Information System (INIS)

    Mujdinov, M.R.; Kiryukhin, D.P.; Barkalov, I.M.; Gol'danskij, V.I.

    1979-01-01

    It is shown that in the process of the slow cooling of vinyl monomer solution in dimethyl siloxane rubber (SKT mark) crystallization of SKT takes place, at that, considerable part of vinyl monomers (up to 70 wt. % of rubber) is sorbed in the pores of crystal matrix and it does not form its proper crystal phase. Slight anomalies in heat capacity in the 120-140 K range, the melting of non-sorbed part of MA and the melting of SKT + MA ''complex'' have been observed on the calorimetric curve at the SKT - methylacrylate (MA) system heating. In the process of heating such samples, irradiated at 77 K by γ-rays of 60 Co, heat evolution connected with sorbed monomer polarization, has been observed starting from 125-130 K. In the 140-200 K range already before MA and SKT melting intense polymerization takes place, which results in practically full monomer consumption and formation of graft copolymer. Radiation-chemical yield of monomer reduction reaches G(-M) approximately equal to 2x10 5 molecules for 100 eV, radiation yield of postpolymerization of crystal MA does not exceed G(-M) approximately equal to 50 molecules for 100 eV

  6. Effect of pH and Monomer Dosing Rate in the Anionic Polymerization of Ethyl Cyanoacrylate in Semicontinuous Operation

    Directory of Open Access Journals (Sweden)

    Hened Saade

    2015-01-01

    Full Text Available Nanoparticles of poly(ethyl cyanoacrylate with more than 10% solids content were prepared by semicontinuous heterophase polymerization at monomer-starved conditions varying the initial pH in the interval of 1–1.75 and at two monomer dosing rates. Measurements by scanning-transmission electron microscopy allowed us to identify an inverse dependence of particle size on pH. Furthermore, all the polymerizations conducted at the slower monomer dosing rate rendered two particle populations, with the larger one formed from the aggregation of a fraction of the smaller particles. It was believed that the so slow addition of the monomer caused the formation of very small but instable particles, thereby a fraction of which aggregated to reduce the total interface particles-aqueous phase, increasing the latex stability. An increase in the monomer dosing rate led to larger and more stable particles in such way that only one population of nanoparticles with around 40 nm in average diameter was obtained.

  7. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto

    2014-01-01

    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  8. In-vitro transdentinal diffusion of monomers from adhesives.

    Science.gov (United States)

    Putzeys, Eveline; Duca, Radu Corneliu; Coppens, Lieve; Vanoirbeek, Jeroen; Godderis, Lode; Van Meerbeek, Bart; Van Landuyt, Kirsten L

    2018-06-01

    Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp. Accurate knowledge of the quantity of monomers reaching the pulp is important to determine potential side effects. The aim of this study was to assess the transdentinal diffusion of residual monomers from dental adhesive systems using an in-vitro pulp chamber model. Dentin disks with a thickness of 300 µm were produced from human third molars. These disks were fixed between two open-ended glass tubes, representing an in-vitro pulp chamber. The etch-and-rinse adhesive OptiBond FL and the self-etch adhesive Clearfil SE Bond were applied to the dentin side of the disks, while on in the pulpal side, the glass tube was filled with 600 µL water. The transdentinal diffusion of different monomers was quantified using ultra-performance liquid chromatography-tandem mass spectrometry. The monomers HEMA, CQ, BisGMA, GPDM, 10-MDP and UDMA eluted from the dental materials and were able to diffuse through the dentin disks to a certain extent. Compounds with a lower molecular weight (uncured group: HEMA 7850 nmol and CQ 78.2 nmol) were more likely to elute and diffuse compared to monomers with a higher molecular weight (uncured group: BisGMA 0.42 nmol). When the adhesives were left uncured, diffusion was up to 10 times higher compared to the cured conditions. This in-vitro research resulted in the quantification of various monomers able to diffuse through dentin and therefore contributes to a more detailed understanding about the potential exposure of the dental pulp to monomers from dental adhesives. Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp, where tubular density and diameter are greatest. Copyright © 2018. Published by Elsevier Ltd.

  9. An ionic force-field study of monomers, dimers and higher polymers in pentafluoride vapors

    Energy Technology Data Exchange (ETDEWEB)

    Cicek Onem, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Akdeniz, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: zakdeniz@istanbul.edu.tr; Tosi, M.P. [Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: tosim@sns.it

    2008-08-01

    Pentafluoride compounds such as NbF{sub 5} and TaF{sub 5} have been reported in the literature to admit various states of polymerization coexisting with monomers in their vapor phase, in relative concentrations that vary with temperature and pressure. We construct a microscopic interionic force-field model for the molecular monomer of these compounds (including VF{sub 5}, SbF{sub 5} and MoF{sub 5} in addition to NbF{sub 5} and TaF{sub 5}), the stable form of the monomer being in the shape of a D{sub 3h} trigonal bipyramid in all cases. The model emulates chemical bonds by allowing for electrical and short-range overlap polarizabilities of the fluorines, and is used to evaluate the structure and the stability of (MF{sub 5}){sub n} molecules with n running from 2 to 6. The dimer is formed by two distorted edge-sharing octahedral, while the trimer and the higher polymers can form rings of distorted corner-sharing octahedra. A chain-like configuration is also found for the trimer of NbF{sub 5}, which consists of a seven-fold coordinated Nb bonded to two distorted octahedra via edge sharing. Comparison of calculated vibrational frequencies and bond lengths with experimental data is made whenever possible. We find that there is a small net gain of energy in the formation of a dimer, while otherwise the static energy of the n-mer is very close to that of n separated monomers. High sensitivity of the state of molecular aggregation to the thermodynamic conditions of the vapor is clearly indicated by our calculations.

  10. Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

    International Nuclear Information System (INIS)

    El-Salmawi, K.M.; El-Naggar, A.M.; Said, H.M.; Zahran, A.H.

    1996-01-01

    Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr's salt), solvent composition (MeOH and H 2 O), radiation dose and dose rate were considered. It was found that the role of Mohr's salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr's salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H 2 O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs

  11. Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

    Energy Technology Data Exchange (ETDEWEB)

    El-Salmawi, K M; El-Naggar, A M; Said, H M; Zahran, A H [Radiation Chemistry Department, National Center for Radiation Research and Technology, Atomic Energy Authority, Cairo, (Egypt)

    1996-03-01

    Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr`s salt), solvent composition (MeOH and H{sub 2} O), radiation dose and dose rate were considered. It was found that the role of Mohr`s salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr`s salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H{sub 2} O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs.

  12. In situ polymerization of vinyl monomers in polyester yarns

    International Nuclear Information System (INIS)

    Avny, Y.; Rebenfeld, L.; Weigmann, H.D.

    1978-01-01

    The effects of a pretreatment of polyester (PET) yarns with a strongly interacting solvent such as dimethylformamide (DMF) on vinyl monomer incorporation were investigated. When the DMF pretreatment is carried out at high temperatures (above 120 0 C), the swollen PET structure is stabilized by solvent-induced secondary crystallization. This substrate is highly suitable for the incorporation of vinyl monomers. In situ polymerization of vinyl monomers in DMF-treated PET was investigated using chemical and γ-irradiation polymerization techniques, both in the presence and in the absence of excess monomer outside the PET fibers. When polymerization was carried out in a system in which a constant supply of free radicals was available from the outside of the PET fibers, lower initiator concentrations and smaller γ-irradiation doses were necessary. These results are attributed to a low efficiency of the initiator inside the PET fiber due to mobility restrictions. Water uptake and moisture regain of PET yarns containing poly(hydroxyethyl methacrylate) and poly(acrylic acid) were also investigated. When most of the vinyl polymer was inside the PET fiber, water absorption was limited. The changes in mechanical properties of the PET yarns resulting from the DMF pretreatment were partially reversed by in situ polymerization of vinyl monomers

  13. The radiation grafting of vinyl monomers to cotton fabrics

    International Nuclear Information System (INIS)

    Shiraishi, N.; Williams, J.L.; Stannett, V.

    1982-01-01

    Cobalt 60 γ and electron beam radiation were used to graft diethylphosphatoethyl methacrylate, pure and in 90:10 methanol solution, to cotton cloth. This monomer, with an 11.64% phosphorus content, was especially developed by the Scott Paper Co. to develop fire retardancy. A simple pad and squeeze application followed by direct irradiation under a nitrogen atmosphere was used. Although excess monomer could be removed by washing with water, no solvent for the polymer was found so only the total 'add-ons' could be measured. With 60 Co irradiation, total polymerization was obtained with more than 1 Mrad but with electron beam irradiation only about 50% conversion was obtained even with 10 Mrad. No acceleration in the rates could be achieved with the viscous pure monomer as opposed to in solution. Yields adequate to impart reasonable fire retardancy could, however, be obtained with about 3 Mrad with electrons. No noticeable degradation of the polymer occurred at the doses used. (author)

  14. Assembly of one-dimensional supramolecular objects: From monomers to networks

    Science.gov (United States)

    Sayar, Mehmet; Stupp, Samuel I.

    2005-07-01

    One-dimensional supramolecular aggregates can form networks at exceedingly low concentrations. Recent experiments in several laboratories, including our own, have demonstrated the formation of gels by these systems at concentrations well under 1% by weight. The systems of interest in our laboratory form either cylindrical nanofibers or ribbons as a result of strong noncovalent interactions among monomers. The stiffness and interaction energies among these thread-like objects can vary significantly depending on the chemical structure of the monomers used. We have used Monte Carlo simulations to study the structure of the threads and their ability to form networks through bundle formation. The persistence length of the threads was found to be strongly affected not only by stiffness, but also by the strength of attractive two-body interactions among thread segments. The relative values of stiffness and attractive two-body interaction strength determine if threads collapse or create bundles. Only in the presence of sufficiently long threads and bundle formation can these systems assemble into networks of high connectivity.

  15. In situ polymerization of monomers for polyphenylquinoxaline/graphite

    Science.gov (United States)

    Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

    1973-01-01

    Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

  16. Studies on curing effect of phosphite monomer by EB radiation in the air

    International Nuclear Information System (INIS)

    Xiao, B.; Zhou, Y.; Li, S.; Luo, M.; Wang, X.; Zhao, P.

    2000-01-01

    A new type phosphite active monomer was synthesized. The resisting oxygen inhibition effect of this monomer and the effects of irradiation dose and concentration of phosphite active monomer on curing were studied. At the same time, curing results were analysed, through gel content and IR spectrum. The excellent resisting oxygen inhibition result of this phosphite active monomer was shown by experiments. EB radiation curing in the air was successfully carried out by the phosphite active monomer. (author)

  17. Influence of vinyl chloride monomer and vinyl chloride monomer derivatives on hepatic DNA synthesis

    International Nuclear Information System (INIS)

    Brenner, E.A.

    1982-01-01

    Vinyl chloride monomer (VCM) is used extensively in the chemical industry, mainly in the production of polyvinyl chloride. It has recently been found to cause hepatic angiosarcoma. As VCM has also been shown to be mutagenic after metabolic activation the effect of VCM on DNA synthesis was investigated. [ 3 H]Thymidine incorporation into DNA was used to measure the rate of DNA synthesis in regenerating rat liver. A possible direct toxic effect of VCM or its metabolites on liver cell metabolism was examined by two unrelated techniques, viz. the measurement of adenine nucleotide concentrations in regenerating livers and the influence on transmembrane potentials in hepatocytes. The distribution of radioactivity in subcellular fractions following [ 14 C]VCM administration suggested microsomal conversion of VCM to an active form which was selectively retained in the nuclear fraction. Measurement of the activities of thymidine kinase and DNA polymerase in regenerating liver indicated that the induction of these enzymes which normally occurs after partial hepatectomy was not prevented by VCM treatment. Three techniques were used to test the hypothesis that the retardation in DNA synthesis was due to DNA damage: the prophage lambda induction test for DNA damage, autoradiographic detection of unscheduled thymidine incorporation into DNA, and detection of DNA strand breaks in alkaline sucrose gradients. All three provided evidence of DNA damage and led to the development of a novel technique to confirm these findings. This involved centrifugation in neutral sucrose gradients on intact double-stranded DNA contained in hepatocyte nucleoids and showed conclusively that VCM administration causes DNA strand breaks. Subsequent repair of DNA was also assessed by this technique. The site of the VCM/metabolite: DNA reaction was characterized by DNA thermal denaturation and renaturation studies

  18. Base-catalyzed depolymerization of lignin : separation of monomers

    Energy Technology Data Exchange (ETDEWEB)

    Vigneault, A. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; Johnson, D.K. [National Renewable Energy Laboratory, Golden, CO (United States); Chornet, E. [Sherbrooke Univ., PQ (Canada). Dept. of Chemical Engineering; National Renewable Energy Laboratory, Golden, CO (United States)

    2007-12-15

    Biofuels produced from residual lignocellulosic biomass range from ethanol to biodiesel. The use of lignin for the production of alternate biofuels and green chemicals has been studied with particular emphasis on the structure of lignin and its oxyaromatic nature. In an effort to fractionate lignocellulosic biomass and valorize specific constitutive fractions, the authors developed a strategy for the separation of 12 added value monomers produced during the hydrolytic base catalyzed depolymerization (BCD) of a Steam Exploded Aspen Lignin. The separation strategy was similar to vanillin purification to obtain pure monomers, but combining more steps after the lignin depolymerization such as acidification, batch liquid-liquid-extraction (LLE), followed by vacuum distillation, liquid chromatography (LC) and crystallization. The purpose was to develop basic data for an industrial size process flow diagram, and to evaluate both the monomer losses during the separation and the energy requirements. Experimentally testing of LLE, vacuum distillation and flash LC in the laboratory showed that batch vacuum distillation produced up to 4 fractions. Process simulation revealed that a series of 4 vacuum distillation columns could produce 5 distinct monomer streams, of which 3 require further chromatography and crystallization operations for purification. 22 refs., 4 tabs., 8 figs.

  19. Two Populations Mean-Field Monomer-Dimer Model

    Science.gov (United States)

    Alberici, Diego; Mingione, Emanuele

    2018-04-01

    A two populations mean-field monomer-dimer model including both hard-core and attractive interactions between dimers is considered. The pressure density in the thermodynamic limit is proved to satisfy a variational principle. A detailed analysis is made in the limit of one population is much smaller than the other and a ferromagnetic mean-field phase transition is found.

  20. The LOMOsup(R) process: a solution for residual monomers

    International Nuclear Information System (INIS)

    Derbyshire, R.L.

    1979-01-01

    Regulatory activity over the last several years has addressed the potential problems associated with the migration of residual monomers from a number of commodity food packages. Regardless of the outcome of current debates, it will always be desirable to reduce monomer levels to as low a level as economically practicable so that they do not become indirect additives. The LOMO process is a body of technology inclusive of an ionizing radiation treatment which can result in sharp reduction of residual monomer levels in commodity plastic resins. The process may be applicable to factory intermediates, raw resins, or finished articles. Depending upon the individual system and its monomers, LOMO treatment can result in reductions to levels which press today's analytical test capability. Industrial radiation processing is normally accomplished with electron beam accelerators. Electron beam processing continues to gain in understanding and acceptance as one of the very few basic methods by which energy can be imparted to an industrial process system. Typically, whole factories are constructed around one accelerator. (author)

  1. Complex-radical copolymerization of vinyl monomers on organoelemental initiators

    International Nuclear Information System (INIS)

    Grishin, D.F.

    1993-01-01

    Data on regularities of the initiation and growth of the (co)polymerization of polar vinyl series monomers on organo-elemental initiator, organo-boron in particular, are generalized. The effect of organo-metallic compounds and some phenol type inhibitors on the rate of acrylate (co)polymerization is analyzed from view of the change of electroacceptor properties (electrophilicity) of macroradicals

  2. Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

    International Nuclear Information System (INIS)

    Kaetsu, I.; Ito, A.; Hayashi, K.

    1975-01-01

    A specific mixture containing at least one polymerizable unsaturated monomer which is not vitrifiable by itself can advantageously be polymerized by irradiating the mixture at a temperature not higher than 100 0 C above glass transition temperature of the mixture with an ionizing radiation and/or a light. 12 claims, 6 drawings, figures

  3. 21 CFR 864.7300 - Fibrin monomer paracoagulation test.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Fibrin monomer paracoagulation test. 864.7300 Section 864.7300 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES HEMATOLOGY AND PATHOLOGY DEVICES Hematology Kits and Packages § 864.7300 Fibrin...

  4. Facile synthesis of allyl resinate monomer in an aqueous solution ...

    Indian Academy of Sciences (India)

    The synthesized monomer product appeared as a viscous liquid, with a viscosity of 460 mPa·s at 25◦C and a density of ... ated under high reaction temperature, which reduces the ... The use of DMF as an organic solvent also comes with.

  5. Monomer-Polymer Chemistry and the Impregnation Process

    Energy Technology Data Exchange (ETDEWEB)

    Stannett, V. [North Carolina State University, Raleigh, NC (United States)

    1968-10-15

    A brief outline of early polymerization techniques is followed by a description of polymerization process chemistry, impregnation and polymerization methods and criteria for the choice of monomer. General considerations, including the effects of polymerization inhibitors, swelling agents, radiation dose rate and sample thickness, are enumerated. (author)

  6. Structural similarity between β(3)-peptides synthesized from β(3)-homo-amino acids and aspartic acid monomers.

    Science.gov (United States)

    Ahmed, Sahar; Sprules, Tara; Kaur, Kamaljit

    2014-07-01

    Formation of stable secondary structures by oligomers that mimic natural peptides is a key asset for enhanced biological response. Here we show that oligomeric β(3)-hexapeptides synthesized from L-aspartic acid monomers (β(3)-peptides 1, 5a, and 6) or homologated β(3)-amino acids (β(3)-peptide 2), fold into similar stable 14-helical secondary structures in solution, except that the former form right-handed 14-helix and the later form left-handed 14-helix. β(3)-Peptides from L-Asp monomers contain an additional amide bond in the side chains that provides opportunities for more hydrogen bonding. However, based on the NMR solution structures, we found that β(3)-peptide from L-Asp monomers (1) and from homologated amino acids (2) form similar structures with no additional side-chain interactions. These results suggest that the β(3)-peptides derived from L-Asp are promising peptide-mimetics that can be readily synthesized using L-Asp monomers as well as the right-handed 14-helical conformation of these β(3)-peptides (such as 1 and 6) may prove beneficial in the design of mimics for right-handed α-helix of α-peptides. © 2014 Wiley Periodicals, Inc.

  7. Macroradical initiated polymerisation of acrylic and methacrylic monomers.

    Science.gov (United States)

    Mijangos, Irene; Guerreiro, António; Piletska, Elena; Whitcombe, Michael J; Karim, Kal; Chianella, Iva; Piletsky, Sergey

    2009-10-01

    An approach has been developed for the grafting of monomers onto poly(trimethylolpropane trimethacrylate) (polyTRIM) particles using 2,2-diethyl dithiocarbamic acid benzyl ester (DDCABE) as an initiator. A set of polymers was prepared with this technique over different lengths of time and the kinetics of the reaction studied experimentally. It was found that the grafting of initiator to the polymeric support followed a second order reaction, while the subsequent addition of monomers from solution into the polyTRIM macroradicals followed a first order reaction. The living nature of the iniferter modified macroradicals permits easy consecutive grafting of multiple polymeric layers, allowing straightforward functionalisation of particles. However, the effectiveness of the grafted initiator decreased with each cycle of polymerisation. This technique can be used for a wide range of applications in analytical and biochemistry.

  8. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers

    Science.gov (United States)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.

    2010-09-01

    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  9. Casting of organic glass by radiation-induced polymerization of glass-forming monomers at low temperature. II. Optical strain of remaining stress type

    International Nuclear Information System (INIS)

    Okubo, H.; Yoshii, F.; Kaetsu, I.; Honda, S.

    1978-01-01

    Previously it was found that casting could be carried out efficiently without strain formation by radiation-induced polymerization of glass-forming monomers. Two types of strain were observed in casting: thermal stream type, which was studied previously, and remained stress type. In this report, the effect of various factors on the formation of remaining stress-type strain in radiation-induced casting polymerization was studied. It was found that the molecular weight of prepolymer did not affect strain formation, while prepolymer concentration and viscosity of the system had a serious influence on strain formation. It could be deduced that this type of strain formed as a result of remaining inner stress due to poor relaxation of the shrinking stress. It was realized that less volume shrinkage of glass-forming monomers accompanying casting polymerization reduced the strain formation of this type in radiation-induced casting polymerization at low temperatures

  10. In situ polymerization of monomers for polyphenylquinoxaline-graphite fiber composites

    Science.gov (United States)

    Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

    1974-01-01

    In situ polymerization of monomers was used to prepare graphite-fiber-reinforced polyphenylquinoxaline composites. Six different monomer combinations were investigated. Composite mechanical property retention characteristics were determined at 316 C (600 F) over an extended time period.

  11. Functionalized Nanoporous Polymer Membranes with Well-Defined Pore Architectures via Lyotropic Liquid-Crystalline Monomers

    National Research Council Canada - National Science Library

    Gin, Douglas

    1997-01-01

    .... Two lyotropic liquid-crystalline monomer platforms have been synthesized. The interchannel separations in the polymerizable materials can be varied in the 30-40 A range by the choice of counterion on the ionic headgroup of the monomers...

  12. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Ghanem, Bader Saleh

    2017-04-13

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  13. Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Ghanem, Bader Saleh; Pinnau, Ingo

    2017-01-01

    Described herein are ortho-dimethyl-substituted and tetramethyi-substituted triptycene-containing diamine monomers and microporous triptycene-based poiyimides and poiyamides, and methods of making the monomers and polymers.

  14. Structure of human insulin monomer in water/acetonitrile solution

    Energy Technology Data Exchange (ETDEWEB)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta [National Medicines Institute (Poland); Tarnowska, Anna; Kawecki, Robert [Institute of Organic Chemistry Polish Academy of Sciences (Poland); Kozerski, Lech [National Medicines Institute (Poland)], E-mail: lkoz@icho.edu.pl

    2008-01-15

    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H{sub 2}O/CD{sub 3}CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER{sub V}C), or including a generalized Born solvent model (AMBER{sub G}B)

  15. Structure of human insulin monomer in water/acetonitrile solution

    International Nuclear Information System (INIS)

    Bocian, Wojciech; Sitkowski, Jerzy; Bednarek, Elzbieta; Tarnowska, Anna; Kawecki, Robert; Kozerski, Lech

    2008-01-01

    Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H 2 O/CD 3 CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER V C), or including a generalized Born solvent model (AMBER G B)

  16. Characterisation of polyhydroxyalkanoate copolymers with controllable four-monomer composition.

    Science.gov (United States)

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

    2008-03-20

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

  17. Influence of monomer on structure, processing and application characteristics of UV curable urethane acrylate composite coatings

    International Nuclear Information System (INIS)

    Grigale-Sorocina, Z; Kalnins, M; Gross, K A

    2016-01-01

    Increased interest in the esthetical natural nail coatings have encouraged more in-depth studies particularly of UV curable coatings: their formation, processing, structure, characteristics and removing. Typical requirement for nail coatings is good adhesion, but preferably for the short time of functioning (usual 2-4 weeks). This study investigated the impact of four different monomers (tertiobutyl cyclohexyl acrylate (TBCHA), ethylene glycol dimethacrylate (EGDMA), tetrahydrofurfuryl acrylate (THFA), hydroxypropyl methacrylate (HPMA)) to viscosity of uncured mixture and degree of conversion, mechanical properties, surface gloss, micro hardness and adhesion loss for cured films. Specific coating application requires comparatively high coating flexibility and stability of deformation characteristics. This can be achieved with composition containing 30% of monomer TBCHA, what shows ultimate elongation ε B = 0,23 - 0,24, modulus of elasticity E = 670-710 MPa and comparatively constant properties in 72 hours (ΔE = 1.3%, Δε B =6.0%). A composition with 40% of TBCHA shows the fastest coating destruction achieving adhesion loss within 3 min. (paper)

  18. Inhibition of Protein Tyrosine Phosphatase 1B by Aurintricarboxylic Acid and Methylenedisalicylic Acid: Polymer versus Monomer

    International Nuclear Information System (INIS)

    Shrestha, Suja; Lee, Keun Hyeung; Cho, Hyeong Jin

    2004-01-01

    In this study, we examined whether the in vitro inhibitory activity of ATA against PTPases resides in the monomer or high molecular weight components. Not to mention commercial ATA, the ATA sample synthesized according to the method previously reported to produce monomer was also found to contain polymeric materials as described below. Therefore, monomeric component of ATA was prepared absolutely free of polymer. Also synthesized in a pure form was methylenedisalicylic acid (MDSA), one of the low molecular weight components formed in the conventional preparation of ATA. Commercial MDSA was also proved to contain polymeric substances. The inhibitory potency of ATA and MDSA synthesized in a polymer-free form was evaluated against human protein tyrosine phosphatase 1B (PTP1B). Commercial ATA, however, contains significant amounts of polymeric materials schematically represented as. In general, ATA is prepared by condensation of salicylic acid with formaldehyde and the branching reaction results in the formation of polymers of molecular weights up to several thousands Dalton

  19. Multiple routes and milestones in the folding of HIV-1 protease monomer.

    Directory of Open Access Journals (Sweden)

    Massimiliano Bonomi

    Full Text Available Proteins fold on a time scale incompatible with a mechanism of random search in conformational space thus indicating that somehow they are guided to the native state through a funneled energetic landscape. At the same time the heterogeneous kinetics suggests the existence of several different folding routes. Here we propose a scenario for the folding mechanism of the monomer of HIV-1 protease in which multiple pathways and milestone events coexist. A variety of computational approaches supports this picture. These include very long all-atom molecular dynamics simulations in explicit solvent, an analysis of the network of clusters found in multiple high-temperature unfolding simulations and a complete characterization of free-energy surfaces carried out using a structure-based potential at atomistic resolution and a combination of metadynamics and parallel tempering. Our results confirm that the monomer in solution is stable toward unfolding and show that at least two unfolding pathways exist. In our scenario, the formation of a hydrophobic core is a milestone in the folding process which must occur along all the routes that lead this protein towards its native state. Furthermore, the ensemble of folding pathways proposed here substantiates a rational drug design strategy based on inhibiting the folding of HIV-1 protease.

  20. Thermodynamics of swelling of latex particles with two monomers: a sensitivity analysis

    NARCIS (Netherlands)

    Maxwell, I.A.; Noel, E.F.J.; Schoonbrood, H.A.S.; German, A.L.

    1993-01-01

    A sensitivity anal. is performed to det. at what conditions the simplified model for swelling of latex particles by two monomers or two solvents is valid. This model proposes that, inter alia, the fractions of two monomers in the latex particles and in the monomer droplets are equal. The model is a

  1. N-Heterocyclic Olefins as Initiators for the Polymerization of (Meth)Acrylic Monomers: A Combined Experimental and Theoretical Approach

    KAUST Repository

    Naumann, Stefan

    2017-08-25

    The zwitterionic organopolymerization of four different acrylic monomers (N,N-dimethylacrylamide, methyl acrylate, methyl methacrylate and tert-butyl methacrylate) based on neutral initiators, so-called N-heterocyclic olefins (NHOs), is presented. Scope and underlying (deactivation-)mechanisms where studied in a combined experimental and computational effort. From a range of differently structured NHOs it emerged that imidazole-, in contrast to imidazoline- and benzimidazole-derivatives, readily polymerize the selected monomers. While the additive-free reactions proceed with a relatively low degree of control to yield largely atactic material, for the acrylamide the addition of LiCl as µ-type ligand has been shown to result in a rapid and quantitative monomer consumption. The thus generated poly(N,N-dimethyl acrylamide) was found to be highly isotactic (>90% isotactic dyads) with high molecular weight (Mn = 250 000 – 650 000 g/mol, ÐM = 1.3- 1.6). Complementing DFT calculations considered the zwitterionic chain growth with respect to competing side reactions, namely spirocycles and enamine formation. It was found that NHOs with unsaturated backbone better support the zwitterionic chain growth, with the spirocycles acting as dormant species that slow down but do not quench the polymerization process. Contrasting this, enamine formation irreversibly terminates the polymerization and is found to be energetically favored. This pathway can be blocked by introduction of substituents on the exocyclic carbon of the NHO, resulting in structures like 2-isopropylidene-1,3,4,5-tetramethylimidazoline (4) which consequently deliver the most controlled polymerizations. Finally, a good correlation of the initiation energy barrier with the buried volume (%VBur) and the Parr electrophilicity index is described, allowing for a quick and reliable screening of potential monomers based on these two readily accessible parameters.

  2. A radiation-sensitive monomer of 2,4-hexadiyn-1,6-bis(p-toluene sulphonyl urethane) in PVA as a radiochromic film dosimeter

    Science.gov (United States)

    Soliman, Yasser S.; Abdel-Fattah, A. A.; Hamed, A. A.; Bayomi, A. M. M.

    2018-03-01

    A conjugated monomer 2,4-hexadiyn-1,6-bis(p-toluene sulphonyl urethane) (HDTU) was synthesized. Thereafter, it was incorporated into polyvinyl alcohol (PVA), and coated on self-adhesive sheet, thus to prepare film dosimeters. The monomer and films were analyzed using X-ray diffraction (XRD), FTIR spectroscopy and specular reflectance colorimetry. This monomer polymerizes in the films by radiation and turns progressively blue in proportion to absorbed dose, indicating the formation of π-conjugated colored poly-HDTU. Color development was investigated at 480 nm and 610 nm for dose monitoring ranging from 10 Gy to 15 kGy. HDTU in PVA film is highly ordered and crystalline and, upon irradiation, it forms a semi-crystalline polymer with nearly the same interplanar distances as the monomer, indicating the occurrence of topochemical polymerization. During irradiation, polymerization of the monomer is nearly independent of humidity in the range of 0-53% and temperature in the range of 25-45 °C. The uncertainty of this system is 5.16% at 95% confidence level.

  3. Radiation Induced Grafting of Acrylate onto Waste Rubber: The Effect of Monomer Type

    Directory of Open Access Journals (Sweden)

    Shirajuddin Siti Salwa M.

    2017-01-01

    Full Text Available The effect of three different acrylate group monomers, namely n-butyl acrylate, methacrylic acid and tripropylene glycol diacrylate of radiation induced grafting onto waste rubber was studied. The electron beam accelerator operated at voltage of 2MeV was used to irradiate the waste rubber at 10 kGy and 100 kGy absorbed radiation dose, respectively. The formation of grafting was observed from the increase in the grafting yield and confirmed by Transformed Infra-Red Spectroscopy results. According to the result obtained, only tripropylene glycol diacrylate was selected to graft onto waste rubber. The carbonyl bond from acrylate groups was seen at 1726 cm-1 band which confirmed the presence of TPGDA in the polymer matrix. This indicates the successful preparation of the TPGDA-grafted waste rubber via radiation induced grafting techniques.

  4. Radiation induced ionic polymerisation and grafting of vinyl monomers

    International Nuclear Information System (INIS)

    Stannett, V.T.

    1981-01-01

    Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dielectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly(vinyl chloride) and to polypropylene will be presented. (author)

  5. Radiation vulcanization of ethylene-propylene rubber with polyfunctional monomers

    Energy Technology Data Exchange (ETDEWEB)

    Jinhua, Wang; Yoshii, Fumio; Makuuchi, Keizo

    2001-01-01

    This paper reports on the sensitizing efficiency of several polyfunctional monomers to radiation vulcanization of ethylene-propylene rubber. And the results show that triethyleneglycol dimethacrylate (TEGDMA) gave the best results. TEGDMA not only lowers the vulcanization dose (D{sub v}), but also increases the tensile strength greatly. The content of TEGDMA does not affect the D{sub v} of TEGDMA-EPM, but affects the tensile strength at the D{sub v}. At best content (0.04 mol/100 g EPM), the tensile strength is increased from 6.0 to 12 MPa, and the elongation is 790% at the D{sub v}. (author)

  6. Breathing zone concentrations of methylmethacrylate monomer during joint replacement operations

    DEFF Research Database (Denmark)

    Darre, E; Jørgensen, L G; Vedel, P

    1992-01-01

    By use of a methylmethacrylate (MMA) Dräger tube and bellow bump, the breathing zone concentrations of MMA monomer were measured for the operating surgeon during cementation of the components of hip and knee joint prostheses. The highest recordings (50-100 p.p.m.) were encountered during cementat...... cementation of the acetabular cups with conventional polymethylmethacrylate cement. Such exposure could be eliminated by the use of personal protection equipment, local punctual field suction or change to a MMA/n-decylmethacrylate/isobornylmethacrylate bone cement....

  7. Cationic Organochalcogen with Monomer/Excimer Emissions for Dual-Color Live Cell Imaging and Cell Damage Diagnosis.

    Science.gov (United States)

    Chao, Xi-Juan; Wang, Kang-Nan; Sun, Li-Li; Cao, Qian; Ke, Zhuo-Feng; Cao, Du-Xia; Mao, Zong-Wan

    2018-04-25

    Studies on the development of fluorescent organic molecules with different emission colors for imaging of organelles and their biomedical application are gaining lots of focus recently. Here, we report two cationic organochalcogens 1 and 2, both of which exhibit very weak green emission (Φ 1 = 0.12%; Φ 2 = 0.09%) in dilute solution as monomers, but remarkably enhanced green emission upon interaction with nucleic acids and large red-shifted emission in aggregate state by the formation of excimers at high concentration. More interestingly, the monomer emission and excimer-like emission can be used for dual color imaging of different organelles. Upon passively diffusing into cells, both probes selectively stain nucleoli with strong green emission upon 488 nm excitation, whereas upon 405 nm excitation, a completely different stain pattern by staining lysosomes (for 1) or mitochondria (for 2) with distinct red emission is observed because of the highly concentrated accumulation in these organelles. Studies on the mechanism of the accumulation in lysosomes (for 1) or mitochondria (for 2) found that the accumulations of the probes are dependent on the membrane permeabilization, which make the probes have great potential in diagnosing cell damage by sensing lysosomal or mitochondrial membrane permeabilization. The study is demonstrative, for the first time, of two cationic molecules for dual-color imaging nucleoli and lysosomes (1)/mitochondria (2) simultaneously in live cell based on monomer and excimer-like emission, respectively, and more importantly, for diagnosing cell damage.

  8. Monomer-dimer problem on random planar honeycomb lattice

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Haizhen [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China); Department of Mathematics, Qinghai Normal University, Xining 810008, Qinghai (China); Zhang, Fuji; Qian, Jianguo, E-mail: jqqian@xmu.edu.cn [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China)

    2014-02-15

    We consider the monomer-dimer (MD) problem on a random planar honeycomb lattice model, namely, the random multiple chain. This is a lattice system with non-periodic boundary condition, whose generating process is inspired by the growth of single walled zigzag carbon nanotubes. By applying algebraic and combinatorial techniques we establish a calculating expression of the MD partition function for bipartite graphs, which corresponds to the permanent of a matrix. Further, by using the transfer matrix argument we show that the computing problem of the permanent of high order matrix can be converted into some lower order matrices for this family of lattices, based on which we derive an explicit recurrence formula for evaluating the MD partition function of multiple chains and random multiple chains. Finally, we analyze the expectation of the number of monomer-dimer arrangements on a random multiple chain and the asymptotic behavior of the annealed MD entropy when the multiple chain becomes infinite in width and length, respectively.

  9. Elution of monomer from different bulk fill dental composite resins.

    Science.gov (United States)

    Cebe, Mehmet Ata; Cebe, Fatma; Cengiz, Mehmet Fatih; Cetin, Ali Rıza; Arpag, Osman Fatih; Ozturk, Bora

    2015-07-01

    The purpose of this study was to evaluate the elution of Bis-GMA, TEGDMA, HEMA, and Bis-EMA monomers from six bulk fill composite resins over four different time periods, using HPLC. Six different composite resin materials were used in the present study: Tetric Evo Ceram Bulk Fill (Ivoclar Vivadent, Amherst, NY), X-tra Fill (VOCO, Cuxhaven, Germany), Sonic Fill (Kerr, Orange, CA, USA), Filtek Bulk Fill (3M ESPE Dental Product, St. Paul, MN), SDR (Dentsply, Konstanz, Germany), EQUIA (GC America INC, Alsip, IL). The samples (4mm thickness, 5mm diameter) were prepared and polymerized for 20s with a light emitted diode unit. After fabrication, each sample was immediately immersed in 75wt% ethanol/water solution used as extraction fluid and stored in the amber colored bottles at room temperature. Ethanol/water samples were taken (0.5mL) at predefined time intervals:10m (T1), 1h (T2), 24h (T3) and 30 days (T4). These samples were analyzed by HPLC. The obtained data were analyzed with one-way ANOVA and Tukey HSD at significance level of pcomposites (pcomposite resins in all time periods and the amount of eluted monomers was increased with time. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  10. Surface modification of commercial seawater reverse osmosis membranes by grafting of hydrophilic monomer blended with carboxylated multiwalled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Vatanpour, Vahid, E-mail: vahidvatanpour@khu.ac.ir; Zoqi, Naser

    2017-02-28

    Highlights: • A commercial PA RO membrane was modified by grafting of hydrophilic acrylic acid. • COOH-MWCNTs were mixed in grafting layer to increase permeability and antifouling. • However, more increase of CNTs caused in reduction of flux of the membranes. • Effect of acrylic acid amount, contact time and curing time was optimized. - Abstract: In this study, modification of commercial seawater reverse osmosis membranes was carried out with simultaneous use of surface grafting and nanoparticle incorporation. Membrane grafting with a hydrophilic acrylic acid monomer and thermal initiator was used to increase membrane surface hydrophilicity. The used nanomaterial was carboxylated multiwalled carbon nanotubes (MWCNTs), which were dispersed in the grafting solution and deposited on membrane surface to reduce fouling by creating polymer brushes and hydrodynamic resistance. Effectiveness of the grafting process (formation of graft layer on membrane surface) was proved by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analyses. Increase of membrane surface hydrophilicity was approved with contact angle test. First, the grafting was performed on the membrane surfaces with different monomer concentrations, various contact times and several membrane curing times (three variables for optimization). The modified membranes were tested by a cross-flow setup using saline solution for permeability and rejection tests, and bovine serum albumin (BSA) solution for fouling test. The results showed that the modified membranes with 0.75 M of monomer, 3 min contact time and 80 min curing time in an oven at 50 °C presented the highest flux and lowest rejection decline related to the commercial reverse osmosis membrane. In the next step, the optimum grafting condition was selected and the nanotubes with different weight percentages were dispersed in the acrylic acid monomer solution. The membrane containing 0.25 wt% COOH-MWCNTs showed the

  11. Surface modification of commercial seawater reverse osmosis membranes by grafting of hydrophilic monomer blended with carboxylated multiwalled carbon nanotubes

    International Nuclear Information System (INIS)

    Vatanpour, Vahid; Zoqi, Naser

    2017-01-01

    Highlights: • A commercial PA RO membrane was modified by grafting of hydrophilic acrylic acid. • COOH-MWCNTs were mixed in grafting layer to increase permeability and antifouling. • However, more increase of CNTs caused in reduction of flux of the membranes. • Effect of acrylic acid amount, contact time and curing time was optimized. - Abstract: In this study, modification of commercial seawater reverse osmosis membranes was carried out with simultaneous use of surface grafting and nanoparticle incorporation. Membrane grafting with a hydrophilic acrylic acid monomer and thermal initiator was used to increase membrane surface hydrophilicity. The used nanomaterial was carboxylated multiwalled carbon nanotubes (MWCNTs), which were dispersed in the grafting solution and deposited on membrane surface to reduce fouling by creating polymer brushes and hydrodynamic resistance. Effectiveness of the grafting process (formation of graft layer on membrane surface) was proved by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) analyses. Increase of membrane surface hydrophilicity was approved with contact angle test. First, the grafting was performed on the membrane surfaces with different monomer concentrations, various contact times and several membrane curing times (three variables for optimization). The modified membranes were tested by a cross-flow setup using saline solution for permeability and rejection tests, and bovine serum albumin (BSA) solution for fouling test. The results showed that the modified membranes with 0.75 M of monomer, 3 min contact time and 80 min curing time in an oven at 50 °C presented the highest flux and lowest rejection decline related to the commercial reverse osmosis membrane. In the next step, the optimum grafting condition was selected and the nanotubes with different weight percentages were dispersed in the acrylic acid monomer solution. The membrane containing 0.25 wt% COOH-MWCNTs showed the

  12. Thermal and Optical Properties of CdS Nanoparticles in Thermotropic Liquid Crystal Monomers

    Directory of Open Access Journals (Sweden)

    Marc Alnot

    2010-03-01

    Full Text Available Two new mesogenic monomers, namely 3,3’-dimethoxy-4,4’-di(hydroxyhexoxy-N-benzylidene-o-Tolidine (Ia and 4,4’-di(6-hydroxyhexoxy-N-benzylidene-o-Tolidine (IIa, were reacted with cadmium sulfide (CdS via an in situ chemical precipitation method in ethanol to produce CdS nanocomposites. A series of different mass compositions of CdS with Ia and IIa ranging from 0.1:1.0 to 1.0:1.0 (w/w were prepared and characterized using X-ray Diffraction (XRD, Raman spectroscopy, Fourier Transform Infrared Spectroscopy (FT-IR, Transmission Electron Microscopy (TEM, Polarizing Optical Microscopy (POM and Differential Scanning Calorimetry (DSC, X-ray Photoelectron Spectroscopy (XPS and Photoluminescence Spectroscopy (PL. XRD showed that the broad peaks are ascribed to the formation of cubic CdS nanoparticles in both Ia and IIa. The average particle size for both nanocomposites was less than 5 nm with a narrower size distribution when compared with pure CdS nanoparticles. The analyses from POM and DSC demonstrated that mass composition from 0.1:1.0 up to 0.5:1.0 of CdS:Ia nanocomposites showed their enantiotropic nematic phase. On the other hand, polarizing optical microscopy (POM for IIa nanocomposites showed that the liquid crystal property vanished completely when the mass composition was at 0.2:1.0. PL emissions for CdS: Ia or IIa nanocomposites indicated deep trap defects occurred in these both samples. The PL results revealed that addition of CdS to Ia monomers suppressed the photoluminescence intensity of Ia. However, the introduction of CdS to IIa monomers increased the photoluminescence and was at a maximum when the mass composition was 0.3:1.0, then decreased in intensity as more CdS was added. The XPS results also showed that the stoichiometric ratios of S/Cd were close to 1.0:1.0 for both types of nanocomposites for a mass composition of 1.0:1.0 (CdS:matrix.

  13. Silyl Ketene Acetals/B(C6F53 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers

    Directory of Open Access Journals (Sweden)

    Lu Hu

    2018-03-01

    Full Text Available This work reveals the silyl ketene acetal (SKA/B(C6F53 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP of polar acrylic monomers, including methyl linear methacrylate (MMA, and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL and α-methylene-γ-butyrolactone (MBL as well. The in situ NMR monitored reaction of SKA with B(C6F53 indicated the formation of Frustrated Lewis Pairs (FLPs, although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C6F53-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C6F53-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C6F53 is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS. Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn and narrow molecular weight distribution (MWD.

  14. Graft copolimerization of hydrophilic monomers onto irradiated polypropylene fibers

    International Nuclear Information System (INIS)

    Sundardi, F.

    1978-01-01

    A method of graft copolymerization of hydrophilic monomers, such as 1-vinyl-2-pyrrolidone, acrylonitrile, acrylic acid, and acrylamide, onto irradiated polypropylene fibers has been studied. γ ray as well as electron beam were employed for the irradiation processes. Graft-copolymerization kinetics and the properties of grafted fibers have been investigated. Moisture regain, dyes absorption, and melting point of the grafted fibers were found to increase with the increasing of the degree of grafting. Polypropylene for 1-vinyl-2-pyrrolidone grafted fibers showed excellent dye absorption for almost all kinds of dyes such as direct, basic, acid, reactive, disper, and naphthol dyes. However, for polypropylene acrylic acid grafted fibers, the colorfastness to washing was found to be unsatisfactory. The colorfastness to washing for polypropylene 1-vinyl-2-pyrrolidone grafted fibers was found to be fairly good for certain types of dyes such as vat and naphthol dyes. (author)

  15. Biobased Epoxy Nanocomposites Derived from Lignin-Based Monomers.

    Science.gov (United States)

    Zhao, Shou; Abu-Omar, Mahdi M

    2015-07-13

    Biobased epoxy nanocomposites were synthesized based on 2-methoxy-4-propylphenol (dihydroeugenol, DHE), a molecule that has been obtained from the lignin component of biomass. To increase the content of hydroxyl groups, DHE was o-demethylated using aqueous HBr to yield propylcatechol (DHEO), which was subsequently glycidylated to epoxy monomer. Optimal conditions in terms of yield and epoxy equivalent weight were found to be 60 °C with equal NaOH/phenolic hydroxyl molar ratio. The structural evolution from DHE to cured epoxy was followed by (1)H NMR and Fourier transform infrared spectroscopy. The nano-montmorillonite modified DHEO epoxy exhibited improved storage modulus and thermal stability as determined from dynamic mechanical analysis and thermogravimetric analysis. This study widens the synthesis routes of biobased epoxy thermosets from lignin-based molecules.

  16. On-line measurement of residual monomer during polymerisation of acrylamide using ultrasonics

    International Nuclear Information System (INIS)

    Ponraju, D.; Sebastian, Letha; Viswanathan, S.; Natarajan, A.; Palanichamy, P.; Jayakumar, T.; Baldev Raj

    1996-01-01

    An ultrasonic technique for the estimation of residual acrylamide monomer during the polymerization of aqueous acrylamide solution has been investigated. Polyacrylamide gel medium serves as a sensitive medium for detection and dosimetry of fast and thermal neutrons. This technique is based on the fact that the velocity of ultrasonic wave increases with the increase in elasticity due to polymerization. The percentage of residual acrylamide monomer is estimated using ultraviolet spectrophotometric analysis. The ultrasonic velocity is correlated with the residual monomer concentration

  17. The VPAC2 agonist peptide histidine isoleucine (PHI) up-regulates glutamate transport in the corpus callosum of a rat model of amyotrophic lateral sclerosis (hSOD1G93A) by inhibiting caspase-3 mediated inactivation of GLT-1a.

    Science.gov (United States)

    Goursaud, Stéphanie; Focant, Marylène C; Berger, Julie V; Nizet, Yannick; Maloteaux, Jean-Marie; Hermans, Emmanuel

    2011-10-01

    Degeneration of corpus callosum appears in patients with amyotrophic lateral sclerosis (ALS) before clinical signs of upper motor neuron death. Considering the ALS-associated impairment of astrocytic glutamate uptake, we have characterized the expression and activity of the glutamate transporter isoforms GLT-1a and GLT-1b in the corpus callosum of transgenic rats expressing a mutated form of the human superoxide dismutase 1 (hSOD1(G93A)). We have also studied the effect of peptide histidine isoleucine (PHI), a vasoactive intestinal peptide (VIP)/pituitary adenylate cyclase-activating polypeptide (PACAP) receptor 2 (VPAC(2)) agonist on glutamate transporters both in vivo and in callosal astrocytes. Before the onset of motor symptoms, the expression of both transporter isoforms was correlated with a constitutive activity of caspase-3. This enzyme participates in the down-regulation of GLT-1 in ALS, and here we demonstrated its involvement in the selective degradation of GLT-1a in the white matter. A single stereotactic injection of PHI into the corpus callosum of symptomatic rats decreased caspase-3 activity and promoted GLT-1a expression and uptake activity. Together, with evidence for a reduced expression of prepro-VIP/PHI mRNA in the corpus callosum of transgenic animals, these data shed light on the modulatory role of the VIP/PHI system on the glutamatergic transmission in ALS.

  18. Electrostatic Interactions between Elongated Monomers Drive Filamentation of Drosophila Shrub, a Metazoan ESCRT-III Protein

    Directory of Open Access Journals (Sweden)

    Brian J. McMillan

    2016-08-01

    Full Text Available The endosomal sorting complex required for transport (ESCRT is a conserved protein complex that facilitates budding and fission of membranes. It executes a key step in many cellular events, including cytokinesis and multi-vesicular body formation. The ESCRT-III protein Shrub in flies, or its homologs in yeast (Snf7 or humans (CHMP4B, is a critical polymerizing component of ESCRT-III needed to effect membrane fission. We report the structural basis for polymerization of Shrub and define a minimal region required for filament formation. The X-ray structure of the Shrub core shows that individual monomers in the lattice interact in a staggered arrangement using complementary electrostatic surfaces. Mutations that disrupt interface salt bridges interfere with Shrub polymerization and function. Despite substantial sequence divergence and differences in packing interactions, the arrangement of Shrub subunits in the polymer resembles that of Snf7 and other family homologs, suggesting that this intermolecular packing mechanism is shared among ESCRT-III proteins.

  19. Influence of template/functional monomer/cross‐linking monomer ratio on particle size and binding properties of molecularly imprinted nanoparticles

    DEFF Research Database (Denmark)

    Yoshimatsu, Keiichi; Yamazaki, Tomohiko; Chronakis, Ioannis S.

    2012-01-01

    A series of molecularly imprinted polymer nanoparticles have been synthesized employing various template/functional monomer/crosslinking monomer ratio and characterized in detail to elucidate the correlation between the synthetic conditions used and the properties (e.g., particle size and templat...... tuning of particle size and binding properties are required to fit practical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012...

  20. Comparison and Analysis of 3,4 dihydrocylmandelic acid (DHMA) and noremetanephrine (NMN) on Amyloid-Beta 40 Monomer for treatment of Alzheimer's Disease using Molecular Dynamics Simulation

    Science.gov (United States)

    Choi, Woosung; Jee, Sang Eun; Jang, Seung Soon

    Alzheimer's disease (AD) is type of degenerative dementia caused memory loss and behavior problem. Main reason of AD is Amyloid-Beta 40(A β) mostly composed of α -helix form misfolds to insoluble fibrils and soluble oilgomer. This insoluble fibrils aggregate with beta sheet structure and form the plaque which is caused nurotoxicity in brain. Both 3,4 dihydrocylmandelic acid (DHMA) and noremetanephrine (NMN) are the metabolite of norepinephrine in brain . Also these are inhibit the changing formation of fibrils and maintain the α -helix structure. In this computational modeling study, both NMN and DHMA molecules were modified and analyzed for specific effect on the A β-monomer using molecular dynamics simulation. Using molecular dynamic simulation, NMN and DHMA act as modulator on three A β-monomer batches and could observe the conformational changing of these A β-monomer under the physiologocal condition. This computational experiment is designed to compare and analyze both of chemicals for determining which chamecal would be more effective on the conformation of A β 40 monomer.

  1. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

  2. Oligodeoxynucleotides containing 2'-amino-LNA nucleotides as constrained morpholino phosphoramidate and phosphorodiamidate monomers

    DEFF Research Database (Denmark)

    Kristensen, Kim Vejlegaard; Paul, Sibasish; Kosbar, Tamer

    2017-01-01

    Incorporation in a 2'→5' direction of a phosphorodiamidite 2'-amino-LNA-T nucleotide as the morpholino phosphoramidate and N,N-dimethylamino phosphorodiamidate monomers into six oligonucleotides is reported. Thermal denaturation studies showed that the novel 2'-amino-LNA-based morpholino monomers...

  3. Modulation of i-motif thermodynamic stability by the introduction of UNA (unlocked nucleic acid) monomers

    DEFF Research Database (Denmark)

    Pasternak, Anna; Wengel, Jesper

    2011-01-01

    The influence of acyclic RNA derivatives, UNA (unlocked nucleic acid) monomers, on i-DNA thermodynamic stability has been investigated. The 22 nt human telomeric fragment was chosen as the model sequence for stability studies. UNA monomers modulate i-motif stability in a position-depending manner...

  4. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo; Ghanem, Bader; Swaidan, Raja

    2015-01-01

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using

  5. Sulfonated copolyimide membranes derived from a novel diamine monomer with pendant benzimidazole groups for fuel cells

    DEFF Research Database (Denmark)

    Li, Wei; Guo, Xiaoxia; Aili, David

    2015-01-01

    . A series of sulfonated copolyimides (SPI) are prepared via random copolymerizatio of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with a new diamine monomer with pendant benzimidazole groups, 2,2'-bis(4-(1H-benzo[d]imidazol-2-yl)phenoxy)benzidine (BIPOB), and a sulfonated diamine monomer 4,4'-bis...

  6. Folding Landscape of Mutant Huntingtin Exon1: Diffusible Multimers, Oligomers and Fibrils, and No Detectable Monomer.

    Directory of Open Access Journals (Sweden)

    Bankanidhi Sahoo

    Full Text Available Expansion of the polyglutamine (polyQ track of the Huntingtin (HTT protein above 36 is associated with a sharply enhanced risk of Huntington's disease (HD. Although there is general agreement that HTT toxicity resides primarily in N-terminal fragments such as the HTT exon1 protein, there is no consensus on the nature of the physical states of HTT exon1 that are induced by polyQ expansion, nor on which of these states might be responsible for toxicity. One hypothesis is that polyQ expansion induces an alternative, toxic conformation in the HTT exon1 monomer. Alternative hypotheses posit that the toxic species is one of several possible aggregated states. Defining the nature of the toxic species is particularly challenging because of facile interconversion between physical states as well as challenges to identifying these states, especially in vivo. Here we describe the use of fluorescence correlation spectroscopy (FCS to characterize the detailed time and repeat length dependent self-association of HTT exon1-like fragments both with chemically synthesized peptides in vitro and with cell-produced proteins in extracts and in living cells. We find that, in vitro, mutant HTT exon1 peptides engage in polyQ repeat length dependent dimer and tetramer formation, followed by time dependent formation of diffusible spherical and fibrillar oligomers and finally by larger, sedimentable amyloid fibrils. For expanded polyQ HTT exon1 expressed in PC12 cells, monomers are absent, with tetramers being the smallest molecular form detected, followed in the incubation time course by small, diffusible aggregates at 6-9 hours and larger, sedimentable aggregates that begin to build up at 12 hrs. In these cell cultures, significant nuclear DNA damage appears by 6 hours, followed at later times by caspase 3 induction, mitochondrial dysfunction, and cell death. Our data thus defines limits on the sizes and concentrations of different physical states of HTT exon1 along the

  7. Ligustrazine monomer against cerebral ischemia-reperfusion injury

    Directory of Open Access Journals (Sweden)

    Hai-jun Gao

    2015-01-01

    Full Text Available Ligustrazine (2,3,5,6-tetramethylpyrazine is a major active ingredient of the Szechwan lovage rhizome and is extensively used in treatment of ischemic cerebrovascular disease. The mechanism of action of ligustrazine use against ischemic cerebrovascular diseases remains unclear at present. This study summarizes its protective effect, the optimum time window of administration, and the most effective mode of administration for clinical treatment of cerebral ischemia/reperfusion injury. We examine the effects of ligustrazine on suppressing excitatory amino acid release, promoting migration, differentiation and proliferation of endogenous neural stem cells. We also looked at its effects on angiogenesis and how it inhibits thrombosis, the inflammatory response, and apoptosis after cerebral ischemia. We consider that ligustrazine gives noticeable protection from cerebral ischemia/reperfusion injury. The time window of ligustrazine administration is limited. The protective effect and time window of a series of derivative monomers of ligustrazine such as 2-[(1,1-dimethylethyloxidoimino]methyl]-3,5,6-trimethylpyrazine, CXC137 and CXC195 after cerebral ischemia were better than ligustrazine.

  8. Adjuvant activity of peptidoglycan monomer and its metabolic products.

    Science.gov (United States)

    Halassy, Beata; Krstanović, Marina; Frkanec, Ruza; Tomasić, Jelka

    2003-02-14

    Peptidoglycan monomer (PGM) is a natural compound of bacterial origin. It is a non-toxic, non-pyrogenic, water-soluble immunostimulator potentiating humoral immune response to ovalbumin (OVA) in mice. It is fast degraded and its metabolic products-the pentapeptide (PP) and the disaccharide (DS)-are excreted from the mammalian organism upon parenteral administration. The present study investigates: (a). whether PGM could influence the long-living memory generation; (b). whether metabolic products retain adjuvant properties of the parent compound and contribute to its adjuvanticity. We report now that mice immunised twice with OVA+PGM had significantly higher anti-OVA IgG levels upon challenge with antigen alone 6 months later in comparison to control group immunised with OVA only. PP and DS were prepared enzymatically in vitro as apyrogenic and chemically pure compounds. When mice were immunised with OVA plus PP and DS, respectively, the level of anti-OVA IgGs in sera was not higher than in mice immunised with OVA alone, while PGM raised the level of specific antibodies. Results implicate that the adjuvant active molecule, capable of enhancing long-living memory generation, is PGM itself, and none of its metabolic products.

  9. Use of Monomer Fraction Data in the Parametrization of Association Theories

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Tsivintzelis, Ioannis; von Solms, Nicolas

    2010-01-01

    the monomer fraction of hydrogen bonding compounds and their mixtures. Monomer fraction data are obtained from spectroscopic measurements and they are available for a few compounds such as pure water and alcohols as well as for some alcohol–alkane and similar mixtures. These data are useful...... “improved” model parameters can be obtained if monomer fraction data are included in the parameter estimation together with vapor pressures and liquid densities. The expression “improved” implies parameters which can represent several pure compound properties as well as monomer fraction data for pure......, liquid densities and monomer fractions of water and alcohols. The 4C scheme is the best choice for water, while for methanol there is small difference between the 2B and 3B association schemes....

  10. Polyfunctional monomers as additives for enhancing the radiation copolymerization of styrene with polyethylene, polypropylene, and PVC

    International Nuclear Information System (INIS)

    Ang, C.H.; Garnett, J.L.; Levot, R.; Long, M.A.

    1982-01-01

    Additives which can increase the yield in the radiation grafting of monomers to polymers are useful. The use of polyfunctional monomers as additives (approx. = 1% v/v) are shown to enhance significantly the copolymerization yields of styrene in methanol to films of polyethylene and polypropylene under certain radiation conditions. The results obtained when the polyolefins are replaced by PVC as backbone polymer in these accelerated grafting reactions are reported. Divinylbenzene (DVB) and trimethylolpropane triacrylate (TMPTA) were used as representative polyfunctional monomers for the enhancement effect. When polypropylene was used as backbone polymer, the inclusion of DVB significantly enhanced the radiation grafting of styrene in methanol at all monomer concentrations studied above 35%. At certain monomer concentrations (50% , 60%), the yield of graft copolymer was almost doubled by the addition of DVB. 3 tables. (DP)

  11. Application of Nuclear Radiation to Textile Materials and Processes. Radiation-induced graft copolymerization of vinyl monomers and fibrous polymers; Applications des rayonnements aux textiles. Formation radiochimique de copolymeres ''greffes'' par l'action de monomeres vinyliques sur des polymeres en fibre; Primenenie yadernogo izlucheniya v tekstil'noj promyshlennosti. Obrazovanie privitykh sopolimerov iz vinilovykh monomerov i voloknistykh polimerov pod dejstviem izlucheniya; Aplicaciones de las radiaciones nucleares a los procesos y materiales textiles. Copolimerizacion por injerto radioinducida de monomeros vinilicos y de polimeros fibrosos

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, Jr., A. A.; Rutherford, H. A. [University of North Carolina at Raleigh, NC (United States)

    1963-11-15

    materials is not good enough for commercial acceptance. The strength of cellulose acetate yam, as well as the modulus, can be materially increased by the addition of polyacrylonitrile. Other monomers do not behave in this manner. There is some indication that the fibre may be improved with one compound, especially with respect to its behaviour in the wet state. Fibre modification by the procedure described might be practical commercially if techniques that will increase the rate of diffusion of the monomer into the fibre structure can be developed. (author) [French] Les auteurs ont mis au point une methode qui permet de realiser par les rayonnements un greffage homogene de monomeres vinyliques volatils sur des polymeres en fibres. Elle consiste a ajouter le compose organique en phase vapeur; on procede, soit par irradiation de l'ensemble, soit par irradiation prealable des polymeres, aux rayons du cobalt-60. Les auteurs ont etudie des systemes qui accelerent la formation des copolymeres ''greffes''; ils ont constate qu'il est possible d'ajouter des quantites significatives de plusieurs des monomeres sans qu'il en resulte de dommages radioinduits dans le substrat fibreux. Les polymeres en fibres relativement instables en presence des rayonnements sont ceux qui fixent le plus facilement les composes vinyliques. C'est le cas des matieres cellulosiques, des esters de cellulose, des polyamides et du polypropylene. Le monomere s'ajoute au substrat fibreux par un mecanisme de radicaux libres, et, comme on l'a indique plus haut, on peut irradier d'abord les polymeres et ensuite provoquer le greffage par exposition de la matiere irradiee S la vapeur du monomere. On a tente de determiner la duree de vie des radicaux libres; il est difficile de donner des chiffres exacts, mais on a demontre qu'ils peuvent subsister dans certaines fibres 15 a 20 heures apres l'irradiation, meme a la temperature ambiante. Des resultats experimentaux preliminaires donnent egalement a penser que le temps

  12. Anionic PPV polymerization from the sulfinyl precursor route : Block copolymer formation from sequential addition of monomers

    NARCIS (Netherlands)

    Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

    2013-01-01

    The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to

  13. Simultaneous membrane interaction of amphipathic peptide monomers, self-aggregates and cargo complexes detected by fluorescence correlation spectroscopy.

    Science.gov (United States)

    Vasconcelos, Luís; Lehto, Tõnis; Madani, Fatemeh; Radoi, Vlad; Hällbrink, Mattias; Vukojević, Vladana; Langel, Ülo

    2018-02-01

    Peptides able to translocate cell membranes while carrying macromolecular cargo, as cell-penetrating peptides (CPPs), can contribute to the field of drug delivery by enabling the transport of otherwise membrane impermeable molecules. Formation of non-covalent complexes between amphipathic peptides and oligonucleotides is driven by electrostatic and hydrophobic interactions. Here we investigate and quantify the coexistence of distinct molecular species in multiple equilibria, namely peptide monomer, peptide self-aggregates and peptide/oligonucleotide complexes. As a model for the complexes, we used a stearylated peptide from the PepFect family, PF14 and siRNA. PF14 has a cationic part and a lipid part, resembling some characteristics of cationic lipids. Fluorescence correlation spectroscopy (FCS) and fluorescence cross-correlation spectroscopy (FCCS) were used to detect distinct molecular entities in solution and at the plasma membrane of live cells. For that, we labeled the peptide with carboxyrhodamine 6G and the siRNA with Cyanine 5. We were able to detect fluorescent entities with diffusional properties characteristic of the peptide monomer as well as of peptide aggregates and peptide/oligonucleotide complexes. Strategies to avoid peptide adsorption to solid surfaces and self-aggregation were developed and allowed successful FCS measurements in solution and at the plasma membrane. The ratio between the detected molecular species was found to vary with pH, peptide concentration and the proximity to the plasma membrane. The present results suggest that the diverse cellular uptake mechanisms, often reported for amphipathic CPPs, might result from the synergistic effect of peptide monomers, self-aggregates and cargo complexes, distributed unevenly at the plasma membrane. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    Science.gov (United States)

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  15. Investigation on physical behavior of styrene wood-polymer in different concentrations of monomer

    Directory of Open Access Journals (Sweden)

    maryam ghorbani

    2016-09-01

    Full Text Available This research was conducted to study the effect of different concentrations of styrene lumen monomer on the physical properties of beech wood. Physical test samples were prepared according to ASTM-D1037 standard and treated with vacuum-pressure method at five concentration levels; 0, 40, 60, 80 and 100 percent of soluble monomer. For polymerization, treated samples were heated in oven for two 24-hour period at 90 and 103ºC respectively. Monomer and polymer absorption, density variation, water absorption, swelling and anti-swelling efficiency (ASE were determined. According to the results, Monomer and polymer absorption were increment by monomer concentration increase, and they were reported 38.2% and 26% in highest level. With polymer absorption enhancement, density of wood increased from 0/63g/cm³ in control to 0/91g/cm³ in the highest monomer concentration level that reduces pores in wood-polymer structure. Absorbed polymer enhancement decreased hydrophilicity and dimensional changes of treated samples, so that water absorption and swelling volume of the samples saturated with 100% concentration of monomer were decreased 64% and 45.3% after the longest immersion time. Highest Anti-swelling efficiency of Styrene-saturated samples was determined 56.15% in the maximum concentration level of treatment.

  16. Solubility of mixed monomers of tetrafluoroethylene and propylene in water and latex

    International Nuclear Information System (INIS)

    Watanabe, Hiromasa; Okamoto, Jiro

    1978-03-01

    For kinetical analysis of the emulsion copolymerization of tetrafluoroethylene with propylene and selection of the optimum reaction conditions, the monomer concentrations and composition of the polymer particle were measured and the relations with reaction conditions were determined. Solubilities of tetrafluoroethylene and propylene in water increase with pressure. solubility of propylene is larger than that of tetrafluoroethylene. Solubility of the mixed monomers in water and latex increases with pressure and propylene concentration and decreases with temperature. Propylene concentration in the dissolved monomers is dependent on its concentration in the gas phase and independent of pressure and temperature. The monomer concentrations and the composition were estimated from measurements. Under propylene concentration in the gas phase of 0 to 40 wt % at 30 Kg/cm 2 G and 40 0 C, the monomer concentration and propylene fraction of the polymer particle are 17 -- 27% and 0 -- 62% respectively. The amount of propylene in the particle increases with its fraction in the gas phase, but the amount of tetrafluoroethylene is independent of its fraction in the gas phase. Monomer composition of the polymer particle is dependent on monomer composition of the gas phase and independent of temperature and pressure. The concentration in the polymer particle is 17% at propylene concentration 10 mole % in the gas phase. (auth.)

  17. Investigation of the Hydantoin Monomer and its Interaction with Water Molecules

    Science.gov (United States)

    Gruet, Sébastien; Perez, Cristobal; Schnell, Melanie

    2017-06-01

    Hydantoin (Imidazolidine-2,4-dione, C_3H_4N_2O_2) is a five-membered heterocyclic compound of astrobiological interest. This molecule has been detected in carbonaceous chondrites [1], and its formation can rise from the presence of glycolic acid and urea, two prebiotic molecules [2]. The hydrolysis of hydantoin under acidic conditions can also produce glycine [3], an amino acid actively searched for in the interstellar medium. Spectroscopic data of hydantoin is very limited and mostly dedicated to the solid phase. The high resolution study in gas phase is restricted to the work recently published by Ozeki et al. reporting the pure rotational spectra of the ground state and two vibrational states of the molecule in the millimeter-wave region (90-370 GHz)[4]. Using chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, we recorded the jet-cooled rotational spectra of hydantoin with water between 2 to 8 GHz. We observed the ground state of hydantoin monomer and several water complexes with one or two water molecules. All the observed species exhibit a hyperfine structure due to the two nitrogen atoms present in the molecule, which were fully resolved and analyzed. Additional experiments with a ^{18}O enriched water sample were realized to determine the oxygen-atom positions of the water monomers. These experiments yielded accurate structural information on the preferred water binding sites. The observed complexes and the interactions that hold them together, mainly strong directional hydrogen bonds, will be presented and discussed. [1] Shimoyama, A. and Ogasawara, R., Orig. Life Evol. Biosph., 32, 165-179, 2002. DOI:10.1023/A:1016015319112. [2] Menor-Salván, C. and Marín-Yaseli, M.R., Chem. Soc. Rev., 41(16), 5404-5415, 2012. DOI:10.1039/c2cs35060b. [3] De Marcellus P., Bertrand M., Nuevo M., Westall F. and Le Sergeant d'Hendecourt L., Astrobiology. 11(9), 847-854, 2011. DOI:10.1089/ast.2011.0677. [4] Ozeki, H., Miyahara R., Ihara H., Todaka S., Kobayashi

  18. Vogel-Fulcher dependence of relaxation rates in a nematic monomer and elastomer

    Science.gov (United States)

    Shenoy, D.; Filippov, S.; Aliev, F.; Keller, P.; Thomsen, D.; Ratna, B.

    2000-12-01

    Dielectric relaxation spectroscopy is used to study the relaxation processes in a nematic monomer and the corresponding cross-linked polymer nematic liquid crystal (elastomer). In the frequency window 10 mHz to 2 GHz the monomer liquid crystal shows a single relaxation whereas the polymer exhibits three relaxation processes, two of which are quantitatively analyzed. The temperature dependence of relaxation times in both the monomer and polymer follows a Vogel-Fulcher behavior. The relaxation processes are identified with specific molecular motions and activation energies are calculated in a linear approximation for comparison with literature data.

  19. Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

    Directory of Open Access Journals (Sweden)

    2009-06-01

    Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

  20. Radiation curing of mixtures of diallylphthalate prepolymer and vinyl monomer, 9

    International Nuclear Information System (INIS)

    Gotoda, Masao; Kitada, Yoshinori.

    1975-01-01

    Radiation curing, mainly by electron beams was studied with mixtures of low molecular weight diallylphthalate prepolymer (DAPsub(p).L) and vinyl monomers with special reference to their workability. Among the vinyl monomers, acrylonitrile gave a solution of low viscosity and methyl acrylate gave a solution of low dose curing. Radiation curing of DAPsub(p).L/vinyl monomer mixtures impregnated in wood was also tried. To obtain uniform wood-polymer composites, γ-irradiation after impregnation at 10 kg/cm 2 was found to be required for thick plate (110 mm), while electron beam irradiation after impregnation at normal pressure was sufficient for thin plate. (author)

  1. Effect of monomer composition on the properties of high temperature polymer concretes

    Energy Technology Data Exchange (ETDEWEB)

    Zeldin, A.; Kukacka, L.E.; Carciello, N.

    1980-01-01

    The effects of organic monomer composition on the thermomechanical properties of polymer concrete (PC) containing sand-cement mixtures as an agregate filler were investigated. The effects of various monomer mixtures on compressive strength and hydrolytic stability are discussed. Composites were fabricated in the same way as ordinary concrete, with monomer solutions of various compositions and concentrations used to bind the sand-cement mixture. The compressive strengths of th composites before and after exposure to air and to brine solutions at 240/sup 0/C are discussed.

  2. Self-assembly of actin monomers into long filaments: Brownian Dynamics simulations

    DEFF Research Database (Denmark)

    Shillcock, Julian C.

    2009-01-01

    Brownian dynamics simulations are used to study the dynamical process of self-assembly of actin monomers into long filaments containing up to 1000 actin protomers. In order to overcome the large separation of time scales between the diffusive motion of the freemonomers and the relatively slow....../detachment events. When a single filament is allowed to grow in a bath of constant concentration of free ADP-actin monomers, its growth rate increases linearly with the free monomer concentration in quantitative agreement with in vitro experiments. Theresults also show that the waiting time is governed by...

  3. DFT approach to (benzylthio)acetic acid: Conformational search, molecular (monomer and dimer) structure, vibrational spectroscopy and some electronic properties

    Science.gov (United States)

    Sienkiewicz-Gromiuk, Justyna

    2018-01-01

    The DFT studies were carried out with the B3LYP method utilizing the 6-31G and 6-311++G(d,p) basis sets depending on whether the aim of calculations was to gain the geometry at equilibrium, or to calculate the optimized molecular structure of (benzylthio)acetic acid (Hbta) in the forms of monomer and dimer. The minimum conformational energy search was followed by the potential energy surface (PES) scan of all rotary bonds existing in the acid molecule. The optimized geometrical monomeric and dimeric structures of the title compound were compared with the experimental structural data in the solid state. The detailed vibrational interpretation of experimental infrared and Raman bands was performed on the basis of theoretically simulated ESFF-scaled wavenumbers calculated for the monomer and dimer structures of Hbta. The electronic characteristics of Hbta is also presented in terms of Mulliken atomic charges, frontier molecular orbitals and global reactivity descriptors. Additionally, the MEP and ESP surfaces were computed to predict coordination sites for potential metal complex formation.

  4. Dynamic conformations of nucleophosmin (NPM1 at a key monomer-monomer interface affect oligomer stability and interactions with granzyme B.

    Directory of Open Access Journals (Sweden)

    Wei D Duan-Porter

    Full Text Available Nucleophosmin (NPM1 is an abundant, nucleolar tumor antigen with important roles in cell proliferation and putative contributions to oncogenesis. Wild-type NPM1 forms pentameric oligomers through interactions at the amino-terminal core domain. A truncated form of NPM1 found in some hepatocellular carcinoma tissue formed an unusually stable oligomer and showed increased susceptibility to cleavage by granzyme B. Initiation of translation at the seventh methionine generated a protein (M7-NPM that shared all these properties. We used deuterium exchange mass spectrometry (DXMS to perform a detailed structural analysis of wild-type NPM1 and M7-NPM, and found dynamic conformational shifts or local "unfolding" at a specific monomer-monomer interface which included the β-hairpin "latch." We tested the importance of interactions at the β-hairpin "latch" by replacing a conserved tyrosine in the middle of the β-hairpin loop with glutamic acid, generating Y67E-NPM. Y67E-NPM did not form stable oligomers and further, prevented wild-type NPM1 oligomerization in a dominant-negative fashion, supporting the critical role of the β-hairpin "latch" in monomer-monomer interactions. Also, we show preferential cleavage by granzyme B at one of two available aspartates (either D161 or D122 in M7-NPM and Y67E-NPM, whereas wild-type NPM1 was cleaved at both sites. Thus, we observed a correlation between the propensity to form oligomers and granzyme B cleavage site selection in nucleophosmin proteins, suggesting that a small change at an important monomer-monomer interface can affect conformational shifts and impact protein-protein interactions.

  5. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi

    2017-01-01

    be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  6. Characterization of γ-radiation induced polymerization in ethyl methacrylate and methyl acrylate monomers solutions

    Science.gov (United States)

    Baccaro, Stefania; Casieri, Cinzia; Cemmi, Alessia; Chiarini, Marco; D'Aiuto, Virginia; Tortora, Mariagrazia

    2017-12-01

    The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere.

  7. Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites.

    Science.gov (United States)

    Pfeifer, Carmem S; Shelton, Zachary R; Braga, Roberto R; Windmoller, Dario; Machado, José C; Stansbury, Jeffrey W

    2011-02-01

    The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion

  8. One-pot synthesis of hybrid gel by use of tributylstannyl ester of polymeric silicic acid, chlorosilane and organic monomer; Keisan no toribuchiru sutanniru esuteru kobuntai, kuroroshiran oyobi yuki monoma wo mochiita haiburiddo geru no ichidankai gosei

    Energy Technology Data Exchange (ETDEWEB)

    Moriya, O. [National Defense Academy, Kanagawa (Japan). Dept. of Chemistry; Sugisaki, T. [Lintec Co. Ltd., Saitama (Japan); Tomono, M.; Oikawa, M.; Kageyama, T. [Kanto-Gakuin Univ., Kanagawa (Japan)

    1999-12-10

    Organic-inorganic hybrid gels were obtained efficiently by one-pot procedure from tributylstannyl ester of polymeric silicic acid (PTBS), chloro (3-methacryloyloxypropyl) dimethylsilane (1a), and common monomers such as styrene, acrylonitrile, and methyl methacrylate. In the reaction system, substitution of tributylstannyl groups of PTBS by silyl groups of 1a and copolymerization of methacryloyloxy group of 1a with a monomer proceeded simultaneously under UV irradiation at room temperature. The resulting gel should be consisted of covalently bonded three components an regarded as a nanocomposite material The use of another chlorosilane 1b, which had cyanopropyl group, with 1a led to formation of a multifunctional hybrid gel. (author)

  9. Molecular recognition at methyl methacrylate/n-butyl acrylate (MMA/nBA) monomer unit boundaries of phospholipids at p-MMA/nBA copolymer surfaces.

    Science.gov (United States)

    Yu, Min; Urban, Marek W; Sheng, Yinghong; Leszczynski, Jerzy

    2008-09-16

    Lipid structural features and their interactions with proteins provide a useful vehicle for further advances in membrane proteins research. To mimic one of potential lipid-protein interactions we synthesized poly(methyl methacrylate/ n-butyl acrylate) (p-MMA/nBA) colloidal particles that were stabilized by phospholipid (PLs). Upon the particle coalescence, PL stratification resulted in the formation of surface localized ionic clusters (SLICs). These entities are capable of recognizing MMA/nBA monomer interfaces along the p-MMA/nBA copolymer backbone and form crystalline SLICs at the monomer interface. By utilizing attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy and selected area electron diffraction (SAD) combined with ab initio calculations, studies were conducted that identified the origin of SLICs as well as their structural features formed on the surface of p-MMA/nBA copolymer films stabilized by 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) PL. Specific entities responsible for SLIC formation are selective noncovalent bonds of anionic phosphate and cationic quaternary ammonium segments of DLPC that interact with two neighboring carbonyl groups of nBA and MMA monomers of the p-MMA/nBA polymer backbone. To the best of our knowledge this is the first example of molecular recognition facilitated by coalescence of copolymer colloidal particles and the ability of PLs to form SLICs at the boundaries of the neighboring MMA and nBA monomer units of the p-MMA/nBA chain. The dominating noncovalent bonds responsible for the molecular recognition is a combination of H-bonding and electrostatic interactions.

  10. Study on grafting of different types of acrylic monomers onto natural rubber by γ-rays

    International Nuclear Information System (INIS)

    Dafader, N.C.; Haque, M.E.; Akhtar, F.; Ahmad, M.U.

    2006-01-01

    A comparative study of various acrylic monomers for grafting onto natural rubber was done. The stability of natural rubber latex (NRL) against coagulum with monomer, mechanical properties of grafted rubbers and percent of grafting were investigated. The NRL with monomers, methylacrylate (MA), ethylacrylate (EA) and n-butylacrylate (n-BA), is unstable but it is stable with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and cyclohexyl methacrylate (CHMA). The mechanical properties and degree of grafting attained a maximum at a total radiation dose of 4 kGy. The values of tensile properties of MMA and CHMA grafted rubbers are almost similar, and higher than those of BMA grafted rubbers. On the other hand, the degree of grafting for CHMA is higher than those of MMA and BMA grafted rubbers. The infrared (IR) spectra of monomer grafted natural rubber were also studied

  11. Determination of unreacted monomers in restorative dental resins based on dimethacrylate by NMR hydrogen

    International Nuclear Information System (INIS)

    Correa, Ivo Carlos; Miranda Junior, Walter G.; Tavares, Maria Ines B.

    2001-01-01

    The presence of unreacted monomers after photo-activation of dental composites causes mechanical and biological properties to decrease and could be detected by NMR analysis. The aim of this study was to evaluate the percentage of leachable monomers of light-cured composites under the effect of variations of exposure time of photo activation by nuclear magnetic resonance of hydrogen in solution (NMR 1 H). The composite resins tested Z250 and Fill Magic obtained similar values of unreacted monomers (%) at photo curing time suggested by the manufacturer and values were also lower than Durafill and A110 concentrations. From the NMR results, one day extractable time was efficient to quantify the amount of residual monomers in the dental composites tested, unless for Durafill composite. (author)

  12. Chimeric polymers formed from a monomer capable of free radical, oxidative and electrochemical polymerisation.

    Science.gov (United States)

    Lakshmi, Dhana; Whitcombe, Michael J; Davis, Frank; Chianella, Iva; Piletska, Elena V; Guerreiro, Antonio; Subrahmanyam, Sreenath; Brito, Paula S; Fowler, Steven A; Piletsky, Sergey A

    2009-05-21

    A new monomer, which incorporates both aniline and methacrylamide functional groups, was shown to possess orthogonal polymerisation behaviour to produce conjugated polyaniline suitable for a wide range of applications.

  13. Radical copolymerization in homogenous medium and emulsion system monomers acrylonitrile/styrene

    Directory of Open Access Journals (Sweden)

    Boussehel H.

    2013-09-01

    Full Text Available This study examines the radical copolymerization in homogeneous and emulsion of the monomer system acrylonitrile/styrene. These copolymers are of great interest to the plastics industry, because they combine the good mechanical properties and implementation provided by the styrene units in the very high solvent resistance and extreme gas impermeability provided by the acrylonitrile units. The properties of a copolymer are directly related to its composition and distribution of monomer units in its macromolecular chains. Based on the reports of the couple reactivity's of monomers (AN/S found in the literature, the objective of the work is to provide theoretical simulation (by analytical and numerical integration of the equation of copolymerization: The kinetics of the reaction copolymerization of AN/S in a homogeneous medium and emulsion (drift composition, azeotropic and the microstructure (distribution of monomer sequences and the glass transition property of the macromolecular chains instant formed throughout the copolymerization reaction.

  14. A comment on water’s structure using monomer fraction data and theories

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Maribo-Mogensen, Bjørn; Tsivintzelis, Ioannis

    2016-01-01

    Monomer fraction data for water (and other compounds) can provide useful information about their structure and can be used in “advanced” equations of state, which account explicitly for association phenomena. Recent findings about the performance of association theories in representing the monomer...... fraction of water are reviewed. Three such theories are considered and all of them perform qualitatively similar. They can all represent phase equilibria for water solutions qualitatively well but with parameters which are not in good agreement with Luck’s famous monomer fraction data. While this could set...... the theoretical basis of these theories in doubt, we also show in this work that the findings with these association models are in agreement with a recently presented theory which links monomer fraction to dielectric constants. This new theory, like the three thermodynamic models, predicts more hydrogen bonding...

  15. Vinyl Monomers Double as UV Stabilizers: 179th ACS Meeting Houston.

    Science.gov (United States)

    Chemical and Engineering News, 1980

    1980-01-01

    Synthesis and polymerization of vinyl monomers that double as stabilizers against degradation of plastics by ultraviolet light has been accomplished. Potential applications include protection of photovoltaic cells in solar power plants. (Author/RE)

  16. Triptycene-based ladder monomers and polymers, methods of making each, and methods of use

    KAUST Repository

    Pinnau, Ingo

    2015-02-05

    Embodiments of the present disclosure provide for a triptycene-based A-B monomer, a method of making a triptycene-based A-B monomer, a triptycene-based ladder polymer, a method of making a triptycene-based ladder polymers, a method of using triptycene-based ladder polymers, a structure incorporating triptycene-based ladder polymers, a method of gas separation, and the like.

  17. The mutual diffusion coefficient for (meth)acrylate monomers as determined with a nuclear microprobe

    International Nuclear Information System (INIS)

    Leewis, Christian M.; Mutsaers, Peter H.A.; Jong, Arthur M. de; Ijzendoorn, Leo J. van; Voigt, Martien J.A. de; Ren, Min Q.; Watt, Frank; Broer, Dirk J.

    2004-01-01

    The value of the mutual diffusion coefficient D V of two acrylic monomers is determined with nuclear microprobe measurements on a set of polymer films. These films have been prepared by allowing the monomers to diffuse into each other for a certain time and subsequently applying fast ultraviolet photo-polymerization, which freezes the concentration profile. The monomer diffusion profiles are studied with a scanning 2.1 MeV proton microprobe. Each monomer contains a marker element, e.g., Cl and Si, which are easily detected with proton induced x-ray emission. From the diffusion profiles, it is possible to determine the mutual diffusion coefficient. The mutual diffusion coefficient is dependent of concentration, which is concluded from the asymmetry in the Cl- and Si-profiles. A linear dependence of the mutual diffusion coefficient on the composition is used as a first order approximation. The best fits are obtained for a value of b=(0.38±0.15), which is the ratio of the diffusion coefficient of 1,3-bis(3-methacryloxypropyl)-1, 1,3,3-tetramethyldisiloxane in pure 2-chloroethyl acrylate and the diffusion coefficient of 2-chloroethyl acrylate in pure 1,3-bis(3-methacryloxypropyl)-1,1,3,3-tetramethyldisiloxane. Under the assumption of a linear dependence of the mutual diffusion coefficient D V on monomer composition, it follows that D V =(2.9±0.6)·10 -10 m 2 /s at a 1:1 monomer ratio. With Flory-Huggins expressions for the monomer chemical potentials, one can derive approximate values for the individual monomer diffusion coefficients

  18. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.

    1977-01-01

    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  19. Effect of food simulating liquids on release of monomers from two dental resin composites

    Directory of Open Access Journals (Sweden)

    Ghavam M

    2010-06-01

    Full Text Available "nBackground and Aims: The elution of residual monomers from cured dental composites to oral cavity has a harmful effect on human health and can affect their clinical durability. The purpose of this study was to evaluate the amount of eluted monomers (Bis-GMA, TEGDMA, UDMA from two types of composites (Gradia and P60 after exposure to food simulating liquids such as ethanol (25, 50, 75 % and heptane 50 % for 24 hours and 7 days. "nMaterials and Methods: Forty specimens of each composite were prepared. Equal numbers of each composite were immersed in tubes containing 2cc volumes of 25, 50, 75 % ethanole and 50 % heptane. The amount of eluted monomers in standard condition such as Bis-GMA, TEGDMA and UDMA was measured by GC/MS (Gas Chromatography/Mass Spectroscopy and results were statistically analysed by three way and one way ANOVA. P<0.05 was considered as the level of significancy. "nResults: The results showed that Gradia released more TEGDMA than P60. In assessing the effect of environment, the result showed that ethanol caused releasing monomers more than heptane and the concentration rate of 75 % ethanole resulted in most releasing of monomers. In assessing the effect of time, the observation showed that more monomers were released 7 days compared to 24 hours. Bis-GMA and UDMA were not detected in any solutions in these conditions. "nConclusion: Ethanole caused more release of monomers than heptane and 75 % ethanole released the most amount of monomers. Gradia released more amount of TEGDMA than P60.

  20. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers

    OpenAIRE

    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol

    2015-01-01

    Background Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24?h prior to the analysis of alkaline p...

  1. Total Sulfate vs. Sulfuric Acid Monomer Concenterations in Nucleation Studies.

    Czech Academy of Sciences Publication Activity Database

    Neitola, K.; Brus, David; Makkonen, U.; Sipilä, M.; Mauldin III, R.L.; Sarnela, N.; Jokinen, T.; Lihavainen, H.; Kulmala, M.

    2015-01-01

    Roč. 15, č. 6 (2015), s. 3429-3443 ISSN 1680-7316 Grant - others:AFCE(FI) 1118615 Institutional support: RVO:67985858 Keywords : ion-induced nucleation * particle formation * experimental setup Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.114, year: 2015

  2. Residual monomer content determination in some acrylic denture base materials and possibilities of its reduction

    Directory of Open Access Journals (Sweden)

    Kostić Milena

    2009-01-01

    Full Text Available Background/Aim. Polymethyl methacrylate is used for producing a denture basis. It is a material made by the polymerization process of methyl methacrylate. Despite of the polymerization type, there is a certain amount of free methyl methacrylate (residual monomer incorporated in the denture, which can cause irritation of the oral mucosa. The aim of this study was to determine the amount of residual monomer in four different denture base acrylic resins by liquid chromatography and the possibility of its reduction. Methods. After the polymerization, a postpolymerization treatment was performed in three different ways: in boiling water for thirty minutes, with 500 W microwaves for three minutes and in steam bath at 22º C for one to thirty days. Results. The obtained results showed that the amount of residual monomer is significantly higher in cold polymerizing acrylates (9.1-11%. The amount of residual monomer after hot polymerization was in the tolerance range (0.59- 0.86%. Conclusion. The obtained results denote a low content of residual monomer in the samples which have undergone postpolymerization treatment. A lower percent of residual monomer is established in samples undergone a hot polymerization.

  3. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.

    Science.gov (United States)

    Hoggett, J G; Kellett, G L

    1992-10-15

    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity.

  4. New phenazine-containing ladder polymer of intrinsic microporosity from a spirobisindane-based AB-type monomer

    KAUST Repository

    Ghanem, Bader

    2016-08-15

    A new solution-processable ladder polymer (PSBI-AB) of intrinsic microporosity with dibenzodioxane linkages and bis(phenazine) units was designed and synthesized by self-polymerization of an AB-type monomer containing both catechol and aromatic dichloride groups. Such polymerization is an effective way to synthesize high molecular weight polymers and has a significant advantage over AA-BB polycondensation due to the lack of the requirement for strict control over stoichiometric balance. This protocol can be used to prepare a variety of phenazine-containing ladder type PIMs from their aromatic tetramethoxy precursors. The obtained polymer had high average molecular mass, excellent thermal stability, a high BET surface area of 705 m(2) g(-1) and good solubility in some organic solvents such as chloroform, m-cresol and dichlorobenzene. Gas permeation measurements showed comparable results to the previously reported analogous PIM-7 for films made under the same formation protocol.

  5. Folding and unfolding pathway of chaperonin GroEL monomer and elucidation of thermodynamic parameters.

    Science.gov (United States)

    Puri, Sarita; Chaudhuri, Tapan K

    2017-03-01

    The conformation and thermodynamic stability of monomeric GroEL were studied by CD and fluorescence spectroscopy. GroEL denaturation with urea and dilution in buffer leads to formation of a folded GroEL monomer. The monomeric nature of this protein was verified by size-exclusion chromatography and native PAGE. It has a well-defined secondary and tertiary structure, folding activity (prevention of aggregation) for substrate protein and is resistant to proteolysis. Being a properly folded and reversibly refoldable, monomeric GroEL is amenable for the study of thermodynamic stability by unfolding transition methods. We present the equilibrium unfolding of monomeric GroEL as studied by urea and heat mediated unfolding processes. The urea mediated unfolding shows two transitions and a single transition in the heat mediated unfolding process. In the case of thermal unfolding, some residual structure unfolds at a higher temperature (70-75°C). The process of folding/unfolding is reversible in both cases. Analysis of folding/unfolding data provides a measure of ΔG NU H 2 O , T m , ΔH van and ΔS van of monomeric GroEL. The thermodynamic stability parameter ΔG NU H 2 O is similar with both CD and intrinsic fluorescence i.e. 7.10±1.0kcal/mol. The calculated T m , ΔH van and ΔS van from the thermal unfolding transition is 46±0.5°C, 43.3±0.1kcal/mol and 143.9±0.1cal/mol/k respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. α-helix to β-hairpin transition of human amylin monomer

    Science.gov (United States)

    Singh, Sadanand; Chiu, Chi-cheng; Reddy, Allam S.; de Pablo, Juan J.

    2013-04-01

    The human islet amylin polypeptide is produced along with insulin by pancreatic islets. Under some circumstances, amylin can aggregate to form amyloid fibrils, whose presence in pancreatic cells is a common pathological feature of Type II diabetes. A growing body of evidence indicates that small, early stage aggregates of amylin are cytotoxic. A better understanding of the early stages of the amylin aggregation process and, in particular, of the nucleation events leading to fibril growth could help identify therapeutic strategies. Recent studies have shown that, in dilute solution, human amylin can adopt an α-helical conformation, a β-hairpin conformation, or an unstructured coil conformation. While such states have comparable free energies, the β-hairpin state exhibits a large propensity towards aggregation. In this work, we present a detailed computational analysis of the folding pathways that arise between the various conformational states of human amylin in water. A free energy surface for amylin in explicit water is first constructed by resorting to advanced sampling techniques. Extensive transition path sampling simulations are then employed to identify the preferred folding mechanisms between distinct minima on that surface. Our results reveal that the α-helical conformer of amylin undergoes a transformation into the β-hairpin monomer through one of two mechanisms. In the first, misfolding begins through formation of specific contacts near the turn region, and proceeds via a zipping mechanism. In the second, misfolding occurs through an unstructured coil intermediate. The transition states for these processes are identified. Taken together, the findings presented in this work suggest that the inter-conversion of amylin between an α-helix and a β-hairpin is an activated process and could constitute the nucleation event for fibril growth.

  7. Porous polymer monoliths functionalized through copolymerization of a C60 fullerene-containing methacrylate monomer for highly efficient separations of small molecules

    KAUST Repository

    Chambers, Stuart D.

    2011-12-15

    Monolithic poly(glycidyl methacrylate-co-ethylene dimethacrylate) and poly(butyl methacrylate-co-ethylene dimethacrylate) capillary columns, which incorporate the new monomer [6,6]-phenyl-C 61-butyric acid 2-hydroxyethyl methacrylate ester, have been prepared and their chromatographic performance have been tested for the separation of small molecules in the reversed phase. While addition of the C60-fullerene monomer to the glycidyl methacrylate-based monolith enhanced column efficiency 18-fold, to 85 000 plates/m at a linear velocity of 0.46 mm/s and a retention factor of 2.6, when compared to the parent monolith, the use of butyl methacrylate together with the carbon nanostructured monomer afforded monolithic columns with an efficiency for benzene exceeding 110 000 plates/m at a linear velocity of 0.32 mm/s and a retention factor of 4.2. This high efficiency is unprecedented for separations using porous polymer monoliths operating in an isocratic mode. Optimization of the chromatographic parameters affords near baseline separation of 6 alkylbenzenes in 3 min with an efficiency of 64 000 plates/m. The presence of 1 wt % or more of water in the polymerization mixture has a large effect on both the formation and reproducibility of the monoliths. Other factors such as nitrogen exposure, polymerization conditions, capillary filling method, and sonication parameters were all found to be important in producing highly efficient and reproducible monoliths. © 2011 American Chemical Society.

  8. Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives.

    Science.gov (United States)

    Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

    2014-09-01

    The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA, 45/55, w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt% water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. Published by Elsevier Ltd.

  9. Thermodynamically stable amyloid-β monomers have much lower membrane affinity than the small oligomers

    Directory of Open Access Journals (Sweden)

    Bidyut eSarkar

    2013-04-01

    Full Text Available Amyloid beta (Aβ is an extracellular 39-43 residue long peptide present in the mammalian cerebrospinal fluid, whose aggregation is associated with Alzheimer’s disease. Small oligomers of Aβ are currently thought to be the key to toxicity. However, it is not clear why the monomers of Aβ are non-toxic, and at what stage of aggregation toxicity emerges. Interactions of Aβ with cell membranes is thought to be the initiator of toxicity, but membrane-binding studies with different preparations of monomers and oligomers have not settled this issue. We have earlier found that thermodynamically stable Aβ monomers emerge spontaneously from oligomeric mixtures upon long term incubation in physiological solutions (Nag et al, JBC, 2011. Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of small oligomers (containing dimers to decamers, providing a clue to the emergence of toxicity. Fluorescently labeled Aβ40 monomers show negligible binding to cell membranes of a neuronal cell line (RN46A at physiological concentrations (250 nM, while oligomers at the same concentrations show strong binding within 30 minutes of incubation. The increased affinity most likely does not require any specific neuronal receptor, since this difference in membrane-affinity was also observed in a somatic cell-line (HEK 293T. Similar results are also obtained for Aβ42 monomers and oligomers. Minimal amount of cell death is observed at these concentrations even after 36 hours of incubation. It is likely that membrane binding precedes subsequent slower toxic events induced by Aβ. Our results a provide an explanation for the non-toxic nature of Aβ monomers, b suggest that Aβ toxicity emerges at the initial oligomeric phase, and c provide a quick assay for monitoring the benign-to-toxic transformation of Aβ.

  10. Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects

    International Nuclear Information System (INIS)

    Bernini, S; Leporini, D

    2016-01-01

    The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system. To disentangle the influence of the local geometry and the bond arrangements, and to reveal their interplay, we define suitable measures of the anisotropy emphasising either the former or the latter aspect. Connectivity anisotropy, as measured by the correlation between the initial bond orientation and the direction of the subsequent monomer displacement, shows a slight enhancement due to the local order at times shorter than the structural relaxation time. At intermediate times—when the monomer displacement is comparable to the bond length—a pronounced peak and then decays slowly as t −1/2 , becoming negligible when the displacement is as large as about five bond lengths, i.e. about four monomer diameters or three Kuhn lengths. Local-geometry anisotropy, as measured by the correlation between the initial orientation of a characteristic axis of the Voronoi cell and the subsequent monomer dynamics, is affected at shorter times than the structural relaxation time by the cage shape with antagonistic disturbance by the connectivity. Differently, at longer times, the connectivity favours the persistence of the local-geometry anisotropy, which vanishes when the monomer displacement exceeds the bond length. Our results strongly suggest that the sole consideration of the local order is not enough to understand the microscopic origin of the rattling amplitude of the trapped monomer in the cage of the neighbours. (paper)

  11. Net expansion of dried demineralized dentin matrix produced by monomer/alcohol saturation and solvent evaporation.

    Science.gov (United States)

    Agee, Kelli A; Becker, Thomas D; Joyce, Anthony P; Rueggeberg, Frederick A; Borke, James L; Waller, Jennifer L; Tay, Franklin R; Pashley, David H

    2006-11-01

    The purpose of this work was to determine if nonaqueous methacrylate monomer/alcohol mixtures could expand dried collapsed demineralized dentin matrix. Thin disks (ca. 200 microm) of human dentin were demineralized and placed in wells beneath contact probes of linear variable differential transformers. The probes were placed on water-saturated expanded matrices to record the shrinkage associated with drying. Monomer mixtures containing hydroxyethyl methacrylate, 2,2-bis[4-(2-hydroxy-3 methacryloyloxy)propoxyphenyl] propane, or triethyleneglycol dimethacrylate were mixed with methanol or ethanol at alcohol/monomer mass fraction % of 90/10, 70/30, 50/50, or 30/70. They were randomly applied to the dried matrices to determine the rate and magnitude of expansion; then shrinkage was recorded during evaporation of the alcohols. The results indicated that matrix expansion was positively correlated with the Hoy's solubility parameters for hydrogen bonding forces (delta(h)) of the monomer/solvent mixtures (p methanol-containing than with ethanol-containing monomer mixtures. For the test solutions, triethyleneglycol dimethacrylate-containing mixtures produced the slowest rate of matrix expansion and hydroxyethyl methacrylate-containing mixtures the most rapid expansion. When the solvents were evaporated, the matrix shrank in proportion to the solvent content and the delta(h) of the monomer-solvent mixtures. The results indicate that expansion of dried, collapsed dentin matrices requires that the delta(h) of the mixtures be larger than 17 (J/cm(3))(1/2). The greater the delta(h) of the monomer solutions, the greater the rate and extent of expansion.

  12. Synthesis of phosphate monomers and bonding to dentin: esterification methods and use of phosphorus pentoxide.

    Science.gov (United States)

    Ogliari, Fabrício Aulo; da Silva, Eduardo de Oliveira; Lima, Giana da Silveira; Madruga, Francine Cardozo; Henn, Sandrina; Bueno, Márcia; Ceschi, Marco Antônio; Petzhold, Cesar Liberato; Piva, Evandro

    2008-03-01

    The aim of this study was to synthesize an acidic monomer using an alternative synthetic pathway and to evaluate the influence of the acidic monomer concentration on the microtensile bond strength to dentin. The intermediary 5-hydroxypentyl methacrylate (HPMA) was synthesized through methacrylic acid esterification with 1,5-pentanediol, catalyzed by p-toluenesulfonic acid. To displace the reaction balance, the water generated by esterification was removed by three different methods: anhydrous sodium sulfate; molecular sieves or azeotropic distillation. In the next step, a phosphorus pentoxide (4.82 mmol) slurry was formed in cold acetone and 29 mmol of HPMA was slowly added by funnel addition. After the reaction ended, solvent was evaporated and the product was characterized by 1HNMR and FTIR. The phosphate monomer was introduced in a self-etch primer at concentrations of 0, 15, 30, 50, 70 and 100 wt%. Clearfil SE Bond was used as commercial reference. Microtensile bond strength to dentin was evaluated 24h after the bonding procedures, followed by fracture analysis (n=20). Data was submitted to ANOVA and Tukey's post hoc test. The highest yield was obtained (62%) when azeotropic distillation was used, while the reaction with molecular sieves was not feasible. The phosphoric moiety attachment to the monomer was successfully performed with a quantitative yield that reached around 100%. The acidic monomer concentration significantly affected the bond strength and the highest mean (55.1+/-12.8 MPa) was obtained when 50% of acidic monomer was used. The synthesis pathways described in the present study appear to be a viable alternative for developing phosphate monomers.

  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. Effect of solubility parameter of monomers on electron beam induced graft-polymerization onto polyethylene films

    International Nuclear Information System (INIS)

    Mori, Koji; Koshiishi, Kenji; Masuhara, Ken-ichi

    1991-01-01

    Electron beam induced graft-polymerization by the mutual irradiation technique of monomers with different solubility parameters δ onto low density polyethylene films (LDPE) and high density polyethylene films (HDPE) were investigated at high dose rates (25 Mrad per second). Graft-polymerization mechanisms were discussed on the basis of grafting rates, surface tensions, atomic ratios of surface by XPS, and SEM images of the grafted films. Grafting rates decreased with increasing δ of monomers, and grafting rates onto LDPE were larger than those onto HDPE. Graft chain contents on surface, which were evaluated in terms of surface tensions and atomic ratios of the surface, increased with increasing δ of monomers, and graft chain contents on surface of HDPE were higher than those of LDPE. It is assumed that mutual solubility of PE and monomers, i.e., infiltration of monomers into PE during graft-polymerization influence grafting rates and graft sites in films. In case of high mutual solubility, grafting rates were large and graft sites spread from the surface into bulk. On the other hand, in case of low mutual solubility, grafting rates were small and graft sites localized on the surface of films. (author)

  15. Do CAD/CAM dentures really release less monomer than conventional dentures?

    Science.gov (United States)

    Steinmassl, Patricia-Anca; Wiedemair, Verena; Huck, Christian; Klaunzer, Florian; Steinmassl, Otto; Grunert, Ingrid; Dumfahrt, Herbert

    2017-06-01

    Computer-aided design (CAD)/computer-aided manufacturing (CAM) dentures are assumed to have more favourable material properties than conventionally fabricated dentures, among them a lower methacrylate monomer release. The aim of this study was to test this hypothesis. CAD/CAM dentures were generated from ten different master casts by using four different CAD/CAM systems. Conventional, heat-polymerised dentures served as control group. Denture weight and volume were measured; the density was calculated, and the denture surface area was assessed digitally. The monomer release after 7 days of water storage was measured by high-performance liquid chromatography. Whole You Nexteeth and Wieland Digital Dentures had significantly lower mean volume and weight than conventional dentures. Baltic Denture System and Whole You Nexteeth had a significantly increased density. Baltic Denture System had a significantly smaller surface area. None of the CAD/CAM dentures released significantly less monomer than the control group. All tested dentures released very low amounts of methacrylate monomer, but not significantly less than conventional dentures. A statistically significant difference might nevertheless exist in comparison to other, less recommendable denture base materials, such as the frequently used autopolymerising resins. CAD/CAM denture fabrication has numerous advantages. It enables the fabrication of dentures with lower resin volume and lower denture weight. Both could increase the patient comfort. Dentures with higher density might exhibit more favourable mechanical properties. The hypothesis that CAD/CAM dentures release less monomer than conventional dentures could, however, not be verified.

  16. Using monomer vibrational wavefunctions to compute numerically exact (12D) rovibrational levels of water dimer

    Science.gov (United States)

    Wang, Xiao-Gang; Carrington, Tucker

    2018-02-01

    We compute numerically exact rovibrational levels of water dimer, with 12 vibrational coordinates, on the accurate CCpol-8sf ab initio flexible monomer potential energy surface [C. Leforestier et al., J. Chem. Phys. 137, 014305 (2012)]. It does not have a sum-of-products or multimode form and therefore quadrature in some form must be used. To do the calculation, it is necessary to use an efficient basis set and to develop computational tools, for evaluating the matrix-vector products required to calculate the spectrum, that obviate the need to store the potential on a 12D quadrature grid. The basis functions we use are products of monomer vibrational wavefunctions and standard rigid-monomer basis functions (which involve products of three Wigner functions). Potential matrix-vector products are evaluated using the F matrix idea previously used to compute rovibrational levels of 5-atom and 6-atom molecules. When the coupling between inter- and intra-monomer coordinates is weak, this crude adiabatic type basis is efficient (only a few monomer vibrational wavefunctions are necessary), although the calculation of matrix elements is straightforward. It is much easier to use than an adiabatic basis. The product structure of the basis is compatible with the product structure of the kinetic energy operator and this facilitates computation of matrix-vector products. Compared with the results obtained using a [6 + 6]D adiabatic approach, we find good agreement for the inter-molecular levels and larger differences for the intra-molecular water bend levels.

  17. The binding of glucose to yeast hexokinase monomers is independent of ionic strength.

    Science.gov (United States)

    Mayes, E L; Hoggett, J G; Kellett, G L

    1982-05-01

    Hoggett & Kellett [Eur. J. Biochem. 66, 65-77 (1976)] have reported that the binding of glucose to the monomer of hexokinase PII isoenzyme is independent of ionic strength, in contrast to the subsequent claim of Feldman & Kramp [Biochemistry 17, 1541-1547 (1978)] that the binding is strongly dependent on ionic strength. Since measurements with native hexokinase P forms are complicated by the fact that the enzyme exists in a monomer-dimer association-dissociation equilibrium, we have now studied the binding of glucose to the proteolytically-modified S forms which are monomeric. At pH 8.5, the affinity of glucose for both SI and SII monomers is independent of salt concentration over the range of KCl concentrations 0-1.0 mol . dm-3 and is in good agreement with that of the corresponding P forms in both low and high salt. These observations confirm that the binding of glucose to hexokinase P monomers is independent of ionic strength and that the affinity of glucose for the hexokinase PII monomer is about an order of magnitude greater than that for the dimer.

  18. TEGDMA and UDMA monomers released from composite dental material polymerized with diode and halogen lamps.

    Science.gov (United States)

    Wacławczyk, Agnieszka; Postek-Stefańska, Lidia; Pietraszewska, Daria; Birkner, Ewa; Zalejska-Fiolka, Jolanta; Wysoczańska-Jankowicz, Iwona

    2018-03-20

    More than 35 substances released from composite fillings have been identified. Among these, basic monomers and the so-called co-monomers are most often reported. The substances released from polymer-based materials demonstrate allergenic, cytotoxic, genotoxic, mutagenic, embryotoxic, teratogenic, and estrogenic properties. The aim of this study was to measure the amounts of triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) monomers released from composite dental fillings to citrate-phosphate buffer with the pH of 4, 6, 8 after 24 h and 6 months from the polymerization. Ten samples for each polymerization method had been made from the composite material (Filtek Supreme XT, 3M ESPE, St. Paul, USA), which underwent polymerization using the following lamps: halogen lamp (Translux CL, Heraeus Kulzer, Hanau, Germany) (sample H) and diode lamp (Elipar Freelight 2, 3M ESPE), with soft start function (group DS) and without that function (group DWS). It has been demonstrated that the type of light-curing units has a significant impact on the amount of TEGDMA and UDMA released. The amount of UDMA and TEGDMA monomers released from composite fillings differed significantly depending on the source of polymerization applied, as well as the pH of the solution and sample storage time. Elution of the monomers from composite material polymerized using halogen lamp was significantly greater as compared to curing with diode lamps.

  19. Design and Applications of Biodegradable Polyester Tissue Scaffolds Based on Endogenous Monomers Found in Human Metabolism

    Directory of Open Access Journals (Sweden)

    Devin G. Barrett

    2009-10-01

    Full Text Available Synthetic polyesters have deeply impacted various biomedical and engineering fields, such as tissue scaffolding and therapeutic delivery. Currently, many applications involving polyesters are being explored with polymers derived from monomers that are endogenous to the human metabolism. Examples of these monomers include glycerol, xylitol, sorbitol, and lactic, sebacic, citric, succinic, α-ketoglutaric, and fumaric acids. In terms of mechanical versatility, crystallinity, hydrophobicity, and biocompatibility, polyesters synthesized partially or completely from these monomers can display a wide range of properties. The flexibility in these macromolecular properties allows for materials to be tailored according to the needs of a particular application. Along with the presence of natural monomers that allows for a high probability of biocompatibility, there is also an added benefit that this class of polyesters is more environmentally friendly than many other materials used in biomedical engineering. While the selection of monomers may be limited by nature, these polymers have produced or have the potential to produce an enormous number of successes in vitro and in vivo.

  20. The influence of monomer concentration on the optical properties of electrochemically synthesized polypyrrole thin films

    International Nuclear Information System (INIS)

    Thombare, J. V.; Fulari, V. J.; Rath, M. C.; Han, S. H.

    2013-01-01

    Polypyrrole (PPy) thin films were deposited on stainless steel and ITO coated glass substrate at a constant deposition potential of 0.8 V versus saturated calomel electrode (SCE) by using the electrochemical polymerization method. The PPy thin films were deposited at room temperature at various monomer concentrations ranging from 0.1 M to 0.3 M pyrrole. The structural and optical properties of the polypyrrole thin films were investigated using an X-ray diffractometer (XRD), FTIR spectroscopy, scanning electron microscopy (SEM), and ultraviolet—visible (UV—vis) spectroscopy. The XRD results show that polypyrrole thin films have a semi crystalline structure. Higher monomer concentration results in a slight increase of crystallinity. The polypyrrole thin films deposited at higher monomer concentration exhibit high visible absorbance. The refractive indexes of the polypyrrole thin films are found to be in the range of 1 to 1.3 and vary with monomer concentration as well as wavelength. The extinction coefficient decreases slightly with monomer concentration. The electrochemically synthesized polypyrrole thin film shows optical band gap energy of 2.14 eV. (semiconductor materials)

  1. Controlled grafting of vinylic monomers on polyolefins: a robust mathematical modeling approach.

    Science.gov (United States)

    Saeb, Mohammad Reza; Rezaee, Babak; Shadman, Alireza; Formela, Krzysztof; Ahmadi, Zahed; Hemmati, Farkhondeh; Kermaniyan, Tayebeh Sadat; Mohammadi, Yousef

    2017-01-01

    Experimental and mathematical modeling analyses were used for controlling melt free-radical grafting of vinylic monomers on polyolefins and, thereby, reducing the disturbance of undesired cross-linking of polyolefins. Response surface, desirability function, and artificial intelligence methodologies were blended to modeling/optimization of grafting reaction in terms of vinylic monomer content, peroxide initiator concentration, and melt-processing time. An in-house code was developed based on artificial neural network that learns and mimics processing torque and grafting of glycidyl methacrylate (GMA) typical vinylic monomer on high-density polyethylene (HDPE). Application of response surface and desirability function enabled concurrent optimization of processing torque and GMA grafting on HDPE, through which we quantified for the first time competition between parallel reactions taking place during melt processing: (i) desirable grafting of GMA on HDPE; (ii) undesirable cross-linking of HDPE. The proposed robust mathematical modeling approach can precisely learn the behavior of grafting reaction of vinylic monomers on polyolefins and be placed into practice in finding exact operating condition needed for efficient grafting of reactive monomers on polyolefins.

  2. Radiation-initiated emulsion copolymerization of styrene and carboxylic acid monomers

    International Nuclear Information System (INIS)

    Egusa, S.; Makuuchi, K.

    1982-01-01

    The emulsion copolymerization of styrene and carboxylic acid monomers such as acrylic, methacrylic, and itaconic acids (AAc, MAAc, IAc) was studied by using 60 Co γ-rays as initiator and sodium dodecylsulfate as emulsifier. The polymerization behavior of these acid monomers was followed by simultaneous conductometric and potentiometric titrations for a latex sample taken in polymerization. The polymerization rate of these acid monomers increases in the following order of hydrophobicity: IAc < AAc < MAAc; this suggests that their polymerization sites are mainly the surface and/or subsurface regions of latex particles. The copolymerization rate of styrene and acid monomer increases with an increase in the acid monomer content for AAc and MAAc, whereas for IAc the rate decreases. The particle sizes determined by the stopped-flow method reveal that this variation of copolymerization rate cannot be explained by the number of growing particles and should be attributed to another factor; for instance, the transfer rate of styrene molecules from oil droplets to growing particles

  3. Inhibition of odontogenic differentiation of human dental pulp cells by dental resin monomers.

    Science.gov (United States)

    Kwon, Ji Hyun; Park, Hee Chul; Zhu, Tingting; Yang, Hyeong-Cheol

    2015-01-01

    Dental resin monomers that are leached from the resin matrix due to incomplete polymerization can affect the viability and various functions of oral tissues and cells. In this study, the effects of triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate (HEMA) on odontogenic differentiation of human dental pulp cells (HDPCs) were examined. To mimic clinical situations, dental pulp cells were treated with resin monomers for 24 h prior to the analysis of alkaline phosphatase (ALP) activity and mRNA expression of genes related to pulp cell differentiation. To elucidate the underlying signaling pathways, regulation of mitogen-activated protein (MAP) kinases by resin monomers was also investigated. The ALP activity of HDPCs was reduced by TEGDMA and HEMA at noncytotoxic concentrations. The mRNA expression of dentin sialophosphoprotein (DSPP), osteocalcin (OCN), and osteopontin (OPN) was also downregulated by resin monomers. However, DSPP expression was not affected by hydrogen peroxide (H2O2). Among the MAP kinases examined, ERK activation (ERK phosphorylation) was not affected by either resin monomers or H2O2, whereas JNK was phosphorylated by TEGDMA and HEMA. Phospho-p38 was upregulated by HEMA, while TEGDMA and H2O2 suppressed p38 phosphorylation. Exposure to TEGDMA and HEMA for a limited period suppresses differentiation of HDPCs via different signaling pathways.

  4. Lewis pair polymerization by classical and frustrated Lewis pairs: Acid, base and monomer scope and polymerization mechanism

    KAUST Repository

    Zhang, Yuetao

    2012-01-01

    is significantly catalyzed by the LA, thus pointing to a bimetallic, activated monomer propagation mechanism. Computational study on the active species formation as well as the chain initiation and propagation events involved in the LPP of MMA with some of the most representative LPs has added our understanding of fundamental steps of LPP. The main difference between NHC and PR 3 bases is in the energetics of zwitterion formation, with the NHC-based zwitterions being remarkably more stable than the PR 3-based zwitterions. Comparison of the monometallic and bimetallic mechanisms for MMA addition shows a clear preference for the bimetallic mechanism. This journal is © 2012 The Royal Society of Chemistry.

  5. Testing of residual monomer content reduction possibility on acrilic resins quality

    Directory of Open Access Journals (Sweden)

    Kostić Milena

    2011-01-01

    Full Text Available Poly (methyl methacrylate (PMMA is material widely used in dentistry. Despite the various methods used to initiate the polymerization of acrylic resins, the conversion of monomer to polymer is not complete thus leaving some unreacted methyl methacrylate (MMA, known as residual monomer (RM, in denture structure. RM in dental acrylic resins has deleterious effects on their mechanical properties and their biocompatibility. The objective of the work was to test the residual monomer reduction possibility by applying the appropriate postpolymerization treatment as well as to determine the effects of this reduction on pressure yields stress and surface structure characteristics of the acrylic resins. Postpolymerization treatments and water storage induced reduction of RM amount in cold-polymerized acrylic resins improved their mechanical properties and the homogenized surface structure. After the polymerization of heat-polymerized acrylic resins the post-polymerization treatments for improving the quality of this material type are not necessary.

  6. Polymeric reaction of polymer-monomer system for pressure sensitive adhesives by low energy electron beam

    International Nuclear Information System (INIS)

    Takiguchi, R.; Uryu, T.

    1985-01-01

    Application of low-energy electron beam to non-solvent type pressure sensitive adhesives is investigated. The adhesive properties such as peel strength and holding time (dead-load strength) were closely related to the reaction of acrylate polymer-monomer systems. The reaction behavior is elucidated by combining the measurement of gel fraction, infrared spectrum of gel, and the molecular weight distribution detected by gel permeation chromatography. It was important for the production of pressure sensitive adhesives by electron beam that the adhesive with high peel strength and long holding time is composed of a proper combination of three factors, that is, about 35% gel fraction, 25% monomer units in gel, and 15% graft efficiency by irradiating the polymer-monomer system containing low molecular weight poly (butyl acrylate). (author)

  7. Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol)-acrylate monomer blends

    International Nuclear Information System (INIS)

    Koshiba, M.; Yamaoka, T.; Tsunoda, T.

    1983-01-01

    Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol) (PVA)-monoacrylate blends were investigated by measuring dynamic shear modulus G' and loss tangent, tan delta. The dynamic mechanical properties of the blends before being exposed to UV irradiation were governed by the weight percent of the monomers which act as plasticizers. On the other hand, the UV-irradiated blends seemed to be typical two-phase materials since they revealed two tan delta maxima whose positions were independent of the monomer content. Those two maxima were assigned to PVA and photopolymerized acrylates with reference to the dynamic mechanical data of PVA and a PVA-polyacrylamide polyblend. Those dynamic mechanical data suggested that insolubilization of the blend type photopolymers should be caused by a decrease in solubility due to graft polymerization of acrylate monomers onto PVA. 9 figures, 3 tables

  8. A study on radiation-induced graft copolymerization of monomer onto natural silk fabric

    International Nuclear Information System (INIS)

    Xiang Zhengyu; Wan Dairong; He Qian

    1995-02-01

    In order to improve the properties of natural silk fabric, the mechanism and method of the radiation induced graft copolymerization of monomers onto natural silk fabric were studied. Three monomers, acrylamide, methylacrylamide and hydroxymethyl acrylamide, were selected for grafting test according to requirements of graft processing. The processing conditions of monomer infusion were studied. The properties of grafted samples were measured. The results are as follows: the rate of weight increasing is 10%∼29%; the rate of thickness increasing is 5%∼20%; the abrupt elasticity rose by 30%; the retarded elasticity rose by 12%; wet elasticity rose by 40%; and the brightness of colour and lustre were improved. It is concluded that while the radiation grafted silk kept its natural characteristics, other properties were improved. It became even chubby and thicker. (4 refs., 3 figs., 3 tabs.)

  9. Considerably Unfolded Transthyretin Monomers Preceed and Exchange with Dynamically Structured Amyloid Protofibrils

    DEFF Research Database (Denmark)

    Groenning, Minna; Campos, Raul I; Hirschberg, Daniel

    2015-01-01

    describe an unexpectedly dynamic TTR protofibril structure which exchanges protomers with highly unfolded monomers in solution. The protofibrils only grow to an approximate final size of 2,900 kDa and a length of 70 nm and a comparative HXMS analysis of native and aggregated samples revealed a much higher...... average solvent exposure of TTR upon fibrillation. With SAXS, we reveal the continuous presence of a considerably unfolded TTR monomer throughout the fibrillation process, and show that a considerable fraction of the fibrillating protein remains in solution even at a late maturation state. Together......, these data reveal that the fibrillar state interchanges with the solution state. Accordingly, we suggest that TTR fibrillation proceeds via addition of considerably unfolded monomers, and the continuous presence of amyloidogenic structures near the protofibril surface offers a plausible explanation...

  10. Precision design of ethylene- and polar-monomer-based copolymers by organometallic-mediated radical polymerization

    Science.gov (United States)

    Kermagoret, Anthony; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

    2014-03-01

    The copolymerization of ethylene with polar monomers is a major challenge when it comes to the manufacture of materials with potential for a wide range of commercial applications. In the chemical industry, free-radical polymerization is used to make a large proportion of such copolymers, but the forcing conditions result in a lack of fine control over the architecture of the products. Herein we introduce a synthetic tool, effective under mild experimental conditions, for the precision design of unprecedented ethylene- and polar-monomer-based copolymers. We demonstrate how an organocobalt species can control the growth of the copolymer chains, their composition and the monomer distribution throughout the chain. By fine tuning the ethylene pressure during polymerization and by exploiting a unique reactive mode of the end of the organometallic chain, novel block-like copolymer structures can be prepared. This highly versatile synthetic platform provides access to a diverse range of polymer materials.

  11. High-speed atomic force microscopy reveals structural dynamics of α -synuclein monomers and dimers

    Science.gov (United States)

    Zhang, Yuliang; Hashemi, Mohtadin; Lv, Zhengjian; Williams, Benfeard; Popov, Konstantin I.; Dokholyan, Nikolay V.; Lyubchenko, Yuri L.

    2018-03-01

    α-Synuclein (α-syn) is the major component of the intraneuronal inclusions called Lewy bodies, which are the pathological hallmark of Parkinson's disease. α-Syn is capable of self-assembly into many different species, such as soluble oligomers and fibrils. Even though attempts to resolve the structures of the protein have been made, detailed understanding about the structures and their relationship with the different aggregation steps is lacking, which is of interest to provide insights into the pathogenic mechanism of Parkinson's disease. Here we report the structural flexibility of α-syn monomers and dimers in an aqueous solution environment as probed by single-molecule time-lapse high-speed AFM. In addition, we present the molecular basis for the structural transitions using discrete molecular dynamics (DMD) simulations. α-Syn monomers assume a globular conformation, which is capable of forming tail-like protrusions over dozens of seconds. Importantly, a globular monomer can adopt fully extended conformations. Dimers, on the other hand, are less dynamic and show a dumbbell conformation that experiences morphological changes over time. DMD simulations revealed that the α-syn monomer consists of several tightly packed small helices. The tail-like protrusions are also helical with a small β-sheet, acting as a "hinge". Monomers within dimers have a large interfacial interaction area and are stabilized by interactions in the non-amyloid central (NAC) regions. Furthermore, the dimer NAC-region of each α-syn monomer forms a β-rich segment. Moreover, NAC-regions are located in the hydrophobic core of the dimer.

  12. Distinct Internalization Pathways of Human Amylin Monomers and Its Cytotoxic Oligomers in Pancreatic Cells

    Science.gov (United States)

    Trikha, Saurabh; Jeremic, Aleksandar M.

    2013-01-01

    Toxic human amylin oligomers and aggregates are implicated in the pathogenesis of type 2 diabetes mellitus (TTDM). Although recent studies have shown that pancreatic cells can recycle amylin monomers and toxic oligomers, the exact uptake mechanism and trafficking routes of these molecular forms and their significance for amylin toxicity are yet to be determined. Using pancreatic rat insulinoma (RIN-m5F) beta (β)-cells and human islets as model systems we show that monomers and oligomers cross the plasma membrane (PM) through both endocytotic and non-endocytotic (translocation) mechanisms, the predominance of which is dependent on amylin concentrations and incubation times. At low (≤100 nM) concentrations, internalization of amylin monomers in pancreatic cells is completely blocked by the selective amylin-receptor (AM-R) antagonist, AC-187, indicating an AM-R dependent mechanism. In contrast at cytotoxic (µM) concentrations monomers initially (1 hour) enter pancreatic cells by two distinct mechanisms: translocation and macropinocytosis. However, during the late stage (24 hours) monomers internalize by a clathrin-dependent but AM-R and macropinocytotic independent pathway. Like monomers a small fraction of the oligomers initially enter cells by a non-endocytotic mechanism. In contrast a majority of the oligomers at both early (1 hour) and late times (24 hours) traffic with a fluid-phase marker, dextran, to the same endocytotic compartments, the uptake of which is blocked by potent macropinocytotic inhibitors. This led to a significant increase in extra-cellular PM accumulation, in turn potentiating amylin toxicity in pancreatic cells. Our studies suggest that macropinocytosis is a major but not the only clearance mechanism for both amylin’s molecular forms, thereby serving a cyto-protective role in these cells. PMID:24019897

  13. Graft copolymerization of water soluble mixed monomers onto polyethylene by the pre-irradiation method

    International Nuclear Information System (INIS)

    Long Fu; Tang Liming; Zhao Jin; Gao Zhenyong

    1993-01-01

    Grafting of water soluble mixed monomers of acrylic acid (AA)/acrylamide (Am) and acrylic acid/methacrylic acid (MA) onto polyethylene film by the pre-irradiation grafting method was investigated. The results showed that the grafting proceeded successfully with the adding of ferric salt in the solution. In the case of AA/Am system, a synergistic effect was noticed. In the case of AA/MA system, the graft percent increased with the increase in the concentration of MA in the feed ratio. Furthermore, the effects of monomer concentration, radiation dose and temperature on the grafting were also studied

  14. Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group

    DEFF Research Database (Denmark)

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

    2013-01-01

    Novel, fluorinated monomer with pendant sulfonate group was synthesized utilizing a two-step derivatization of 2,3,4,5,6-pentafluorostyrene (FS). The first step was a nucleophilic substitution of the fluorine atom in para position by hydroxyl group followed by sulfopropylation. The monomer...... was polymerized under aqueous ATRP conditions to yield phenyl-fluorinated aromatic homopolymer bearing pendant sulfonates on each repeating unit. Furthermore, this polymer was used as macroinitiator for the ATRP of poly(ethylene glycol) methacrylate. The polymers were characterized by 1H NMR, SEC and FTIR...

  15. Cyclic 3-alkyl pyridinium alkaloid monomers from a New Zealand Haliclona sp. marine sponge.

    Science.gov (United States)

    Damodaran, Vidhiya; Ryan, Jason L; Keyzers, Robert A

    2013-10-25

    Bioassay and NMR approaches have been used to guide the isolation of one known and two new cyclic 3-alkyl pyridinium alkaloid (3-APA) monomers from the New Zealand marine sponge Haliclona sp. The new compounds, dehydrohaliclocyclins C (3) and F (4), are the first reported examples of cyclic 3-APA monomers with unsaturation in the alkyl chain. The known compound haliclocyclin C (2) was also isolated from a mixture with 4. The structures of compounds 2-4 were elucidated using NMR spectroscopy, mass spectrometry, and chemical degradation.

  16. Preparation of poly (vinyl alcohol) membranes grafted with n-vinyl pyridine/ acrylic acid binary monomers

    International Nuclear Information System (INIS)

    Ajji, A.; Ali, A.

    2014-03-01

    Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl pyridine. The influence of different parameters on the grafting yield was investigated as: the comonomer concentration and composition, and irradiation dose. The suitable conditions of the process had been determined to prepare PVA membranes have both properties of the two monomers, acrylic acid and vinyl pyridine as comonomer concentration and composition, and irradiation dose. Some properties of the membranes had been investigated as maximum swelling and grafting. Also the ability of the grafted films to adsorb some heavy metals and dyes was elaborated and discussed.(author)

  17. High monomer content batch microemulsion polymerization of butyl acrylate initiated with gamma ray

    Energy Technology Data Exchange (ETDEWEB)

    Chen Jun [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: chjun04@mail.ustc.edu.cn; Zhang Zhicheng [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: zczhang@ustc.edu.cn

    2007-05-15

    Radiation polymerization of butyl acrylate was performed in a microemulsion stabilized with a mixture of sodium of 12-acryloxy-9-octadecenoic acid and sodium dodecyl sulfate in a weight ratio of 2 at room temperature. BA content in microemulsion can be successfully improved up to 40 wt% with low surfactant concentration (lower than 10 wt%). The resulted stable, translucent microlatex contain particles with average diameter from 28.1 to 38.1 nm with different monomer content. Particle size depends on the dose rate and surfactant concentration. Effects of monomer content and dose rate on the maximum polymerization rate are discussed.

  18. PMR Polyimide prepreg with improved tack characteristics. [Polymerization of Monomer Reactants applications to fiber reinforced plastics

    Science.gov (United States)

    Serafini, T. T.; Delvigs, P.

    1978-01-01

    Current PMR Polyimide prepreg technology utilizes methanol or ethanol solvents for preparation of the PMR prepreg solutions. The volatility of these solvents limits the tack and drape retention characteristics of unprotected prepreg exposed to ambient conditions. Studies conducted to achieve PMR 15 Polyimide prepreg with improved tack and drape characteristics are described. Improved tack and drape retention were obtained by incorporation of an additional monomer. The effects of various levels of the added monomer on the thermo-oxidative stability and mechanical properties of graphite fiber reinforced PMR 15 composites exposed and tested at 316 C (600 F) are discussed.

  19. In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites

    Science.gov (United States)

    Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

    1974-01-01

    Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

  20. New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

    Science.gov (United States)

    Wolfe, James F.

    1993-01-01

    The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

  1. Effect of mineral acid on polymer produced during radiation-induced grafting of styrene monomer

    International Nuclear Information System (INIS)

    Garnett, J.L.; Jankiewicz, S.V.; Sangster, D.F.

    1982-01-01

    The inclusion of mineral acid in a solution of styrene in methanol subjected to 60 Co γ irradiation markedly enhances the yield of monomer grafted to cellulose and other radiation grafting systems. Results were reported from a preliminary investigation into the mechanism of this acid effect through a study of the action of acid during the solution polymerization process. It was found that the presence of acid in a monomer solution such as styrene in 1, 4-dioxan led to an enhancement in the homopolymer yield of styrene; and it was showed that the acid also effected the number-average molecular weight of this homopolymer. 1 figure, 4 tables

  2. Penelitian penggunaan monomer n-butil akrilat untuk peningkatan mutu kulit secara iradiasi

    OpenAIRE

    Dwi Wahini Nurhajati; Suliestiyah Wiryodiningrat; Kadarijah Kadarijah; Penny Setyowati

    1996-01-01

    Research on the utilization of n-butyl acrylate monomer for quality improvement leather by irradiation cobalt-60 gamma-rays is carried out as follows: Javanese crust hide was impregnated with water emulsions of n-butyl acrylate monomer for 2 hours, packed in to poly ethylene bags, sealed, then irradiated by cobalt-60 gamma rays (doses : 5 to 25 kGy). The irradiated leather was washed by water, dried and then physical tested. The results of physical test of leather modified with n-butyl acryl...

  3. Flavanol monomer-induced changes to the human faecal microflora.

    Science.gov (United States)

    Tzounis, Xenofon; Vulevic, Jelena; Kuhnle, Gunter G C; George, Trevor; Leonczak, Jadwiga; Gibson, Glenn R; Kwik-Uribe, Catherine; Spencer, Jeremy P E

    2008-04-01

    We have investigated the bacterial-dependent metabolism of ( - )-epicatechin and (+)-catechin using a pH-controlled, stirred, batch-culture fermentation system reflective of the distal region of the human large intestine. Incubation of ( - )-epicatechin or (+)-catechin (150 mg/l or 1000 mg/l) with faecal bacteria, led to the generation of 5-(3',4'-dihydroxyphenyl)-gamma-valerolactone, 5-phenyl-gamma-valerolactone and phenylpropionic acid. However, the formation of these metabolites from (+)-catechin required its initial conversion to (+)-epicatechin. The metabolism of both flavanols occurred in the presence of favourable carbon sources, notably sucrose and the prebiotic fructo-oligosaccharides, indicating that bacterial utilisation of flavanols also occurs when preferential energy sources are available. (+)-Catechin incubation affected the growth of select microflora, resulting in a statistically significant increase in the growth of the Clostridium coccoides-Eubacterium rectale group, Bifidobacterium spp. and Escherichia coli, as well as a significant inhibitory effect on the growth of the C. histolyticum group. In contrast, the effect of ( - )-epicatechin was less profound, only significantly increasing the growth of the C. coccoides-Eubacterium rectale group. These potential prebiotic effects for both (+)-catechin and ( - )-epicatechin were most notable at the lower concentration of 150 mg/l. As both ( - )-epicatechin and (+)-catechin were converted to the same metabolites, the more dramatic change in the growth of distinct microfloral populations produced by (+)-catechin incubation may be linked to the bacterial conversion of (+)-catechin to (+)-epicatechin. Together these data suggest that the consumption of flavanol-rich foods may support gut health through their ability to exert prebiotic actions.

  4. Characteristic features of heterophase polymerisation of styrene with simultaneous formation of surfactants at the interface

    International Nuclear Information System (INIS)

    Prokopov, Nikolai I; Gritskova, Inessa A

    2001-01-01

    Data on the heterophase polymerisation of styrene under conditions of surfactant formation at the monomer-water interface are generalised. A new, in principle, approach is proposed the essence of which is to obtain a monomer emulsion simultaneously with the synthesis of an emulsifier at the monomer-water interface and with initiation of the polymerisation in the interfacial layer. The preparation of surfactants at the interface allows one to control efficiently the degree of dispersion and the stability of the emulsions formed. By varying the nature of the acid and the metal counter-ion used in the surfactant synthesis at the interface, it is possible to change the interfacial tension, to influence the microemulsification, disintegration of the monomer, and the formation of structure of interfacial adsorption layers. The mechanism of formation of polymer-monomeric particles as well as their diameter and size distribution depend substantially on the solubility of the resulting surfactants in water. The bibliography includes 47 references.

  5. Characteristic features of heterophase polymerisation of styrene with simultaneous formation of surfactants at the interface

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-09-30

    Data on the heterophase polymerisation of styrene under conditions of surfactant formation at the monomer-water interface are generalised. A new, in principle, approach is proposed the essence of which is to obtain a monomer emulsion simultaneously with the synthesis of an emulsifier at the monomer-water interface and with initiation of the polymerisation in the interfacial layer. The preparation of surfactants at the interface allows one to control efficiently the degree of dispersion and the stability of the emulsions formed. By varying the nature of the acid and the metal counter-ion used in the surfactant synthesis at the interface, it is possible to change the interfacial tension, to influence the microemulsification, disintegration of the monomer, and the formation of structure of interfacial adsorption layers. The mechanism of formation of polymer-monomeric particles as well as their diameter and size distribution depend substantially on the solubility of the resulting surfactants in water. The bibliography includes 47 references.

  6. Do the monomers release from the composite resins after artificial aging?

    Science.gov (United States)

    Tokay, Ugur; Koyuturk, Alp Erdin; Aksoy, Abdurrahman; Ozmen, Bilal

    2015-04-01

    The aim of this study is to measure the effect of thermal cycling on the amount of monomer released from three different composite materials by HPLC analysis method. Three different composite materials, inlay composite, posterior composite and micro-hybrid composite were used. Sixty cylinder specimens each with a dimension of approximately 1 cm width and 3 mm depth, were prepared before experiments were carried out. Inlay composite material was polymerized according to manufacturers' instructions. Thermal cycling device was used to simulate thermal differences which occur in the mouth media. Monomers were analyzed using HPLC technic after thermal cycling process. The amount of ethoxylated Bis-GMA and urethane dimethacrylate (UDMA) in inlay composite material, the amount of ethoxylated Bis-GMA in posterior composite material, the amount of ethoxylated Bis-GMA and triethyleneglycol dimethacrylate (TEGDMA) in micro-hybrid composite material were investigated. Monomer release of thermal cycles levels showed a linear increase in UDMA and TEGDMA (P < 0.05). In terms of thermal cycles levels, Bis-EMA released from posterior composite showed a cubic change (P < 0.001). It was observed that use of additional polymerization processes might have positive effect on the decrease of residual monomer. In the light of the results, we suggest that indirect composite resins have more outstanding features than direct composite resins in terms of biocompatibility. © 2015 Wiley Periodicals, Inc.

  7. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  8. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA

    NARCIS (Netherlands)

    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.

    2014-01-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of

  9. Reduction of residual monomer in latex products by enhanced polymerization and extraction in supercritical carbon dioxide

    NARCIS (Netherlands)

    Kemmere, M.F.; Schilt, van M.A.; Cleven, M.H.W.; Herk, van A.M.; Keurentjes, J.T.F.

    2002-01-01

    The redn. of Me methacrylate (MMA) in a PMMA latex was chosen as a representative model system. Pulsed electron beam expts. were performed to study the effect of supercrit. carbon dioxide (scCO2) on the monomer concn. inside the polymer particles during the polymn. reaction. The partitioning

  10. Polyimide, dianhydride monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Pinnau, Ingo; Ghanem, Bader Saleh; Abdulhamid, Mahmoud Atef

    2017-01-01

    Embodiments of the present disclosure include, a dianhydride monomer, a polyimide, a method of making a dianhydride, a method of making a polyimide, and the like. Embodiments of the present disclosure can be used in membrane-based gas separation applications.

  11. Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to ''living'' polymers

    International Nuclear Information System (INIS)

    Farnham, W.B.; Hertler, W.R.

    1988-01-01

    This patent describes a process for preparing ''living'' polymer. The process comprises contacting one or more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetra-coordinate organotitanium, organozirconium or organo-hafnium polymerization initiator, and ''living'' polymers produced thereby

  12. Microwave-assisted cationic ring-opening polymerization of a soy-based 2-oxazoline monomer

    NARCIS (Netherlands)

    Hoogenboom, R.; Wiesbrock, F.D.; Schubert, U.S.

    2005-01-01

    The microwave-assisted cationic ring-opening polymn. of a soy based 2-oxazoline monomer (SoyOx) is described. The microwave irradn. provides more efficient heating when compared to conventional heating and, in addn., the SoyOx was prepd. starting from a sustainable resource (soy beans). The

  13. The Off-rate of Monomers Dissociating from Amyloid-β Protofibrils*

    Science.gov (United States)

    Grüning, Clara S. R.; Klinker, Stefan; Wolff, Martin; Schneider, Mario; Toksöz, Küpra; Klein, Antonia N.; Nagel-Steger, Luitgard; Willbold, Dieter; Hoyer, Wolfgang

    2013-01-01

    The interconversion of monomers, oligomers, and amyloid fibrils of the amyloid-β peptide (Aβ) has been implicated in the pathogenesis of Alzheimer disease. The determination of the kinetics of the individual association and dissociation reactions is hampered by the fact that forward and reverse reactions to/from different aggregation states occur simultaneously. Here, we report the kinetics of dissociation of Aβ monomers from protofibrils, prefibrillar high molecular weight oligomers previously shown to possess pronounced neurotoxicity. An engineered binding protein sequestering specifically monomeric Aβ was employed to follow protofibril dissociation by tryptophan fluorescence, precluding confounding effects of reverse or competing reactions. Aβ protofibril dissociation into monomers follows exponential decay kinetics with a time constant of ∼2 h at 25 °C and an activation energy of 80 kJ/mol, values typical for high affinity biomolecular interactions. This study demonstrates the high kinetic stability of Aβ protofibrils toward dissociation into monomers and supports the delineation of the Aβ folding and assembly energy landscape. PMID:24247242

  14. Polyimide, dianhydride monomers, and polymers, methods of making and uses thereof

    KAUST Repository

    Pinnau, Ingo

    2017-11-16

    Embodiments of the present disclosure include, a dianhydride monomer, a polyimide, a method of making a dianhydride, a method of making a polyimide, and the like. Embodiments of the present disclosure can be used in membrane-based gas separation applications.

  15. Visualization of monomer and polymer inside porous stones by using X-ray tomography

    International Nuclear Information System (INIS)

    Brunetti, Antonio; Princi, Elisabetta; Vicini, Silvia; Pincin, Silvia; Bidali, Simone; Mariani, Alberto

    2004-01-01

    Estimate of sorption of liquid materials inside porous stones is an important parameter in industrial material testing and cultural heritage conservation. In the latter case, a suitable polymer can be used for both consolidation and conservation, it being applied either in the final form or as its parent monomer, which is subsequently allowed to polymerize in situ by the classical method or by frontal polymerization. However, the sorption of such materials through the stone is often difficult because of their viscosity and/or stone porosity. For this reason, the amount of monomer (or polymer) is a parameter of great interest in order to determine the extent of protection reachable by the treatment. In this paper a new methodology based on X-ray tomography is presented. The methodology makes use of a contrast agent added to the monomer that does not interact with its propagation inside the stone and allows to increase the absorption coefficient and so to observe the monomer inside the sample, which is finally frontally polymerized

  16. Syntheses of monomers in the reaction of hexamethylolmelamine with 2-hydroxyethyl acrylate and their photocuring

    International Nuclear Information System (INIS)

    Huhui Houlianbo Hufei

    1999-01-01

    A process has been developed for the syntheses of monomers from 2-hydroxyethyl acrylate and hexamethylolmelamine. Their structure were identified by IR and sub 1H-NMR. The photocuring characteristics of these compound and properties of the UV-cured films have been studied

  17. Regulation of the PI3K pathway through a p85a monomer-homodimer equilibrium

    KAUST Repository

    Aljedani, Safia Salim Eid

    2017-01-08

    The phosphatidylinositol-3-kinase a (PI3Ka) is heterodimeric enzyme that is composed of p85a regulatory subunit and a p110a catalytic subunit. PI3Ka plays a key role in cell survival, growth and differentation. Owing to its role as a key regulator, the PI3Ka pathway is the most frequently mutated pathway in human cancers, and is targeted by many viruses to insure their survival and successful reproduction. Previous studies have shown that the equilibrium of p85 monomers and dimers regulates the PI3K pathway, suggesting that interrupting this equilibrium could lead to disease development. Moreover, studies suggest that the p85a monomers and dimers have opposing effects on PI3Ka signaling as only the p85a dimers bind to the PTEN phosphatase, whereas p85a monomers bind to the catalytic p110 subunit. However, the mechanism for dimerisation is controversial, and it is unknown why PTEN or p110a bind only dimer or monomer. Therefore, we combine molecular biology, biophsical, computational and structural methods to investigate the suprosingly complex p85 dimerisation mechanism and its control by ligands. Results may inspire novel theraputic approaches.

  18. High-resolution structure of a retroviral protease folded as a monomer

    Czech Academy of Sciences Publication Activity Database

    Gilski, M.; Kazmierczyk, M.; Krzywda, S.; Zábranská, Helena; Cooper, S.; Popovic, Z.; Khatíb, F.; Dímaio, F.; Thompson, J.; Baker, D.; Pichová, Iva; Jaskolski, M.

    D67, č. 11 (2011), s. 907-914 ISSN 0907-4449 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : M-PMV protease * crystal structure * monomer * dimerization inhibitors Subject RIV: CE - Biochemistry Impact factor: 12.619, year: 2011

  19. Environmental effects on the lignin model monomer, vanillyl alcohol, studied by raman spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Kiki Lyster; Barsberg, Søren Talbro

    2011-01-01

    model monomer, vanillyl alcohol (G type), dissolved in different solvents were compared to investigate such effects on the Raman band shapes and positions. Density functional theory combined with the polarizable continuum model were applied to assign the observed bands and tested for prediction accuracy...

  20. Enzymatic polymerization of bio-based monomers for applications in hydrogels and coatings

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Nguyen, Hiep Dinh; Storgaard, Thomas

    of the enzymatic catalysts that can provide control over polymer structure in functional polymers. Lipase catalyzed polymerizations (specifically CALB) has been applied to prepare functional polyesters and to evaluate the possibilities of using less stable bio-based monomers such as itaconic acid or its...

  1. Effect of reactive monomer on PS-b-P2VP film with UV irradiation

    Science.gov (United States)

    Kim, H. J.; Shin, D. M.

    2012-03-01

    Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block hydrophilic polyelectrolyte block polymer of 52 kg/mol -b- 57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic part of PS-b-P2VP. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. And band gaps of the lamellar films shifted by the time of UV light irradiation. That Photonic gel films were measured with the UV spectrophotometer. As a result the photonic gel film with reactive monomer had more clear color. The lamellar films were swollen by DI water, Ethyl alcohol (aq) and calcium carbonate solution. Since the domain spacing of dried photonic gel films were not showing any color in visible wavelength. The band gap of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution (absorbance peak 565nm-->617nm). And the lamellar films were shifted to shorter wave length swollen by ethanol (absorbance peak 565nm-->497nm). So each Photonic gel film showed different color.

  2. Monitoring of originated polymer in pure monomer with gradient polymer elution chromatography (GPEC)

    NARCIS (Netherlands)

    Staal, W.J.; Cools, P.J.C.H.; Herk, van A.M.; German, A.L.

    1994-01-01

    The anal. of the amt. of polymer in pure monomer with cloudpoint measurements gives only a qual. answer. Now by use of a liq. chromatograph and gradient elution a fully automated detn. the amt. of polymer can be measured and an impression of the molar mass can be achieved

  3. Residual monomer reduction in polymer latex products by extraction with supercritical carbon dioxide

    NARCIS (Netherlands)

    Aerts, M.; Meuldijk, J.; Kemmere, M.F.; Keurentjes, J.T.F.

    2011-01-01

    Extraction of residual monomer from a latex product with supercritical carbon dioxide ((sc)CO2) in a column was studied. Operating conditions were chosen at 35¿°C and 100 bar. For reducing the residual styrene level in a polystyrene latex from 104 ppm to 100¿ppm and from 104 ppm to 10¿ppm, a

  4. Stark effect measurements on monomers and trimers of reconstituted light-harvesting complex II of plants

    NARCIS (Netherlands)

    Palacios, M.A.; Caffarri, S.; Bassi, R.; Grondelle, van R.; Amerongen, van H.

    2004-01-01

    The electric-field induced absorption changes (Stark effect) of reconstituted light-harvesting complex II (LHCII) in different oligomerisation states - monomers and trimers - with different xanthophyll content have been probed at 77 K. The Stark spectra of the reconstituted control samples,

  5. Fatty Acid-Based Monomers as Styrene Replacements for Liquid Molding Resins

    Science.gov (United States)

    2005-05-01

    fatty acid length and unsaturation level on resin and polymer properties. Fig. 2. The addition of fatty acids ( oleic acid ) to glycidyl methacylate to...the synthetic route used to form the methacrylated fatty acids (MFA). The carboxylic acid of fatty acids undergoes a simple addition reaction with... form methacrylated fatty acid monomer

  6. The role of polycarbonate monomer bisphenol-A in insulin resistance.

    Science.gov (United States)

    Pjanic, Milos

    2017-01-01

    Bisphenol A (BPA) is a synthetic unit of polycarbonate polymers and epoxy resins, the types of plastics that could be found in essentially every human population and incorporated into almost every aspect of the modern human society. BPA polymers appear in a wide range of products, from liquid storages (plastic bottles, can and glass linings, water pipes and tanks) and food storages (plastics wraps and containers), to medical and dental devices. BPA polymers could be hydrolyzed spontaneously or in a photo- or temperature-catalyzed process, providing widespread environmental distribution and chronic exposure to the BPA monomer in contemporary human populations. Bisphenol A is also a xenoestrogen, an endocrine-disrupting chemical (EDC) that interferes with the endocrine system mimicking the effects of an estrogen and could potentially keep our endocrine system in a constant perturbation that parallels endocrine disruption arising during pregnancy, such as insulin resistance (IR). Gestational insulin resistance represents a natural biological phenomenon of higher insulin resistance in peripheral tissues of the pregnant females, when nutrients are increasingly being directed to the embryo instead of being stored in peripheral tissues. Gestational diabetes mellitus may appear in healthy non-diabetic females, due to gestational insulin resistance that leads to increased blood sugar levels and hyperinsulinemia (increased insulin production from the pancreatic beta cells). The hypothesis states that unnoticed and constant exposure to this environmental chemical might potentially lead to the formation of chronic low-level endocrine disruptive state that resembles gestational insulin resistance, which might contribute to the development of diabetes. The increasing body of evidence supports the major premises of this hypothesis, as exemplified by the numerous publications examining the association of BPA and insulin resistance, both epidemiological and mechanistic. However, to

  7. The difference of acrylic resin residual monomer levels with various polymerization method

    Directory of Open Access Journals (Sweden)

    Sherman Salim

    2011-12-01

    Full Text Available Background: After polymerization process, heat cured acrylic resin denture base actually still contains residual monomers that can become potential irritants later in oral cavity. Polymerization process is essential to obtain acrylic resin which can meet the requirements of the biocompatible and good physical properties. To meet the requirements, there are several methods of polymerization process used. Purpose: The purpose of this study was to determine the differences of the residual monomer levels of acrylic resin processed by various polymerization methods. Methods: Acrylic resin powder and liquid were mixed based on the rules of factory, and sample was made with size of 30 mm × 50 mm × 3 mm and then polymerized by using microwave at 70° C for 24 hours based on the methods of Japan Industrial Standard (JIS. Each group of samples was cut with weight of ± 0.2 g, dissolved in 5 ml of methyl ethyl ketone in test tubes, and then stored at ± 5° C for four days. Residual monomer level was conducted by using gas chromatograph mass spectrometer. Data obtained were then analyzed by using One-Way ANOVA test with p < 0.05. Results: After the level of polymerizing residual monomer with JIS method was compared to that at 70° C for 24 hours using microwave, it is known that there were significant differences (p < 0.05. Conclusion: The highest level of residual monomer of acrylic resin was that polymerized at 70° C for 24 hours.Latar belakang: Basis gigi tiruan yang berbahan dasar resin akrilik jenis heat cured setelah proses polimerisasi selesai masih mengandung monomer sisa yang berpotensi sebagai bahan iritan dalam rongga mulut. Proses polimerisasi sangat penting untuk mendapatkan resin akrilik yang memenuhi persyaratan biokompatibilitas dan fisik yang baik. Untuk persyaratan tersebut digunakan berbagai macam proses polimerisasi. Tujuan: Penelitian ini bertujuan untuk menentukan kadar monomer sisa resin akrilik yang diproses dengan metode

  8. Concomitant sensitization to glutaraldehyde and methacrylic monomers among dentists and their patients

    Directory of Open Access Journals (Sweden)

    Maya Grigorievna Lyapina

    2016-06-01

    Full Text Available Background: A multitude of methacrylic monomers is used in dentistry. Glutaraldehyde (G is used in dental practice and consumer products as a broad-spectrum antimicrobial agent. The purpose of our study is to evaluate the frequency and the risk of concomitant sensitization to some methacrylic monomers (methyl methacrylate (MMA, triethyleneglycol dimethacrylate (TEGDMA, ethyleneglycol dimethacrylate (EGDMA, 2,2-bis-[4-(2-hydroxy-3-methacrylo-xypropoxyphenyl]-propane (Bis-GMA, 2-hydroxy-ethyl methacrylate (2-HEMA and tetrahydrofurfuryl methacrylate (THFMA and glutaraldehyde in students of dentistry, students from the dental technician school, dental professionals and dental patients. Material and Methods: A total of 262 participants were included in the study: students of dentistry, students from the dental technician school, dental professionals, and dental patients as a control group. All were patch-tested with methacrylic monomers and glutaraldehyde. The results were subject to the statistical analysis (p < 0.05. Results: Among the group of dental students, the highest frequency of concomitant sensitization was to TEGDMA and G (15.5%. In the group of patients the highest frequency of concomitant sensitization was to EGDMA and G (16.4%. The frequency of concomitant sensitization among dental professionals was much lower, with the highest rate to TEGDMA and G (7.7%, too. We consider the students from the dental technician school, where the exposure to glutaraldehyde is less likely, to be the group at a lesser risk of concomitant sensitization. Conclusions: Dental students and dental patients could be outlined as groups at the risk of concomitant sensitization to glutaraldehyde and methacrylic monomers. For dental professionals, we assumed an increased risk for concomitant sensitization to TEGDMA and aldehydes that are commonly used in dentistry. We consider the students from the dental technician school to be the group at a lesser risk of

  9. Coupling of g proteins to reconstituted monomers and tetramers of the M2 muscarinic receptor.

    Science.gov (United States)

    Redka, Dar'ya S; Morizumi, Takefumi; Elmslie, Gwendolynne; Paranthaman, Pranavan; Shivnaraine, Rabindra V; Ellis, John; Ernst, Oliver P; Wells, James W

    2014-08-29

    G protein-coupled receptors can be reconstituted as monomers in nanodiscs and as tetramers in liposomes. When reconstituted with G proteins, both forms enable an allosteric interaction between agonists and guanylyl nucleotides. Both forms, therefore, are candidates for the complex that controls signaling at the level of the receptor. To identify the biologically relevant form, reconstituted monomers and tetramers of the purified M2 muscarinic receptor were compared with muscarinic receptors in sarcolemmal membranes for the effect of guanosine 5'-[β,γ-imido]triphosphate (GMP-PNP) on the inhibition of N-[(3)H]methylscopolamine by the agonist oxotremorine-M. With monomers, a stepwise increase in the concentration of GMP-PNP effected a lateral, rightward shift in the semilogarithmic binding profile (i.e. a progressive decrease in the apparent affinity of oxotremorine-M). With tetramers and receptors in sarcolemmal membranes, GMP-PNP effected a vertical, upward shift (i.e. an apparent redistribution of sites from a state of high affinity to one of low affinity with no change in affinity per se). The data were analyzed in terms of a mechanistic scheme based on a ligand-regulated equilibrium between uncoupled and G protein-coupled receptors (the "ternary complex model"). The model predicts a rightward shift in the presence of GMP-PNP and could not account for the effects at tetramers in vesicles or receptors in sarcolemmal membranes. Monomers present a special case of the model in which agonists and guanylyl nucleotides interact within a complex that is both constitutive and stable. The results favor oligomers of the M2 receptor over monomers as the biologically relevant state for coupling to G proteins. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  10. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura

    2017-02-13

    We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  11. Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

    Science.gov (United States)

    Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

    2010-09-13

    The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

  12. Luminal and parenteral TFF2 and TFF3 dimer and monomer in two models of experimental colitis in the rat

    DEFF Research Database (Denmark)

    Poulsen, Steen Seier; Kissow, Hannelouise; Hare, Kristine

    2005-01-01

    % dextran sodium sulphate in the drinking water or by one intraperitoneal injection of mitomycin C, 3.75 mg/kg. TFF peptides were administered as subcutaneous injections or directly into the lumen via a catheter placed in the proximal colon. Treatments were saline, TFF2, TFF3 monomer or TFF3 dimer 5 mg......2 had positive effect only in DSS-induced colitis. The TFF3 monomer was without any effects in both models. Treatment effect was most pronounced in the middle part of the colon, closest to the tip of the catheter. Injected TFF peptides, especially the TFF3 monomer, aggravated the colitis score...... in both colitis models. CONCLUSIONS: Intracolonic administration of TFF3 dimer and TFF2 improves experimentally induced colitis in rats. The TFF3 monomer has no effect. Parenteral administration of TFF peptides aggravates the colitis especially the TFF3 monomer....

  13. Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

    KAUST Repository

    Zhang, Yuetao; Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

    2013-01-01

    This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

  14. Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

    KAUST Repository

    Zhang, Yuetao

    2013-11-27

    This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

  15. The contrasting effect of macromolecular crowding on amyloid fibril formation.

    Directory of Open Access Journals (Sweden)

    Qian Ma

    Full Text Available Amyloid fibrils associated with neurodegenerative diseases can be considered biologically relevant failures of cellular quality control mechanisms. It is known that in vivo human Tau protein, human prion protein, and human copper, zinc superoxide dismutase (SOD1 have the tendency to form fibril deposits in a variety of tissues and they are associated with different neurodegenerative diseases, while rabbit prion protein and hen egg white lysozyme do not readily form fibrils and are unlikely to cause neurodegenerative diseases. In this study, we have investigated the contrasting effect of macromolecular crowding on fibril formation of different proteins.As revealed by assays based on thioflavin T binding and turbidity, human Tau fragments, when phosphorylated by glycogen synthase kinase-3β, do not form filaments in the absence of a crowding agent but do form fibrils in the presence of a crowding agent, and the presence of a strong crowding agent dramatically promotes amyloid fibril formation of human prion protein and its two pathogenic mutants E196K and D178N. Such an enhancing effect of macromolecular crowding on fibril formation is also observed for a pathological human SOD1 mutant A4V. On the other hand, rabbit prion protein and hen lysozyme do not form amyloid fibrils when a crowding agent at 300 g/l is used but do form fibrils in the absence of a crowding agent. Furthermore, aggregation of these two proteins is remarkably inhibited by Ficoll 70 and dextran 70 at 200 g/l.We suggest that proteins associated with neurodegenerative diseases are more likely to form amyloid fibrils under crowded conditions than in dilute solutions. By contrast, some of the proteins that are not neurodegenerative disease-associated are unlikely to misfold in crowded physiological environments. A possible explanation for the contrasting effect of macromolecular crowding on these two sets of proteins (amyloidogenic proteins and non-amyloidogenic proteins has been

  16. Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel

    International Nuclear Information System (INIS)

    Shin, Jinsub; Han, Sung Gu; Lee, Wonmok

    2012-01-01

    Highlights: ► We polymerized four different inverse opal pH sensors by using vinyl monomers containing acidic or basic substituents. ► Stepwise swelling response from polyprotic acid sensor was investigated. ► Opposite color changing responses were obtained for acidic and basic sensors. ► Composite pH sensor with wide pH sensing range was fabricated by mixing different monomers. ► Both acid and base sensors show the response time as fast as ∼10 s. - Abstract: pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK a1 and pK a2 respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK b s were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the

  17. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    International Nuclear Information System (INIS)

    Rahim, Afidah A.; Rocca, E.; Steinmetz, J.; Kassim, M.J.; Adnan, R.; Sani Ibrahim, M.

    2007-01-01

    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection

  18. Radiation initiated grafting of hydrophilic and reactive monomers on polyetherurethane for biomedical application

    International Nuclear Information System (INIS)

    Jansen, B.; Ellinghorst, G.

    1981-01-01

    Hydrogels such poly(hydroxyethylmethacrylate), poly (acrylamide) and poly(2,3-dihydroxypropylmethacrylate) are a class of well-known materials with good to excellent biomedical properties. Unfortunately the mechanical behaviour of the water-swollen gels is poor, and thus their application in pure state is limited. Much work has been done, especially by the grafting technique, on supporting the hydrogels by several techniques in order to improve their mechanical properties. In this work grafting of hydrogel forming or reactive monomers (which can be made hydrophilic by a following chemical process) onto a polyetherurethane was performed by a technique in which the trunk polymer is swollen in the graft monomer before irradiation. (author)

  19. Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

    Science.gov (United States)

    Su, Ming; Aslam, Mohammed; Fu, Lei; Wu, Nianqiang; Dravid, Vinayak P.

    2004-05-01

    Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer "ink" in dip-pen nanolithography (DPN). The nominal monomer "ink" is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters.

  20. Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

    International Nuclear Information System (INIS)

    Su Ming; Aslam, Mohammed; Fu Lei; Wu Nianqiang; Dravid, Vinayak P.

    2004-01-01

    Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer 'ink' in dip-pen nanolithography (DPN). The nominal monomer 'ink' is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters

  1. Mangrove tannins and their flavanoid monomers as alternative steel corrosion inhibitors in acidic medium

    Energy Technology Data Exchange (ETDEWEB)

    Rahim, Afidah A. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)]. E-mail: afidah@usm.my; Rocca, E. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Steinmetz, J. [Laboratoire de Chimie du Solide Mineral, Universite Henri Poincare, Nancy I BP 239, 54506 Vandoeuvre Les Nancy (France); Kassim, M.J. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Adnan, R. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia); Sani Ibrahim, M. [School of Chemical Sciences, University Sains Malaysia, 11800 Penang (Malaysia)

    2007-02-15

    The inhibitive behaviour on steel of flavanoid monomers that constitute mangrove tannins namely catechin, epicatechin, epigallocatechin and epicatechingallate was investigated in an aerated HCl solution via electrochemical methods. The monomers were found to be mainly cathodic inhibitors and the inhibition efficiency was dependent on concentration. To explain the adsorptive behaviour of the molecules on the steel surface, a semiempirical approach involving quantum chemical calculations using HyperChem 6.0 was undertaken. The HOMO electronic density of the molecule was used to explain the inhibiting mechanism. The most probable adsorption centers were found in the vicinity of the phenolic groups. In a second part, the use of mangrove tannin, extracted from the mangrove barks as steel corrosion inhibitors in acidic media was investigated and its inhibitive efficiency was compared with that of commercial mimosa, quebracho and chestnut tannins. The inhibitive performance of mangrove tannins was comparable to the other tannins investigated, indicating their potential in corrosion protection.

  2. Penelitian penggunaan monomer n-butil akrilat untuk peningkatan mutu kulit secara iradiasi

    Directory of Open Access Journals (Sweden)

    Dwi Wahini Nurhajati

    1996-06-01

    Full Text Available Research on the utilization of n-butyl acrylate monomer for quality improvement leather by irradiation cobalt-60 gamma-rays is carried out as follows: Javanese crust hide was impregnated with water emulsions of n-butyl acrylate monomer for 2 hours, packed in to poly ethylene bags, sealed, then irradiated by cobalt-60 gamma rays (doses : 5 to 25 kGy. The irradiated leather was washed by water, dried and then physical tested. The results of physical test of leather modified with n-butyl acrylate showed the increasing of tensile strength and elongation, decreasing of water absorption, resistance against the flexing test of 20,000 times, and PH was constant. Organoleptic test showed that the softly of the modified leather was no different with unmodified leather.

  3. GPCR homomers and heteromers: a better choice as targets for drug development than GPCR monomers?

    Science.gov (United States)

    Casadó, Vicent; Cortés, Antoni; Mallol, Josefa; Pérez-Capote, Kamil; Ferré, Sergi; Lluis, Carmen; Franco, Rafael; Canela, Enric I

    2009-11-01

    G protein-coupled receptors (GPCR) are targeted by many therapeutic drugs marketed to fight against a variety of diseases. Selection of novel lead compounds are based on pharmacological parameters obtained assuming that GPCR are monomers. However, many GPCR are expressed as dimers/oligomers. Therefore, drug development may consider GPCR as homo- and hetero-oligomers. A two-state dimer receptor model is now available to understand GPCR operation and to interpret data obtained from drugs interacting with dimers, and even from mixtures of monomers and dimers. Heteromers are distinct entities and therefore a given drug is expected to have different affinities and different efficacies depending on the heteromer. All these concepts would lead to broaden the therapeutic potential of drugs targeting GPCRs, including receptor heteromer-selective drugs with a lower incidence of side effects, or to identify novel pharmacological profiles using cell models expressing receptor heteromers.

  4. Synthesis and Characterization of Oligodeoxyribonucleotides Modified with 2'-Amino-α-l-LNA Adenine Monomers

    DEFF Research Database (Denmark)

    Andersen, Nicolai K; Anderson, Brooke A; Wengel, Jesper

    2013-01-01

    The development of conformationally restricted nucleotide building blocks continues to attract considerable interest because of their successful use within antisense, antigene, and other gene-targeting strategies. Locked nucleic acid (LNA) and its diastereomer α-l-LNA are two interesting examples...... (ONs) modified with 2'-amino-α-l-LNA adenine monomers W-Z. The synthesis of the target phosphoramidites 1-4 is initiated from pentafuranose 5, which upon Vorbrüggen glycosylation, O2'-deacylation, O2'-activation and C2'-azide introduction yields nucleoside 8. A one-pot tandem Staudinger....... ONs modified with pyrene-functionalized 2'-amino-α-l-LNA adenine monomers X-Z display greatly increased affinity toward DNA targets (ΔTm/modification up to +14 °C). Results from absorption and fluorescence spectroscopy suggest that the duplex stabilization is a result of pyrene intercalation...

  5. Effect of Monomer Dosing Rate in the Preparation of Mesoporous Polystyrene Nanoparticles by Semicontinuous Heterophase Polymerization

    Directory of Open Access Journals (Sweden)

    Dalia Y. Sosa

    2014-12-01

    Full Text Available The semicontinuous heterophase polymerization of styrene in the presence of cross-linking and porogen agents was carried out. Latexes with close to 20% solid content, which contained mesoporous nanoparticles with 28 nm in average diameters, up to 0.5 cm3/g in porosity and 6–8 nm in pore diameters were obtained. By varying the monomer dosing rate over the micellar solution, an unexpected direct dependence of instantaneous conversion on the monomer dosing rate was found. This was ascribed to the higher average number of radicals per particle attained in the polymerization at the higher dosing rate, which in turn would arise from the higher gel percentage in the polymer. It is believed that the cross-linked chains prevent encounters between radicals, delaying the bimolecular termination reactions and allowing the existence of more than one radical inside the particles, which in turn increases the propagation rate.

  6. Immobilization of enzymes by radiation-induced polymerization of glass-forming monomers

    International Nuclear Information System (INIS)

    Yoshida, M.; Kumakura, M.; Kaetsu, I.

    1979-01-01

    The effect of cooling rate of a monomeric system on the porosity and activity of an immobilized enzyme prepared by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperatures has been studied. Slow cooling gave the same effect on porosity of the polymer as decreasing the monomer concentration. A glass-forming solvent such as diethylene glycol was added to water to study the effect of the supercooling tendency of the solvent. Addition of diethylene glycol decreased porosity and also enzymic activity. Water was replaced by the miscible solvent p-dioxane and the immiscible solvent n-decane in order to clarify the effect of solvent. p-Dioxane had a similar effect to water on the relation between the monomer concentration, porosity and activity. On the other hand, polymer prepared from the system containing n-decane showed different immobilization properties owing to the presence of independent pores in the matrix. (author)

  7. Effect of cork loading on mechanical and thermal properties of silica-Ethylene-propylene-diene monomer composite

    International Nuclear Information System (INIS)

    Gul, J.; Mirza, S.

    2011-01-01

    Ethylene-propylene diene ter-monomer (EPDM) filled with asbestos are widely used as thermal insulation in space vehicles because of its low specific gravity, low temperature flexibility, high ozone and oxygen resistant, superior thermal and ablation characteristics. However, asbestos has been banned worldwide because of its carcinogenic nature. This study was aimed to replace asbestos by environmental friendly and low specific gravity filler, cork in thermal insulation for space vehicles. Various batches of cork filled EPDM were obtained by compounding 0, 10, 20, 40, 50, 60, 70 and 100 Phr (parts per hundred parts of rubber) of cork powder with EPDM in Two-roll-mill in presence of other necessary compounding ingredients. The resulted vulcanizates were characterized for mechanical, thermal and ablation performances. It was observed that cork loadings significantly enhanced tensile strength and hardness of EPDM. However, elongation at break of EPDM decreased with the increase of cork concentration. Moreover, no significant reduction in density of EPDM was obtained instead of compounding with lower specific gravity cork powder. Temperatures cures in Thermo-gravimetric analysis shifted to lower temperature with increasing of cork percentage in the formulation. Furthermore, char formation of the EPDM composites decreased with the increase of cork Phr in the composition which was the indication of degrading thermal stability of EPDM by cork powders. It can be concluded that on the basis of mechanical properties asbestos can be replaced by cork powder however, cork filled EPDM exhibited inferior thermal properties as compared to asbestos filled EPDM. (author)

  8. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via γ-ray irradiation

    International Nuclear Information System (INIS)

    Chirachanchai, S.; Kumkrong, A.; Ishida, Hatsuo

    2000-01-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3α, 12α -dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by γ-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  9. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via {gamma}-ray irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Chirachanchai, S.; Kumkrong, A. [The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok (Thailand); Ishida, Hatsuo [Department of Macromolecular Science, Case Western Reserve University, Cleveland, OH (United States)

    2000-03-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3{alpha}, 12{alpha} -dihydroxy-5{beta}-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by {gamma}-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  10. Polymerization of unsaturated monomers with radiation in the presence of salts

    International Nuclear Information System (INIS)

    Phalangas, C.J.; Restaino, A.J.; Yun, H.B.

    1977-01-01

    Improved process is claimed for the preparation of water-soluble, substantially linear, high molecular weight polymers, comprising irradiating an aqueous solution of an ethylenically unsaturated monomer and a water-soluble salt under controlled conditions of concentration, radiation intensity, conversion, and total radiation dose. The polymers may be obtained in aqueous gel form or recovered in the form of powder. The polymers are useful as flocculating, thickening, and mobility control agents

  11. Effect of radiation combined with Chinese medicinal monomers on Me180 cells

    International Nuclear Information System (INIS)

    Geng Chuanying; Xu Bo; Li Hongyan; Chen Zhihua; Xia Qisheng; Xu Mei; Liu Xuan; Xiang Qing; Liu Yufeng

    2009-01-01

    Objective: To observe the effect of radiation treatment combined with Chinese medicinal monomers on the proliferation function, telomerase activity, expressions of apoptosis- and proliferation-related genes of Me180 cells. Methods: Me180 cells were cultured in the medium with oleanolic acid, curcumin and allicin. The survival rates of cells were detected by the methods of MTT, the telomerase activity by the method of telomeric repeat amplification protocol (TRAP) and the apoptosis -and proliferation-related genes by the method of reverse transeriptase-PCR. Me180 cells were cultured in the medium with Chinese medicinal monomers, and exposed to X-ray irradiation and the survival rates were detected. Results: The results of MTY showed that survival rates of tumor cells exposed to X rays in combination with oleanolic acid, curcumin and allicin were decreased significantly(t=2.81, 4.16, and 3.42, P<0.05). Chinese medicinal monomers inhibited the telomerase activity of MelS0 cells and the inhibiting function changed with time. At 16 h, the telomerase activities of MelS0 cells administered with oleanolic acid and allicin were reduced markedly (t=5.11 and 5.29, P<0.05). After 48 h, the telomerase activities returned to the normal level. The gene expressions of p21 and p16 in Me180 cells treated with oleanolic acid were 2.43 and 2.78 times higher than the control, respectively, while those of cyclin D1 and CDK4 were 56% and 41% of the control, respectively. Conclusions: Chinese medicinal monomers could effectively kill tumor cells, inhibit the telomerase activity and the expression of proliferation-related genes, and enhance the radiosensitivity of tumor cells. (authors)

  12. Solubility enhancement of dioxins and PCBs by surfactant monomers and micelles quantified with polymer depletion techniques.

    Science.gov (United States)

    Schacht, Veronika J; Grant, Sharon C; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

    2016-06-01

    Partitioning of super-hydrophobic organic contaminants (SHOCs) to dissolved or colloidal materials such as surfactants can alter their behaviour by enhancing apparent aqueous solubility. Relevant partition constants are, however, challenging to quantify with reasonable accuracy. Partition constants to colloidal surfactants can be measured by introducing a polymer (PDMS) as third phase with known PDMS-water partition constant in combination with the mass balance approach. We quantified partition constants of PCBs and PCDDs (log KOW 5.8-8.3) between water and sodium dodecyl sulphate monomers (KMO) and micelles (KMI). A refined, recently introduced swelling-based polymer loading technique allowed highly precise (4.5-10% RSD) and fast (KMO. SHOC losses to experimental surfaces were substantial (8-26%) in monomer solutions, but had a low impact on KMO (0.10-0.16 log units). Log KMO for PCDDs (4.0-5.2) were approximately 2.6 log units lower than respective log KMI, which ranged from 5.2 to 7.0 for PCDDs and 6.6-7.5 for PCBs. The linear relationship between log KMI and log KOW was consistent with more polar and moderately hydrophobic compounds. Apparent solubility increased with increasing hydrophobicity and was highest in micelle solutions. However, this solubility enhancement was also considerable in monomer solutions, up to 200 times for OCDD. Given the pervasive presence of surfactant monomers in typical field scenarios, these data suggest that low surfactant concentrations may be effective long-term facilitators for subsurface transport of SHOCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Enhanced lignin monomer production caused by cinnamic Acid and its hydroxylated derivatives inhibits soybean root growth.

    Directory of Open Access Journals (Sweden)

    Rogério Barbosa Lima

    Full Text Available Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H, guaiacyl (G and syringyl (S monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway in a growth chamber for 24 h. In general, the results showed that 1 cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2 cinnamic and p-coumaric acids increased p-hydroxyphenyl (H monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G content, and sinapic acid increased sinapyl (S content; 3 when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H, cinnamic acid reduced H, G and S contents; and 4 when applied in conjunction with 3,4-(methylenedioxycinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL, p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth.

  14. Interactions between resin monomers and commercial composite resins with human saliva derived esterases.

    Science.gov (United States)

    Jaffer, F; Finer, Y; Santerre, J P

    2002-04-01

    Cholesterol esterase (CE) and pseudocholinesterase (PCE) have been reported to degrade commercial and model composite resins containing bisphenylglycidyl dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA) or the latter in combination with urethane modified BisGMA monomer systems. In addition, human saliva has been shown to contain esterase like activities similar to CE and PCE. Hence, it was the aim of the current study to determine to what extent human saliva could degrade two common commercial composite resins (Z250 from 3M Inc. and Spectrum TPH from L.D. Caulk) which contain the above monomer systems. Saliva samples from different volunteers were collected, processed, pooled, and freeze-dried. TEGDMA and BisGMA monomers were incubated with human saliva derived esterase activity (HSDEA) and their respective hydrolysis was monitored using high performance liquid chromatography (HPLC). Both monomers were completely hydrolyzed within 25 h by HSDEA. Photopolymerized composites were incubated with buffer or human saliva (pH 7.0 and 37 C) for 2, 8 and 16 days. The incubation solutions were analyzed using HPLC and mass spectrometry. Surface morphology characterization was carried out using scanning electron microscopy. Upon biodegradation, the Z250 composite yielded higher amounts of BisGMA and TEGDMA related products relative to the TPH composite. However, there were higher amounts of ethoxylated bis-phenol A released from the TPH material. In terms of total mass of products released, human saliva demonstrated a greater ability to degrade Z250. In summary, HSDEA has been shown to contain esterase activities that can readily catalyze the biodegradation of current commercial composite resins.

  15. Solid-support Electron Paramagnetic Resonance (EPR) Studies of Aβ40 Monomers Reveal a Structured State with Three Ordered Segments*

    Science.gov (United States)

    Gu, Lei; Ngo, Sam; Guo, Zhefeng

    2012-01-01

    Alzheimer disease is associated with the pathological accumulation of amyloid-β peptide (Aβ) in the brain. Soluble Aβ oligomers formed during early aggregation process are believed to be neurotoxins and causative agents in Alzheimer disease. Aβ monomer is the building block for amyloid assemblies. A comprehensive understanding of the structural features of Aβ monomer is crucial for delineating the mechanism of Aβ oligomerization. Here we investigated the structures of Aβ40 monomer using a solid-support approach, in which Aβ40 monomers are tethered on the solid support via an N-terminal His tag to prevent further aggregation. EPR spectra of tethered Aβ40 with spin labels at 18 different positions show that Aβ40 monomers adopt a completely disordered structure under denaturing conditions. Under native conditions, however, EPR spectra suggest that Aβ40 monomers adopt both a disordered state and a structured state. The structured state of Aβ40 monomer has three more ordered segments at 14–18, 29–30, and 38–40. Interactions between these segments may stabilize the structured state, which likely plays an important role in Aβ aggregation. PMID:22277652

  16. Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

    Science.gov (United States)

    Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

    2017-02-15

    Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

  17. Selective extraction of bisphenol A from water by one-monomer molecularly imprinted magnetic nanoparticles.

    Science.gov (United States)

    Lin, Zhenkun; Zhang, Yanfang; Su, Yu; Qi, Jinxia; Jia, Yinhang; Huang, Changjiang; Dong, Qiaoxiang

    2018-01-15

    One-monomer molecularly imprinted magnetic nanoparticles were prepared as adsorbents for selective extraction of bisphenol A from water in this study. A single bi-functional monomer was adopted for preparation of the molecularly imprinted polymer, avoiding the tedious trial-and-error optimizations as traditional strategy. Moreover, bisphenol F was used as the dummy template for bisphenol A to avoid the interference from residual template molecules. These nanoparticles showed not only large adsorption capacity and good selectivity to the bisphenol A but also outstanding magnetic response performance. Furthermore, they were successfully used as magnetic solid-phase extraction adsorbents of bisphenol A from various water samples, including tap water, river water, and seawater. The developed method was found to be much more efficient, convenient, and economical for selective extraction of bisphenol A compared with the traditional solid-phase extraction. Separation of these nanoparticles can be easily achieved with an external magnetic field, and the optimized adsorption time was only 15 min. The recoveries of bisphenol A in different water samples ranged from 85.38 to 93.75%, with relative standard deviation lower than 7.47%. These results showed that one-monomer molecularly imprinted magnetic nanoparticles had the potential to be popular adsorbents for selective extraction of pollutants from water. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Enzyme-catalyzed hydrolysis of dentin adhesives containing a new urethane-based trimethacrylate monomer

    Science.gov (United States)

    Park, Jong-Gu; Ye, Qiang; Topp, Elizabeth M.; Spencer, Paulette

    2009-01-01

    A new trimethacrylate monomer with urethane-linked groups, 1,1,1-tri-[4-(methacryloxyethylamino-carbonyloxy)-phenyl]ethane (MPE), was synthesized, characterized, and used as a co-monomer in dentin adhesives. Dentin adhesives containing 2-hydroxyethyl methacrylate (HEMA, 45% w/w) and 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane (BisGMA, 30% w/w) in addition to MPE (25% w/w) were formulated with H2O at 0 (MPE0), 8 (MPE8) and 16 wt % water (MPE16) to simulate the wet demineralized dentin matrix and compared with controls [HEMA/BisGMA, 45/55 w/w, at 0 (C0), 8 (C8) and 16 wt% water (C16)]. The new adhesive showed a degree of double bond conversion and mechanical properties comparable with control, with good penetration into the dentin surface and a uniform adhesive/dentin interface. On exposure to porcine liver esterase, the net cumulative methacrylic acid (MAA) release from the new adhesives was dramatically (P < 0.05) decreased relative to the control, suggesting that the new monomer improves esterase resistance. PMID:19582843

  19. Jellium-model calculation for monomer and dimer decays of some potassium clusters

    International Nuclear Information System (INIS)

    Saito, Susumu; Cohen, M.L.; Lawrence Berkeley Lab., CA

    1989-01-01

    We have studied several decay processes of potassium clusters and found that a dimer-decay mechanism can explain the observed lowest abundance of K 10 in the K n mass spectra. Total-energy curves for decay processes are calculated using a jellium-background model for positive-ion cores and the local-spin-density-functional approximation for valence electrons. The energy-barrier height for a dimer decay of K 10 from the energy-minimum point is found to be 0.18 eV, which is a reasonable magnitude for the decay to take place thermally in the experiment. The monomer decay of K 9 and the dimer decay of K 11 , which are expected to be the most favorable decays of K 9 and K 11 , are found to have high barriers. Monomer and dimer decays of K 8 are also studied and the monomer decay is found to be more favorable, in accord with the high-nozzle-temperature mass spectrum. (orig.)

  20. Modification of polyethersulfone films by grafting hydrophilic monomers with 60Co γ-rays

    International Nuclear Information System (INIS)

    Hou Zhengchi; Deng Bo; Li Jing

    2006-01-01

    Polyethersulfone (PES), with its high strength, high temperature resistance, corrosion- resistance, oxidation resistance and applicability under wide pH range, is used extensively as ultrafiltration and nanofiltration membrane. However, PES membranes foul easily in such an application because of hydrophobic nature of PES raw materials. Improving the hydrophilicity of PES by grafting hydrophilic monomers onto it is of potential to solve the problem. At present, common approaches to improve hydrophilicity of PES membranes are UV grafting modification, plasma modification, and chemical modification, whereas grafting and modifying PES films by 60 Co γ-rays has rarely been reported. Studies have been carried out in our laboratory to graft hydrophilic monomers onto PES membranes directly or PES powders via simultaneous radiation grafting with the rays. Acrylic acid, methyl acrylic acid or acrylamide was used to study effects of the monomer concentration, irradiation dose and dose rate, solvent, inhibitor and pH of the grafting solution on the degree of grafting. The results showed that hydrophilicity of all the PES membranes could be improved, with the extent of improvement being dependent on the grafting conditions. (authors)

  1. NGAL (Lcn2) monomer is associated with tubulointerstitial damage in chronic kidney disease.

    Science.gov (United States)

    Nickolas, Thomas L; Forster, Catherine S; Sise, Meghan E; Barasch, Nicholas; Solá-Del Valle, David; Viltard, Melanie; Buchen, Charles; Kupferman, Shlomo; Carnevali, Maria Luisa; Bennett, Michael; Mattei, Silvia; Bovino, Achiropita; Argentiero, Lucia; Magnano, Andrea; Devarajan, Prasad; Mori, Kiyoshi; Erdjument-Bromage, Hediye; Tempst, Paul; Allegri, Landino; Barasch, Jonathan

    2012-09-01

    The type and the extent of tissue damage inform the prognosis of chronic kidney disease (CKD), but kidney biopsy is not a routine test. Urinary tests that correlate with specific histological findings might serve as surrogates for the kidney biopsy. We used immunoblots and ARCHITECT-NGAL assays to define the immunoreactivity of urinary neutrophil gelatinase-associated lipocalin (NGAL) in CKD, and we used mass spectroscopy to identify associated proteins. We analyzed kidney biopsies to determine whether specific pathological characteristics associated with the monomeric NGAL species. Advanced CKD urine contained the NGAL monomer as well as novel complexes of NGAL. When these species were separated, we found a significant correlation between the NGAL monomer and glomerular filtration rate (r=-0.53, P<0.001), interstitial fibrosis (mild vs. severe disease; mean 54 vs. 167 μg uNGAL/g Cr, P<0.01), and tubular atrophy (mild vs. severe disease; mean 54 vs. 164 μg uNGAL/g Cr, P<0.01). Monospecific assays of the NGAL monomer demonstrated a correlation with histology that typifies progressive, severe CKD.

  2. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

    International Nuclear Information System (INIS)

    Abdel-Fattah, A.A.; Abdel-Rehim, F.; Soliman, Y.S.

    2012-01-01

    The dosimetric characteristics of γ-radiation sensitive labels based on polyvinyl butyral (PVB) and a conjugated diacetylene monomer, 10,12-pentacosa-diynoic acid (PCDA) have been investigated using reflectance colorimeter. Two types of labels (colourless and yellow) based on PCDA monomer were prepared using an Automatic Film Applicator System. Upon γ-ray exposure, the colourless label turns progressively blue, while the yellow colour label turns to green then to dark blue. The colour intensity of the labels is proportional to the radiation absorbed dose. The useful dose range was 15 Gy-2 kGy depending on PCDA monomer concentration. The expanded uncertainty of dose measurement of the colourless label was 6.06 (2σ). - Highlights: → Using 10,12-pentacosa-diynoic acid (PCDA) in preparation of label dosimeter. → PCDA polymerises upon γ-rays exposure producing a blue coloured polymer. → Useful dose range is 15 Gy to 2 kGy depending on concentration of PCDA. → Overall uncertainty of label dosimeter was 6.06 at 2σ.

  3. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Fattah, A.A.; Abdel-Rehim, F. [National Center for Radiation Research and Technology, Atomic Energy Authority, P.O. Box 8029, Nasr City, Cairo (Egypt); Soliman, Y.S., E-mail: yasser_shabaan@hotmail.com [National Center for Radiation Research and Technology, Atomic Energy Authority, P.O. Box 8029, Nasr City, Cairo (Egypt)

    2012-01-15

    The dosimetric characteristics of {gamma}-radiation sensitive labels based on polyvinyl butyral (PVB) and a conjugated diacetylene monomer, 10,12-pentacosa-diynoic acid (PCDA) have been investigated using reflectance colorimeter. Two types of labels (colourless and yellow) based on PCDA monomer were prepared using an Automatic Film Applicator System. Upon {gamma}-ray exposure, the colourless label turns progressively blue, while the yellow colour label turns to green then to dark blue. The colour intensity of the labels is proportional to the radiation absorbed dose. The useful dose range was 15 Gy-2 kGy depending on PCDA monomer concentration. The expanded uncertainty of dose measurement of the colourless label was 6.06 (2{sigma}). - Highlights: > Using 10,12-pentacosa-diynoic acid (PCDA) in preparation of label dosimeter. > PCDA polymerises upon {gamma}-rays exposure producing a blue coloured polymer. > Useful dose range is 15 Gy to 2 kGy depending on concentration of PCDA. > Overall uncertainty of label dosimeter was 6.06 at 2{sigma}.

  4. Kinetic behaviour of graft copolymerisation of nitrogenous heterocyclic monomer onto EB-irradiated ETFE films

    International Nuclear Information System (INIS)

    Paveswari Sithambaranathan; Arshad Ahmad; Mohamed Mahmoud Nasef; Universiti Teknologi Malaysia Campus, Kuala Lumpur

    2015-01-01

    Kinetic behaviour of graft copolymerisation of a nitrogenous heterocyclic monomer, 4-vinylpyridine (4-VP), onto electron beam irradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) films was investigated in correlation with reaction parameters (absorbed dose, monomer concentration and reaction temperature). This was established by determination of initial polymerisation rate (r p0 ), characteristic radical recombination rate (γ) and delay time (t 0 ). The orders of the dependence of the initial rate of grafting on the absorbed dose and monomer concentration were found to be 2.28 and 3.49, respectively. The effect of temperature was investigated in the range of 50-70 deg C and the activation energy was determined. The incorporation of poly(4-VP) grafts and the accompanied chemical changes in the grafted ETFE films were monitored using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The results of the present study showed that a quantitative kinetic description for grafting of 4-VP onto ETFE can be established and the degree of grafting can be tuned by controlling the reaction parameters. (author)

  5. Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

    Science.gov (United States)

    Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

    2016-05-17

    As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

  6. Permeability of different types of medical protective gloves to acrylic monomers.

    Science.gov (United States)

    Lönnroth, Emma-Christin; Wellendorf, Hanne; Ruyter, Eystein

    2003-10-01

    Dental personnel and orthopedic surgeons are at risk when manually handling products containing methyl methacrylate (MMA). Dental products may also contain cross-linking agents such as ethylene glycol dimethacrylate (EGDMA) or 1,4-butanediol dimethacrylate (1,4-BDMA). Skin contact with monomers can cause hand eczema, and the protection given by gloves manufactured from different types of material is not well known. The aim of this study was to determine the breakthrough time (BTT, min) as a measure of protection (according to the EU standard EN-374-3) for a mixture consisting of MMA, EGDMA and 1,4-BDMA. Fifteen different gloves representing natural rubber latex material, synthetic rubber material (e.g. nitrile rubbers), and synthetic polymer material were tested. The smallest monomer MMA permeated within 3 min through all glove materials. A polyethylene examination glove provided the longest protection period to EGDMA and 1, 4-BDMA (> 120 min and 25.0 min), followed by the surgical glove Tactylon (6.0 min and 8.7 min) and the nitrile glove Nitra Touch (5.0 min and 8.7 min). This study showed that the breakthrough time (based on permeation rate) cannot be regarded as a 'safe limit'. When the permeation rate is low, monomers may have permeated before BTT can be determined. Using double gloves with a synthetic rubber inner glove and a natural rubber outer glove provided longer protection when the inner glove was rinsed in water before placing the outer glove on top.

  7. 1 / n Expansion for the Number of Matchings on Regular Graphs and Monomer-Dimer Entropy

    Science.gov (United States)

    Pernici, Mario

    2017-08-01

    Using a 1 / n expansion, that is an expansion in descending powers of n, for the number of matchings in regular graphs with 2 n vertices, we study the monomer-dimer entropy for two classes of graphs. We study the difference between the extensive monomer-dimer entropy of a random r-regular graph G (bipartite or not) with 2 n vertices and the average extensive entropy of r-regular graphs with 2 n vertices, in the limit n → ∞. We find a series expansion for it in the numbers of cycles; with probability 1 it converges for dimer density p diverges as |ln(1-p)| for p → 1. In the case of regular lattices, we similarly expand the difference between the specific monomer-dimer entropy on a lattice and the one on the Bethe lattice; we write down its Taylor expansion in powers of p through the order 10, expressed in terms of the number of totally reducible walks which are not tree-like. We prove through order 6 that its expansion coefficients in powers of p are non-negative.

  8. Improved i-motif thermal stability by insertion of anthraquinone monomers

    DEFF Research Database (Denmark)

    Gouda, Alaa S; Amine, Mahasen S.; Pedersen, Erik Bjerregaard

    2017-01-01

    In order to gain insight into how to improve thermal stability of i-motifs when used in the context of biomedical and nanotechnological applications, novel anthraquinone-modified i-motifs were synthesized by insertion of 1,8-, 1,4-, 1,5- and 2,6-disubstituted anthraquinone monomers into the TAA...... loops of a 22mer cytosine-rich human telomeric DNA sequence. The influence of the four anthraquinone linkers on the i-motif thermal stability was investigated at 295 nm and pH 5.5. Anthraquinone monomers modulate the i-motif stability in a position-depending manner and the modulation also depends...... unlocked nucleic acid monomers or twisted intercalating nucleic acid. The 2,6-disubstituted anthraquinone linker replacing T10 enabled a significant increase of i-motif thermal melting by 8.2 °C. A substantial increase of 5.0 °C in i-motif thermal melting was recorded when both A6 and T16 were modified...

  9. Effect of reactive monomer on PS-b-P2VP film.

    Science.gov (United States)

    Kim, H J; Shin, D M

    2014-08-01

    Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 52 kg/mol-b-57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic moiety of PS-b-P2VP, were obtained by exposing the spin coated film under chloroform vapor. The lamellar films were quaternized with 5 wt% of iodomethane diluted by n-hexane. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. As a result the photonic gel film with RM had more clear color. The lamellar films were swollen by DI water, ethanol (aq) and calcium carbonate solution. The band gaps of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution. And the lamellar films were shifted to shorter wave length swollen by ethanol. So each lamellar film showed different color.

  10. Copolymerization parameters of N-Methacryloyloxy tetrabromophthalimide with different vinyl monomers

    International Nuclear Information System (INIS)

    Mahmoud, A.A.

    2005-01-01

    N-Methacryloyloxytetrabromophthalimide (NMTP) was synthesized by the reaction of N-hydroxytetrabromophthalimide with either methacryloyl chloride or methacrylic acid in the presence of triethylamine or N, Ndicyclohexylcarbodiimide respectively. Binary copolymerization reactions of the prepared monomer with ethyl acrylate (EA), n-butyl methacrylate (n.BMA), tertiary butylacrylate (t.BA) and vinyl acetate (VA) were performed in methylene chloride at 65 degree C using 1 mol % azobisisobutylronitrile (AIBN) as initiator. The structure of the prepared monomer was investigated by IR and 1H NMR spectroscopy. The copolymer compositions were determined from bromine analysis. Copolymerization parameters for each system were calculated by the Fineman-Ross and Kelen-Tudos methods. The monomer reactivity ratios for the systems NMTP-EA, NMTP-n.BMA, NMTP-t.BA and NMTP-VA were found to be r1 0.180, r2 = 0.893, r1 = 0.025, r2 = 0.680, r1 0.014, r2 0.956 and r1 1.002, r2 1.004 respectively

  11. Two Functionally Distinct Sources of Actin Monomers Supply the Leading Edge of Lamellipodia

    Science.gov (United States)

    Vitriol, Eric A.; McMillen, Laura M.; Kapustina, Maryna; Gomez, Shawn M.; Vavylonis, Dimitrios; Zheng, James Q.

    2015-01-01

    Summary Lamellipodia, the sheet-like protrusions of motile cells, consist of networks of actin filaments (F-actin) regulated by the ordered assembly from and disassembly into actin monomers (G-actin). Traditionally, G-actin is thought to exist as a homogeneous pool. Here, we show that there are two functionally and molecularly distinct sources of G-actin that supply lamellipodial actin networks. G-actin originating from the cytosolic pool requires the monomer binding protein thymosin β4 (Tβ4) for optimal leading edge localization, is targeted to formins, and is responsible for creating an elevated G/F-actin ratio that promotes membrane protrusion. The second source of G-actin comes from recycled lamellipodia F-actin. Recycling occurs independently of Tβ4 and appears to regulate lamellipodia homeostasis. Tβ4-bound G-actin specifically localizes to the leading edge because it doesn’t interact with Arp2/3-mediated polymerization sites found throughout the lamellipodia. These findings demonstrate that actin networks can be constructed from multiple sources of monomers with discrete spatiotemporal functions. PMID:25865895

  12. Effect of polyfunctional monomers on properties of radiation crosslinked EPDM/waste tire dust blend

    International Nuclear Information System (INIS)

    Yasin, Tariq; Khan, Sajid; Nho, Young-Chang; Ahmad, Rashid

    2012-01-01

    In this study, waste tire dust is recycled as filler and blended with ethylene-propylene diene monomer (EPDM) rubber. Three different polyfuntional monomers (PFMs) are incorporated into the standard formulation and irradiated under electron beam at different doses up to maximum of 100 kGy. The combined effects of PFMs and absorbed dose on the physical properties of EPDM/WTD blend are measured and compared with sulfur crosslinked formulation. Thermogravimetric analysis showed that radiation developed better crosslinked network with higher thermal stability than sulfur crosslinked structure. The physical properties of radiation crosslinked blend are similar to the sulfur crosslinked blend. The absence of toxic chemicals/additives in radiation crosslinked blends made them an ideal candidate for many applications such as roof sealing sheets, water retention pond, playground mat, sealing profile for windows etc. - Highlights: ► We have recycled waste tire dust and blended it with EPDM. ► EB crosslinking is carried in the presence of polyfuntional monomers. ► Radiation gave better network with higher thermal stability than sulfur. ► The absence of toxic chemicals in EB blends will increase its acceptability.

  13. Radiation Vulcanization of Polymeric Blends Based on Ethylene Propylene Diene Monomer Rubber/ Waste Materials in Presence of Different Additives

    International Nuclear Information System (INIS)

    MOHAMED, R.M.

    2015-01-01

    as an enhancing polyfunctional monomer, i.e. co-agent Properties obtained showed further improvement due to its participation in gel formation.

  14. Bioaccumulation study of acrylate monomers in algae (Chlorella Kessleri) by PY-GC and PY-GC/MS

    International Nuclear Information System (INIS)

    Halas, L.; Orinak, A.; Adamova, M.; Ladomersky, J.

    2004-01-01

    Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the paralytic cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2 -, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied. (authors)

  15. Simple introduction of sulfonic acid group onto polyethylene by radiation-induced cografting of sodium styrenesulfonate with hydrophilic monomers

    International Nuclear Information System (INIS)

    Tsuneda, Satoshi; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Makuuchi, Keizo

    1993-01-01

    The sulfonic acid (SO 3 H) group was readily introduced into a polyethylene (PE) membrane by radiation-induced cografting of sodium styrenesulfonate (SSS) with hydrophilic monomers such as acrylic acid (AAc) and hydroxyethyl methacrylate (HEMA). The density of SSS grafted onto the PE membrane was determined as a function of molar ratio of hydrophilic monomer to SSS in the monomer mixture. Immersion of the electron-beam-irradiated PE membrane into the mixture of SSS and HEMA for 5 h at 323 K provided to the SO 3 H density of 2.5 mol/kg of the H-type product

  16. A DFT based analysis of adsorption of Hg2+ ion on chitosan monomer and its citralidene and salicylidene derivatives: Prior to the removal of Hg toxicity.

    Science.gov (United States)

    Hassan, Basila; Rajan, Vijisha K; Mujeeb, V M Abdul; K, Muraleedharan

    2017-06-01

    A Density functional theory based study of adsorption of the toxic metal Hg (II) ion by chitosan monomer and two of its derivatives; citralidene and salicylidene chitosan, has been performed. The effect of structural features on the stability of studied complexes has been analyzed by using Gaussian03 software package. All the possible conformations of these adsorbents were studied using the global minimum geometries. All the adsorbing sites were studied by placing the metal ion on the centroid of the atoms and the stable conformer of the adsorbent-metal ion complex was identified. Interaction between Hg (II) and the adsorbents is found to be electrostatic. Metal ion binding with nitrogen atom is stronger than that with oxygen atoms in all the cases as the charge density of nitrogen is enhanced on Schiff base formation. The advantage of derivatives over chitosan monomer is their stability in acidic media. ΔE value of the complexes are in the order SC-Hg (II)>chitosan-Hg (II)>CC-Hg (II) which indicates that the stability of complexes increases with increase in energy gap. The study reveals that aromatic Schiff base derivatives of chitosan is better for Hg(II) intake than aliphatic derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Mechanism for Controlling the Dimer-Monomer Switch and Coupling Dimerization to Catalysis of the Severe Acute Respiratory Syndrome Coronavirus 3C-Like Protease

    Energy Technology Data Exchange (ETDEWEB)

    Shi,J.; Sivaraman, J.; Song, J.

    2008-01-01

    Unlike 3C protease, the severe acute respiratory syndrome coronavirus (SARS-CoV) 3C-like protease (3CLpro) is only enzymatically active as a homodimer and its catalysis is under extensive regulation by the unique extra domain. Despite intense studies, two puzzles still remain: (i) how the dimer-monomer switch is controlled and (ii) why dimerization is absolutely required for catalysis. Here we report the monomeric crystal structure of the SARS-CoV 3CLpro mutant R298A at a resolution of 1.75 Angstroms . Detailed analysis reveals that Arg298 serves as a key component for maintaining dimerization, and consequently, its mutation will trigger a cooperative switch from a dimer to a monomer. The monomeric enzyme is irreversibly inactivated because its catalytic machinery is frozen in the collapsed state, characteristic of the formation of a short 310-helix from an active-site loop. Remarkably, dimerization appears to be coupled to catalysis in 3CLpro through the use of overlapped residues for two networks, one for dimerization and another for the catalysis.

  18. Effect of monomer concentration on the kinetics of emulsifier-free emulsion polymerization of Vinyl Acetate and Methyl Acrylate

    International Nuclear Information System (INIS)

    Mohammad Beigi, H. R.

    2001-01-01

    The effect of monomer concentration on the kinetics of the emulsifier-free emulsion polymerization of vinyl acetate and methyl acrylate were studied. The polymerizations were carried out using potassium persulfate as the initiator. Form the electron micrographs of the resulting lattices, monodisperse PVAc and PMA lattices with particle diameters varying between 149-443 mm and 112-497 nm, respectively were processed. Uniformity of particle size indicated that nucleation of stable particle occurs early in the polymerization process. The polymerization rate was found to be proportional to the 0.88 and 1.5 power of the initial monomer concentration of vinyl acetate and methyl acrylate, respectively. Higher monomer concentration results in fewer particles and larger final particle diameter. With increasing monomer solubility in water the size of particle decreases and its distribution broadens

  19. Fluorescent oligonucleotides containing a novel perylene 2′-amino-α-L-LNA monomer: Synthesis and analytical potential

    DEFF Research Database (Denmark)

    Astakhova, Irina; Kumar, Santhosh T.; Wengel, Jesper

    2011-01-01

    efficiency of the resulting perylene-2'-amino-alpha-L-LNA monomer (T*) into synthetic oligonucleotides was significantly improved by replacement of the typically used 1H-tetrazole activator with pyridine hydrochloride. Generally, oligonucleotides containing monomer T* showed high binding affinity towards...... incorporations of monomers T* was quenched (quantum yield Phi(F) = 0.21) relative to duplexes of this probe with complementary DNA and RNA (Phi(F) = 0.42 and 0.35, respectively). On the contrary, a strong fluorescence quenching upon target binding was demonstrated by two short oligonucleotides of analogues...... sequences containing monomers T* at 5'- and 3'-terminal positions. We explain the hybridization-induced light-up effect observed for double-labeled probe by a reduction of fluorescence quenching due to precise positioning of the fluorophores within the double-stranded complexes. Furthermore, we propose...

  20. Conformationally locked aryl C-nucleosides: synthesis of phosphoramidite monomers and incorporation into single-stranded DNA and LNA (locked nucleic acid)

    DEFF Research Database (Denmark)

    Babu, B. Ravindra; Prasad, Ashok K.; Trikha, Smriti

    2002-01-01

    . The phosphoramidite approach was used for automated incorporation of the LNA-type beta-configured C-aryl monomers 17a-17e into short DNA and 2'-OMe-RNA/LNA strands. It is shown that universal hybridization can be obtained with a conformationally restricted monomer as demonstrated most convincingly for the pyrene LNA...... monomer 17d, both in a DNA context and in an RNA-like context. Increased binding affinity of oligonucleotide probes for universal hybridization can be induced by combining the pyrene LNA monomer 17d with affinity-enhancing 2'-OMe-RNA/LNA monomers....

  1. Computational Modeling and Theoretical Calculations on the Interactions between Spermidine and Functional Monomer (Methacrylic Acid in a Molecularly Imprinted Polymer

    Directory of Open Access Journals (Sweden)

    Yujie Huang

    2015-01-01

    Full Text Available This paper theoretically investigates interactions between a template and functional monomer required for synthesizing an efficient molecularly imprinted polymer (MIP. We employed density functional theory (DFT to compute geometry, single-point energy, and binding energy (ΔE of an MIP system, where spermidine (SPD and methacrylic acid (MAA were selected as template and functional monomer, respectively. The geometry was calculated by using B3LYP method with 6-31+(d basis set. Furthermore, 6-311++(d, p basis set was used to compute the single-point energy of the above geometry. The optimized geometries at different template to functional monomer molar ratios, mode of bonding between template and functional monomer, changes in charge on natural bond orbital (NBO, and binding energy were analyzed. The simulation results show that SPD and MAA form a stable complex via hydrogen bonding. At 1 : 5 SPD to MAA ratio, the binding energy is minimum, while the amount of transferred charge between the molecules is maximum; SPD and MAA form a stable complex at 1 : 5 molar ratio through six hydrogen bonds. Optimizing structure of template-functional monomer complex, through computational modeling prior synthesis, significantly contributes towards choosing a suitable pair of template-functional monomer that yields an efficient MIP with high specificity and selectivity.

  2. Effect of Laser-assisted and Conventional In-office Bleaching on Monomer Release from Microhybrid and Nanohybrid Composite.

    Science.gov (United States)

    Omrani, Ladan Ranjbar; Farjadfar, Shayan; Pedram, Parham; Sadray, Sima; Kamangar, Sedighe Sadat Hashemi; Chiniforoush, Nasim

    2017-06-30

    Bleaching might affect structural properties of composite materials, and lead to monomer release. This study aimed to evaluate the effect of Laser-assisted and conventional in-office bleaching on the release of BIS-GMA, TEGDMA, and UDMA monomers from a nanohybrid and a microhybrid BIS-GMA based composite. 32 samples of each composite, were divided into 4 subgroups; subgroup 1: Conventional in-office bleaching (CIB) with the Opalescence Boost PF 38% gel, subgroup 2: Laser-assisted bleaching (LBO) with the Opalescence Boost PF 38% gel, subgroup 3: Laser-assisted bleaching (LBH) with the JW Power bleaching gel, subgroup 4: (CO) control without bleaching. All the samples were immersed in tubes of 2cc Ethanol 75% medium. The released monomers were analyzed using the high performance liquid chromatography (HPLC) method 24 h, 7, and 28 days. Data's were analyzed by Univariate Analysis of Variance test followed by Tukeys HSD. The amount of TEGDMA monomer released was not significant. However, nanohybrid composites showed significantly more monomer release than microhybrid composites (P Bleaching by laser with JW Power Bleaching gel led to more monomer release in nanohybrid composite.

  3. An all-aromatic polypyridine: Monomer and polymer synthesis; Film formation and crosslinking; A candidate fuel cell membrane

    Science.gov (United States)

    Sikkema, Doetze J.; Versteegen, Ron M.; Pouderoijen, Maarten J.; Janssen, Henk M.; Boere, Ben; Brands, Ferry; Kemperman, GerJan; Rewinkel, Jos B. M.; Koeman, Menno

    2018-03-01

    2,6-di (3-pyridyl)phenol and the title polymer are synthesized at 1 kg scale. Polymer is processed and crosslinked without the introduction of non-aromatic moieties after shaping into membranes. Attractive proton conduction, at high temperature (140-180 °C: 300 mS cm-1) and at room temperature (60 mS cm-1) are recorded in the dry state (higher numbers at modest humidity) and excellent retention of properties after challenge by humidity (in contrast with state-of-the-art PBI membranes). Functional fuel cells are made and tested. In prolonged use the membrane is plasticized and this seems attributable to curing reversal at the hydrogen electrode. For high temperature fuel cell use, another curing scheme (again without the introduction of aliphatic character) must be found.

  4. Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hua [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China); Wang Mozhen [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail: pstwmz@ustc.edu.cn; Ge Xuewu [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China (USTC), Hefei, Anhui 230026 (China)], E-mail: xwge@ustc.edu.cn

    2009-02-15

    Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 deg. C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by {gamma}-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer (G{sub PU/monomer}) was calculated from {sup 1}H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. G{sub PU/monomer} varied as G{sub PU/styrene}(37%)>G{sub PU/butyl} {sub acrylate} {sub (BA)}(21%)>G{sub PU/methyl} {sub methacrylate} {sub (MMA)}(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.

  5. A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

    Science.gov (United States)

    Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

    2018-03-26

    The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Fabrication of Surface Protein-Imprinted Nanoparticles Using a Metal Chelating Monomer via Aqueous Precipitation Polymerization.

    Science.gov (United States)

    Li, Wei; Sun, Yan; Yang, Chongchong; Yan, Xianming; Guo, Hao; Fu, Guoqi

    2015-12-16

    Molecular imprinting is a promising way for constructing artificial protein recognition materials, but it has been challenged by difficulties such as restricted biomacromolecule transfer in the cross-linked polymer networks, and reduced template-monomer interactions that are due to the required aqueous media. Herein, we propose a strategy for imprinting of histidine (His)-exposed proteins by combining previous approaches such as surface imprinting over nanostructures, utilization of metal coordination interactions, and adoption of aqueous precipitation polymerization capable of forming reversible physical crosslinks. With lysozyme as a model template bearing His residues, imprinted polymer nanoshells were grafted over vinyl-modified nanoparticles by aqueous precipitation copolymerization of a Cu(2+) chelating monomer with a temperature-responsive monomer carried out at 37 °C, above the volume phase-transition temperature (VPTT) of the final copolymer. The imprinted nanoshells showed significant temperature sensitivity and the template removal could be facilitated by swelling of the imprinted layers at 4 °C, below the VPTT. The resultant core-shell imprinted nanoparticles exhibited strikingly high rebinding selectivity against a variety of nontemplate proteins. An imprinting factor up to 22.7 was achieved, which is among the best values reported for protein imprinting, and a rather high specific binding capacity of 67.3 mg/g was obtained. Moreover, this approach was successfully extended to preliminary imprinting of hemoglobin, another protein with accessible His. Therefore, it may be a versatile method for fabrication of high-performance surface-imprinted nanoparticles toward His-exposed proteins.

  7. High-resolution structure of a retroviral protease folded as a monomer

    International Nuclear Information System (INIS)

    Gilski, Miroslaw; Kazmierczyk, Maciej; Krzywda, Szymon; Zábranská, Helena; Cooper, Seth; Popović, Zoran; Khatib, Firas; DiMaio, Frank; Thompson, James; Baker, David; Pichová, Iva; Jaskolski, Mariusz

    2011-01-01

    The crystal structure of Mason–Pfizer monkey virus protease folded as a monomer has been solved by molecular replacement using a model generated by players of the online game Foldit. The structure shows at high resolution the details of a retroviral protease folded as a monomer which can guide rational design of protease dimerization inhibitors as retroviral drugs. Mason–Pfizer monkey virus (M-PMV), a D-type retrovirus assembling in the cytoplasm, causes simian acquired immunodeficiency syndrome (SAIDS) in rhesus monkeys. Its pepsin-like aspartic protease (retropepsin) is an integral part of the expressed retroviral polyproteins. As in all retroviral life cycles, release and dimerization of the protease (PR) is strictly required for polyprotein processing and virion maturation. Biophysical and NMR studies have indicated that in the absence of substrates or inhibitors M-PMV PR should fold into a stable monomer, but the crystal structure of this protein could not be solved by molecular replacement despite countless attempts. Ultimately, a solution was obtained in mr-rosetta using a model constructed by players of the online protein-folding game Foldit. The structure indeed shows a monomeric protein, with the N- and C-termini completely disordered. On the other hand, the flap loop, which normally gates access to the active site of homodimeric retropepsins, is clearly traceable in the electron density. The flap has an unusual curled shape and a different orientation from both the open and closed states known from dimeric retropepsins. The overall fold of the protein follows the retropepsin canon, but the C α deviations are large and the active-site ‘DTG’ loop (here NTG) deviates up to 2.7 Å from the standard conformation. This structure of a monomeric retropepsin determined at high resolution (1.6 Å) provides important extra information for the design of dimerization inhibitors that might be developed as drugs for the treatment of retroviral infections

  8. Prediction of monomer isomery in Florine: a workflow dedicated to nonribosomal peptide discovery.

    Directory of Open Access Journals (Sweden)

    Thibault Caradec

    Full Text Available Nonribosomal peptides represent a large variety of natural active compounds produced by microorganisms. Due to their specific biosynthesis pathway through large assembly lines called NonRibosomal Peptide Synthetases (NRPSs, they often display complex structures with cycles and branches. Moreover they often contain non proteogenic or modified monomers, such as the D-monomers produced by epimerization. We investigate here some sequence specificities of the condensation (C and epimerization (E domains of NRPS that can be used to predict the possible isomeric state (D or L of each monomer in a putative peptide. We show that C- and E- domains can be divided into 2 sub-regions called Up-Seq and Down-Seq. The Up-Seq region corresponds to an InterPro domain (IPR001242 and is shared by C- and E-domains. The Down-Seq region is specific to the enzymatic activity of the domain. Amino-acid signatures (represented as sequence logos previously described for complete C-and E-domains have been restricted to the Down-Seq region and amplified thanks to additional sequences. Moreover a new Down-Seq signature has been found for Ct-domains found in fungi and responsible for terminal cyclization of the peptides. The identification of these signatures has been included in a workflow named Florine, aimed to predict nonribosomal peptides from NRPS sequence analyses. In some cases, the prediction of isomery is guided by genus-specific rules. Florine was used on a Pseudomonas genome to allow the determination of the type of pyoverdin produced, the update of syringafactin structure and the identification of novel putative products.

  9. A model study of aggregates composed of spherical soot monomers with an acentric carbon shell

    Science.gov (United States)

    Luo, Jie; Zhang, Yongming; Zhang, Qixing

    2018-01-01

    Influences of morphology on the optical properties of soot particles have gained increasing attentions. However, studies on the effect of the way primary particles are coated on the optical properties is few. Aimed to understand how the primary particles are coated affect the optical properties of soot particles, the coated soot particle was simulated using the acentric core-shell monomers model (ACM), which was generated by randomly moving the cores of concentric core-shell monomers (CCM) model. Single scattering properties of the CCM model with identical fractal parameters were calculated 50 times at first to evaluate the optical diversities of different realizations of fractal aggregates with identical parameters. The results show that optical diversities of different realizations for fractal aggregates with identical parameters cannot be eliminated by averaging over ten random realizations. To preserve the fractal characteristics, 10 realizations of each model were generated based on the identical 10 parent fractal aggregates, and then the results were averaged over each 10 realizations, respectively. The single scattering properties of all models were calculated using the numerically exact multiple-sphere T-matrix (MSTM) method. It is found that the single scattering properties of randomly coated soot particles calculated using the ACM model are extremely close to those using CCM model and homogeneous aggregate (HA) model using Maxwell-Garnett effective medium theory. Our results are different from previous studies. The reason may be that the differences in previous studies were caused by fractal characteristics but not models. Our findings indicate that how the individual primary particles are coated has little effect on the single scattering properties of soot particles with acentric core-shell monomers. This work provides a suggestion for scattering model simplification and model selection.

  10. Pseudomonas syringae evades host Immunity by degrading flagellin monomers with alkaline protease AprA

    OpenAIRE

    Pel, M.J.C.; Van Dijken, A.J.H.; Bardoel, B.W.; Seidl, M.F; Van der Ent, S.; Van Strijp, J.A.G.

    2014-01-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant athogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantl...

  11. Inverse problem for the mean-field monomer-dimer model with attractive interaction

    International Nuclear Information System (INIS)

    Contucci, Pierluigi; Luzi, Rachele; Vernia, Cecilia

    2017-01-01

    The inverse problem method is tested for a class of monomer-dimer statistical mechanics models that contain also an attractive potential and display a mean-field critical point at a boundary of a coexistence line. The inversion is obtained by analytically identifying the parameters in terms of the correlation functions and via the maximum-likelihood method. The precision is tested in the whole phase space and, when close to the coexistence line, the algorithm is used together with a clustering method to take care of the underlying possible ambiguity of the inversion. (paper)

  12. Migration of formaldehyde and melamine monomers from kitchen- and tableware made of melamine plastic

    DEFF Research Database (Denmark)

    Lund, K.H.; Petersen, J.H.

    2006-01-01

    Migration of one or both formaldehyde and/or melamine monomers was found in seven of ten tested melamine samples bought on the Danish market. The samples were a bowl, a jug, a mug, a ladle, and different cups and plates. No violation of the European Union-specific migration limits for melamine (30...... mg kg(-1)) and formaldehyde (15 mg kg(-1)) was found after three successive exposures to the food stimulant 3% acetic acid after 2 h at 70 degrees C. To investigate the effects of long-term use, migration tests were performed with two types of cups from a day nursery. Furthermore, medium-term use...

  13. Radiation induced grafting of monomers onto natural rubber : processes and applications

    International Nuclear Information System (INIS)

    Sunny Sebastian, M.

    2001-01-01

    Full text: Certain inherent mechanical properties of natural rubber (NR) can be modified by grafting vinyl monomers onto the polymer backbone. This paper described the gamma radiation induced graft copolymerization of methyl methacrylate (MMA), styrene and acrylonitrile (AN) onto NR. The graft copolymers can be crosslinked by sulphur and organic accelerators. The crosslinked graft copolymers show improved modulus and hardness in their films compared to NR. However the tensile strength of the films is reduced by grafting. The methods for preparing the graft copolymers, their properties and applications are briefly described

  14. Radiation grafting from binary monomer mixtures. II. Vinyl ether of monoethanolamine and N-vinylpyrrolidone

    International Nuclear Information System (INIS)

    Nurkeeva, Zauresh S.; Abdel Aal, A.-S.; Kupchishin, Anatoliy I.; Khutoryanskiy, Vitaliy V.; Mun, Grigoriy A.; Beksyrgaeva, Aida G.

    2003-01-01

    Radiation grafting from binary monomer mixtures of vinyl ether of monoethanolamine and N-vinylpyrrolidone onto polyethylene films has been studied. The structure of the grafted films was characterized by FTIR spectroscopy. Water uptake and contact angle measurements confirmed that the grafting leads to a considerable hydrophilization of the films surface. The presence of the more active N-vinylpyrrolidone enhances the grafting of the less active vinyl ether of monoethanolamine. Sorption properties of grafted films with respect to copper (II) ions have been studied

  15. INS as a probe of inter-monomer angles in polymers

    CERN Document Server

    Eijck, L V; Grozema, F C; Schepper, I M D; Kearley, G J

    2002-01-01

    The angle between monomers in conjugated polymers plays an important role in their conductivity. The vibrational spectrum is sensitive to this angle and can be used to probe the distribution of angles in poorly crystalline systems. We show that the INS spectrum is correctly calculated for bithiophene and shows the molecule to be planar in the solid - in agreement with crystallographic measurements. Poor agreement between observed and calculated spectra in the 700-cm sup - sup 1 region may be due to dynamic coupling, but this does not detract from the angle-sensitivity of the spectra. (orig.)

  16. Effect of Rhizopus oryzae Fermentation on Kenaf-Based Polylactic Acid’s Monomer

    OpenAIRE

    Nur Aimi Mohd Nasir; Mohd Adlan Mustafa Kamalbahrin; Nurhafizah Mohamad; Hazleen Anuar; Maizirwan Mel; and Rashidi Othman

    2011-01-01

    Kenaf biomass is the potential as raw materials used to produce polylactic acid's monomer which is lactic acid via fermentation by Rhizopus oryzae. Kenaf biomass' structure is complex due to its lignin and cellulose content. This matter had encouraged it to undergo pre- treatment process as the initial step before fermentation process can be done. In this paper, kenaf biomass was treated with dilute sulphuric acid (H2SO4) to hydrolyze the cellulose content in it as well as to convert the cell...

  17. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej

    2014-01-01

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  18. Effect of the fluorinated groups on nematic liquid crystal alignment on monomer crosslinked film

    International Nuclear Information System (INIS)

    Yu Tao; Peng Zenghui; Ruan Shengping; Xuan Li

    2004-01-01

    It was found in this work that photosensitive monomers, bisphenol A dicinnamate ester and hexafluorobiphenol a dicinnamate ester were crosslinked under irradiation of linearly polarized ultraviolet light. The exposed films induced homogeneous and homeotropic alignment of liquid crystals (LC), respectively. We verified through experiments that it was fluorinated groups that caused the generation of LC homeotropic alignment on the crosslinked film. Photoreaction process was revealed by Fourier transform infrared spectra. There was no clear morphological anisotropy on these aligned films observed through atomic force microscope analysis. The surface energies were measured and homeotropic alignment reason was discussed in this work

  19. A density functional theory study on the conversion of ethylene to carbon monomer on PdAu(1 0 0) surface

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Minhua; Yang, Bing [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

    2015-11-30

    Graphical abstract: - Highlights: • The successive decomposition of ethylene on PdAu(1 0 0) was studied with DFT method. • The C−H, C−C bond scission and a hydrogen-shift process were investigated. • The alloying of Au with Pd affects the studied reactions on PdAu(1 0 0) greatly. - Abstract: Calculations based on the first-principles density functional theory (DFT) were performed to study the possible transformation pathways of ethylene on PdAu(1 0 0) surface to investigate the effect of Au atom alloying with Pd on the formation of CHx (x = 0–2), which may eventually form carbon monomer and lead to the deactivation of catalysts. The energetic properties of reactions including the scission of the C−H, C−C bond and a hydrogen-shift process were determined. The C−H bond scission is confirmed to be prone to happen on the studied surface, while it is difficult for the C−C bond scission to occur due to relatively high barriers, the values of which are as high as 2.72–4.62 eV. The activation barriers for all related reactions except for the dehydrogenation of vinyl, vinylidene and acetenyl demonstrate that it is harder for the conversion of ethylene to occur on PdAu(1 0 0) surface than on Pd(1 0 0) surface, especially for the C−C bond scission. All the results indicate that the alloying of Au atom with pure Pd catalyst can prevent the formation of carbon monomer, which may notably affect properties of catalysts.

  20. Formation of multinucleated giant cells and microglial degeneration in rats expressing a mutant Cu/Zn superoxide dismutase gene

    Directory of Open Access Journals (Sweden)

    Streit Wolfgang J

    2007-02-01

    Full Text Available Abstract Background Microglial neuroinflammation is thought to play a role in the pathogenesis of amyotrophic lateral sclerosis (ALS. The purpose of this study was to provide a histopathological evaluation of the microglial neuroinflammatory response in a rodent model of ALS, the SOD1G93A transgenic rat. Methods Multiple levels of the CNS from spinal cord to cerebral cortex were studied in SOD1G93A transgenic rats during three stages of natural disease progression, including presymptomatic, early symptomatic (onset, and late symptomatic (end stage, using immuno- and lectin histochemical markers for microglia, such as OX-42, OX-6, and Griffonia simplicifolia isolectin B4. Results Our studies revealed abnormal aggregates of microglia forming in the spinal cord as early as the presymptomatic stage. During the symptomatic stages there was prominent formation of multinucleated giant cells through fusion of microglial cells in the spinal cord, brainstem, and red nucleus of the midbrain. Other brain regions, including substantia nigra, cranial nerve nuclei, hippocampus and cortex showed normal appearing microglia. In animals during end stage disease at 4–5 months of age virtually all microglia in the spinal cord gray matter showed extensive fragmentation of their cytoplasm (cytorrhexis, indicative of widespread microglial degeneration. Few microglia exhibiting nuclear fragmentation (karyorrhexis indicative of apoptosis were identified at any stage. Conclusion The current findings demonstrate the occurrence of severe abnormalities in microglia, such as cell fusions and cytorrhexis, which may be the result of expression of mutant SOD1 in these cells. The microglial changes observed are different from those that accompany normal microglial activation, and they demonstrate that aberrant activation and degeneration of microglia is part of the pathogenesis of motor neuron disease.

  1. Synthesis and characterization of the monomer 2,2'-dialylbisphenol-A (ABFA) for production of proton exchange membranes based on sulphonated poly(arylene ether sulphone)s reticulated

    International Nuclear Information System (INIS)

    Souza, Julio C.; Souza, Carlos H.F.B.; Silva, Maria Elisa S.R.; Sousa, Ricardo G.; Freitas, Roberto F.S.; Silva, Claudio Homero F.

    2011-01-01

    In the present work, a methodology of synthesis and characterization of the monomer 2,2'- dialylbisphenol A was developed, aiming at getting a precursor, with adequate purity, for obtaining cross-linked membranes based on sulfonated poly(arylene ether sulfone)s. The monomer 2,2'- dialylbisphenol A was obtained through Claisen rearrangement of the 2,2-Bis(4-alyloxiphenyl)propane, synthesized from Bisphenol A. All the products and reagents were characterized by Fourier Transform infrared spectroscopy, Thermo-gravimetric analysis and High-performance liquid chromatography. The thermal Claisen rearrangement process was conducted by using Differential Scanning Calorimetry technique, from a factorial experiment planning, with temperature and time being the variables. The above cited techniques were used for monitoring the Claisen rearrangement and for the characterization of the final product. The best results yield an ABFA purity between 85 and 90%. The obtained results suggest that, in the studied range, polymerization and degradation of the monomer ABFA occur, simultaneously to its formation. (author)

  2. Initial Reactivity of Linkages and Monomer Rings in Lignin Pyrolysis Revealed by ReaxFF Molecular Dynamics.

    Science.gov (United States)

    Zhang, Tingting; Li, Xiaoxia; Guo, Li

    2017-10-24

    The initial conversion pathways of linkages and their linked monomer units in lignin pyrolysis were investigated comprehensively by ReaxFF MD simulations facilitated by the unique VARxMD for reaction analysis. The simulated molecular model contains 15 920 atoms and was constructed on the basis of Adler's softwood lignin model. The simulations uncover the initial conversion ratio of various linkages and their linked aryl monomers. For linkages and their linked monomer aryl rings of α-O-4, β-O-4 and α-O-4 & β-5, the C α /C β ether bond cracking dominates the initial pathway accounting for at least up to 80% of their consumption. For the linkage of β-β & γ-O-α, both the C α -O ether bond cracking and its linked monomer aryl ring opening are equally important. Ring-opening reactions dominate the initial consumption of other 4-O-5, 5-5, β-1, β-2, and β-5 linkages and their linked monomers. The ether bond cracking of C α -O and C β -O occurs at low temperature, and the aryl ring-opening reactions take place at relatively high temperature. The important intermediates leading to the stable aryl ring opening are the phenoxy radicals, the bridged five-membered and three-membered rings and the bridged six-membered and three-membered rings. In addition, the reactivity of a linkage and its monomer aryl ring may be affected by other linkages. The ether bond cracking of α-O-4 and β-O-4 linkages can activate its neighboring linkage or monomer ring through the formed phenoxy radicals as intermediates. The important intermediates revealed in this article should be of help in deepening the understanding of the controlling mechanism for producing aromatic chemicals from lignin pyrolysis.

  3. Effects of (monomer - crosslinker – initiator) composition during non imprinted polymers synthesis for catechin retention

    Science.gov (United States)

    Triadhi, U.; Zulfikar, M. A.; Setiyanto, H.; Amran, M. B.

    2018-05-01

    MISPE (molecularly imprinted Solid Phase Extraction) is a separation technique using a solid adsorbent as a principle of MI (molecularly imprinted). Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, benzoyl peroxide (BPO) as an initiator and acetonitrile (ACN) as a porogen. Catechin will be used as the template. Thermal and microwave methods were employed in the synthesis method. When analyzed using FTIR spectra, it was found that there were no significant differences between NIP (non-imprinted polymer) resulting from thermal method and that resulting from microwave method. Preparation of polymers by microwave method required 4 mins at 60-65 °C, significantly less than thermal method, that took 60 minutes at the same temperature. The variations of mole ratios of the monomer, the crosslinker, and the initiator were also performed. Based on the FTIR spectra, intensity of some peaks were changed due to the decreases of concentration. The optimum composition for NIP synthesis was MAA: EGDMA: BPO ratio of 5:30:0.5 (in mmole). The TGA curve showed that the NIP sythesized using microwave method experienced mass loss of around 98.50% at 604.8 °C.

  4. Electron beam initiated modification of acrylic elastomer in presence of polyfunctional monomers

    International Nuclear Information System (INIS)

    Vijayabaskar, V.; Bhattacharya, S.; Tikku, V.K.; Bhowmick, A.K.

    2004-01-01

    The structural changes of an acrylic rubber (ACM) in presence and absence of polyfunctional monomers like trimethylolpropane triacrylate, tripropyleneglycol diacrylate, trimethylolmethane tetraacrylate and trimethylolpropane trimethacrylate at different doses of electron beam (EB) irradiations were investigated with the help of FTIR spectroscopy (in the attenuated total reflectance mode) and sol-gel analysis. As the radiation dose increases, the concentration of carbonyl group increases in the ACM rubber due to aerial oxidation. This is corroborated from the increase in the absorbance values at 1734 and 1160 cm -1 , which are due to carbonyl and C-O-C stretching frequencies, respectively. The increase in crosslinking is revealed by the increase in percentage gel content with radiation dose. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs have been determined for both grafted and ungrafted ACM rubber using a mathematical model. The predominance of crosslinking by electronic stopping with energetic EB projectile and the increase in effective radius of crosslinking have also been verified by this model. The doses at which the synergistic occurrence of both dislinking and endlinking steps originate have been calculated using linear energy transfer of EB. The ratio of scissioning to crosslinking for ACM rubber has been determined by using Charlesby-Pinner equation. The mechanical properties have been studied for different modified and unmodified systems and the tensile strength is found to increase with grafting of polyfunctional monomers

  5. Roasting conditions for preserving cocoa flavan-3-ol monomers and oligomers: interesting behaviour of Criollo clones.

    Science.gov (United States)

    De Taeye, Cédric; Bodart, Marie; Caullet, Gilles; Collin, Sonia

    2017-09-01

    Cocoa bean roasting is important for creating the typical chocolate aroma through Maillard reactions, but it is also a key step deleterious to the polyphenol content and profile. Compared with usual roasting at 150 °C, keeping the beans for 30 min at 120 °C or for 1 h at 90 °C proved much better for preventing strong degradation of native P1, P2 and P3 flavan-3-ols in cocoa (shown for Forastero, Trinitatio and Criollo cultivars). Surprisingly, Cuban, Mexican and Malagasy white-seeded beans behaved atypically when roasted for 30 min at 150 °C, releasing a pool of catechin. Enantiomeric chromatographic separation proved that this pool contained mainly (-)-catechin issued from (-)-epicatechin by epimerisation. As the (-)-epicatechin content remained relatively constant through Criollo bean roasting, flavan-3-ol monomers must have been regenerated from oligomers. This emergence of (-)-catechin in Criollo beans only, reported here for the first time, could be due to increased flavan-3-ol monomer stability in the absence of anthocyanidin-derived products. The degradation rate of flavan-3-ols through roasting is higher in cocoa beans containing anthocyani(di)ns. The liberation of a pool of (-)-catechin when submitted to roasting at 150 °C allows to distinguish white-seeded cultivars. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  6. Redesign of the monomer–monomer interface of Cre recombinase yields an obligate heterotetrameric complex

    Science.gov (United States)

    Zhang, Chi; Myers, Connie A.; Qi, Zongtai; Mitra, Robi D.; Corbo, Joseph C.; Havranek, James J.

    2015-01-01

    Cre recombinase catalyzes the cleavage and religation of DNA at loxP sites. The enzyme is a homotetramer in its functional state, and the symmetry of the protein complex enforces a pseudo-palindromic symmetry upon the loxP sequence. The Cre-lox system is a powerful tool for many researchers. However, broader application of the system is limited by the fixed sequence preferences of Cre, which are determined by both the direct DNA contacts and the homotetrameric arrangement of the Cre monomers. As a first step toward achieving recombination at arbitrary asymmetric target sites, we have broken the symmetry of the Cre tetramer assembly. Using a combination of computational and rational protein design, we have engineered an alternative interface between Cre monomers that is functional yet incompatible with the wild-type interface. Wild-type and engineered interface halves can be mixed to create two distinct Cre mutants, neither of which are functional in isolation, but which can form an active heterotetramer when combined. When these distinct mutants possess different DNA specificities, control over complex assembly directly discourages recombination at unwanted half-site combinations, enhancing the specificity of asymmetric site recombination. The engineered Cre mutants exhibit this assembly pattern in a variety of contexts, including mammalian cells. PMID:26365240

  7. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, M.S.

    1976-10-06

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure.

  8. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    International Nuclear Information System (INIS)

    Joshi, M.S.

    1976-01-01

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure

  9. Preliminary study of acrylamide monomer decomposition during methane fermentation of dairy waste sludge.

    Science.gov (United States)

    Mroczek, Ewelina; Konieczny, Piotr; Lewicki, Andrzej; Waśkiewicz, Agnieszka; Dach, Jacek

    2016-07-01

    Polyacrylamide (PAM) used in sludge dewatering exists widely in high-solid anaerobic digestion. Acrylamide is registered in the list of chemicals demonstrating toxic, carcinogenic and mutagenic properties. Therefore, it is reasonable to ask about the mobility of such residual substances in the environment. The study was carried out to assess the impact of the mesophilic (39±1°C) and thermophilic (54±1°C) fermentation process on the level of acrylamide monomer (AMD) content in the dairy sludge. The material was analysed using high-performance liquid chromatography (HPLC) for quantification of AMD. The results indicate that the process of methane fermentation continues regardless of the temperature effects on the degradation of AMD in dairy sludge. The degree of reduction of acrylamide monomer for thermophilic fermentation is 100%, while for mesophilic fermentation it is 91%. In practice, this means that biogas technology eliminates the risk of AMD migration to plant tissue. Moreover, it should be stressed that 90% of cumulative biogas and methane production was reached one week earlier under thermophilic conditions - the dynamics of the methanisation process were over 20% faster. Copyright © 2016. Published by Elsevier B.V.

  10. [Preparation of clear thermosetting resin for veneered crown from several bisMEPP monomers (author's transl)].

    Science.gov (United States)

    Tanaka, T; Nakabayashi, N; Masuhara, E

    1978-07-01

    The whitish translucent shade of a thermosetting resin cured from a mixture of a 2,2-Bis (p-methacryloxy (ethoxy)1-2 phenyl)-propane monomer and PMMA pearls makes it difficult to reconstruct a shade of the natural tooth. The attempt to improve the transparency of the mixed polymer was made in this study. Varying the molecular weight of BisMEPP monomer, PMMA polymer and curing temperature, cured specimens were prepared and their transparency was measured with a spectrophotometer. The results obtained are as follows. 1) In any molecular weight of PMMA, BisMEPP with 2.3 to 3.3 average number of ethylene oxide linkage showed the highest transpalency on the specimen. 2) With increasing the curing temperature, transpalency of the specimens made from BisME4.0 PP increased. With another molecular of BisMEPP, transpalency of the cured specimens showed the highest transpalency at the curing temperature of 120 degrees C. 3) With increasing the molecular weight of PMMA, the transpalency increased.

  11. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1988-01-01

    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  12. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes.

    Science.gov (United States)

    Xiao, Dongdong; Wu, Zhigang; Song, Miao; Chun, Jaehun; Schenter, Gregory K; Li, Dongsheng

    2018-01-30

    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to the lack of direct observation. Using an in situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in an aqueous solution through both classical monomer-by-monomer addition and nonclassical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars were formed via both oriented and nonoriented attachment. Our calculations, along with the dynamics of the observed attachment, showed that the van der Waals force overcomes hydrodynamic and friction forces and drives the particles toward each other at separations of 10-100 nm in our experiments. During classical growth, anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on (001) surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag + near the surface and the diffusion of Ag + from the bulk to the surface.

  13. Synthesis and characterisation of new Schiff base monomers containing N-(alkyl and phenyl) pyrrole moieties

    Science.gov (United States)

    Amer, Ahcene Ait; Ilikti, Hocine; Maschke, Ulrich

    2017-11-01

    This article deals with the synthesis and characterisation of seven new functional Schiff base monomers, such as: M1: 1-(3-Pyrrole-1-yl-propylimino-methyl)-naphtalen-2-ol; M2: 2-(3-Pyrrole-1-yl-phenylimino-methyl)-phenol; M3: 1-(3-Pyrrole-1-yl-phenylimino-methyl)-naphtalen-2-ol; M4: N-(pyridin-2-yl-methylene)-2-(pyrrol-1-yl)-benzenamine; M5: N-(pyridin-2-yl-methylene)-3-(pyrrol-1-yl)-propan-1-amine; M6: 2-(3-pyrrol-1-yl-propylimino-methyl)-quinolin-8-ol; M7: 2-(3-pyrrol-1-yl-phenylimino-methyl)-quinolin-8-ol. Two series of compounds emerged from this study, N-propyl pyrrole derivatives (M1, M5, M6) and N-phenyl pyrrole compounds (M2, M3, M4, M7). All monomers were elaborated by condensation reactions between appropriate amines and aldehydes, and their molecular structures were confirmed by spectroscopic analysis methods like FT-IR, 1H NMR, 13C NMR, and GC-MS.

  14. Direct nanoimprint lithography of Al2O3 using a chelated monomer-based precursor

    International Nuclear Information System (INIS)

    Ganesan, Ramakrishnan; Dinachali, Saman Safari; Lim, Su Hui; Saifullah, M S M; He, Chaobin; Low, Hong Yee; Chong, Wee Tit; Lim, Andrew H H; Yong, Jin Jie; Thian, Eng San

    2012-01-01

    Nanostructuring of Al 2 O 3 is predominantly achieved by the anodization of aluminum film and is limited to obtaining porous anodized aluminum oxide (AAO). One of the main restrictions in developing approaches for direct fabrication of various types of Al 2 O 3 patterns, such as lines, pillars, holes, etc, is the lack of a processable aluminum-containing resist. In this paper, we demonstrate a stable precursor prepared by reacting aluminum tri-sec-butoxide with 2-(methacryloyloxy)ethyl acetoacetate, a chelating monomer, which can be used for large area direct nanoimprint lithography of Al 2 O 3 . Chelation in the precursor makes it stable against hydrolysis whilst the presence of a reactive methacrylate group renders it polymerizable. The precursor was mixed with a cross-linker and their in situ thermal free-radical co-polymerization during nanoimprinting rigidly shaped the patterns, trapped the metal atoms, reduced the surface energy and strengthened the structures, thereby giving a ∼100% yield after demolding. The imprinted structures were heat-treated, leading to the loss of organics and their subsequent shrinkage. Amorphous Al 2 O 3 patterns with line-widths as small as 17 nm were obtained. Our process utilizes the advantages of sol–gel and methacrylate routes for imprinting and at the same time alleviates the disadvantages associated with both these methods. With these benefits, the chelating monomer route may be the harbinger of the universal scheme for direct nanoimprinting of metal oxides. (paper)

  15. Copolymerization of 4-Acetylphenyl Methacrylate with Ethyl Methacrylate: Synthesis, Characterization, Monomer Reactivity Ratios, and Thermal Properties

    Directory of Open Access Journals (Sweden)

    Gamze Barim

    2014-01-01

    Full Text Available Methacrylates have high glass transition temperature (Tg values and high thermal stability. A new methacrylate copolymer, poly(4-acetylphenyl methacrylate-co-ethyl methacrylate (APMA-co-EMA, was synthesized. The thermal behaviors of copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. They behaved as new single polymers with single Tg’s and the thermal stability of the copolymers increased with increasing 4-acetylphenyl methacrylate (APMA fraction, leading to the manufacture of copolymers with desired Tg values. Structure and composition of copolymers for a wide range of monomer feed ratios were determined by Fourier transform infrared (FT-IR and 1H-nuclear magnetic resonance (1H-NMR spectroscopic techniques. Copolymerization reactions were continued up to 40% conversions. The monomer reactivity ratios for copolymer system were determined by the Kelen-Tüdös (ra(APMA=0.81; rb(EMA=0.61 and extended Kelen-Tüdös (ra=0.77; rb=0.54 methods and a nonlinear least squares (ra=0.74; rb=0.49 method.

  16. An investigation of the chemical stability of a monomer/polymer gel dosimeter

    International Nuclear Information System (INIS)

    De Deene, Y.; De Wagter, C.; De Neve, W.; Achten, E.

    2000-01-01

    The aim of this work is to investigate the temporal stability of a polyacrylamide gelatin hydrogel used for 3D monomer/polymer gel dosimetry techniques involving different methods of analysis. Long-term instabilities for a similar gel have recently been reported, but differ markedly from those described in this work. Two kinds of long-term instabilities are described. One affects the slope of the dose-R 2 plot and is related to post-irradiation polymerization of the comonomer/polymer aggregates. It is observed that post-irradiation polymerization only lasts 12 hours after irradiation. The other instability affects the intercept of the dose-R 2 plot, lasts for up to 30 days and is related to the gelation process of gelatin. Further studies were performed on gelatin gels of varying compositions to obtain a better understanding of the molecular mechanism that causes the instability due to gelation. The studies included observations of the spin-spin and spin-lattice relaxation rates in combination with diffusion measurements and optical measurements. It is shown that the heating history during the manufacture of the gel affects the absolute R 2 value of the gel but not its variation. The findings presented in this study may help in producing more stable and reproducible monomer/polymer gel dosimeters. (author)

  17. Monomer-dimer control of the ColE1 P(cer) promoter.

    Science.gov (United States)

    Chatwin, H M; Summers, D K

    2001-11-01

    XerCD-mediated recombination at cer converts multimers of plasmid ColE1 to monomers, maximizing the number of independently segregating molecules and minimizing the frequency of plasmid loss. In addition to XerCD, recombination requires the accessory factors ArgR and PepA. The promoter P(cer), located centrally within cer, is also required for stable plasmid maintenance. P(cer) is active in plasmid multimers and directs transcription of a short RNA, Rcd, which appears to inhibit cell division. It has been proposed that Rcd is part of a checkpoint which ensures that multimer resolution is complete before the cell divides. This study has shown that ArgR does not act as a transcriptional repressor of P(cer) in plasmid monomers. P(cer) is unusual in that the -35 and -10 hexamers are separated by only 15 bp and this study has demonstrated that increasing this to a more conventional spacing results in elevated activity. An increase to 17 bp resulted in a 10- to 20-fold increase in activity, while smaller effects were seen when the spacer was increased to 16 bp or 18 bp. These observations are consistent with the hypothesis that P(cer) activation involves realignment of the -35 and -10 sequences within a recombinational synaptic complex. This predicts that a 17 bp spacer promoter derivative should be down-regulated by plasmid multimerization, and this is confirmed experimentally.

  18. Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Sharmaine B. Luk

    2017-10-01

    Full Text Available The radical copolymerization kinetics of acrylamide (AM and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB, formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL, are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (kt. The estimate for kt,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

  19. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  20. New Insights Toward Quantitative Relationships between Lignin Reactivity to Monomers and Their Structural Characteristics.

    Science.gov (United States)

    Ma, Ruoshui; Zhang, Xiumei; Wang, Yi; Zhang, Xiao

    2018-04-27

    The heterogeneous and complex structural characteristics of lignin present a significant challenge to predict its processability (e.g. depolymerization, modifications etc) to valuable products. This study provides a detailed characterization and comparison of structural properties of seven representative biorefinery lignin samples derived from forest and agricultural residues, which were subjected to representative pretreatment methods. A range of wet chemistry and spectroscopy methods were applied to determine specific lignin structural characteristics such as functional groups, inter-unit linkages and peak molecular weight. In parallel, oxidative depolymerization of these lignin samples to either monomeric phenolic compounds or dicarboxylic acids were conducted, and the product yields were quantified. Based on these results (lignin structural characteristics and monomer yields), we demonstrated for the first time to apply multiple-variable linear estimations (MVLE) approach using R statistics to gain insight toward a quantitative correlation between lignin structural properties and their conversion reactivity toward oxidative depolymerization to monomers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

    Directory of Open Access Journals (Sweden)

    Dagmar R. D'hooge

    2014-04-01

    Full Text Available Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000, optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP. Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr2/PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation ( polymer property. Careful selection or fed-batch addition of the conventional radical initiator I2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1. Fed-batch addition of not only I2, but also comonomer and deactivator (50 ppm under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

  2. Chemo-enzymatic Synthesis of Clickable Xylo-oligosaccharide Monomers from Hardwood 4-O-Methylglucuronoxylan.

    Science.gov (United States)

    MacCormick, Benjamin; Vuong, Thu V; Master, Emma R

    2018-02-12

    A chemo-enzymatic pathway was developed to transform 4-O-methylglucuronic acid (MeGlcpA) containing xylo-oligosaccharides from beechwood into clickable monomers capable of polymerizing at room temperature and in aqueous conditions to form unique polytriazoles. While the gluco-oligosaccharide oxidase (GOOX) from Sarocladium strictum was used to oxidize C6-propargylated oligosaccharides, the acid-amine coupling reagents 1-ethyl-3-(3-(dimethylamino)propyl) carbodiimide (EDAC) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) were employed and compared for their ability to append click functionalities to carboxylic acid groups of enzyme-treated oligosaccharides. While DMT-MM was a superior coupling reagent for this application, a triazine side product was observed during C-1 amidation. Resulting bifunctional xylo-oligosaccharide monomers were polymerized using a Cu(I) catalyst, forming a soft gel which was characterized by 1 H NMR, confirming the triazole product.

  3. A novel antibacterial orthodontic cement containing a quaternary ammonium monomer dimethylaminododecyl methacrylate

    Science.gov (United States)

    Melo, Mary A.S.; Wu, Junling; Weir, Michael D.; Xu, Hockin H. K.

    2015-01-01

    Demineralized lesions in tooth enamel around orthodontic brackets are caused by acids from cariogenic biofilm. This study aimed to develop a novel antibacterial orthodontic cement by incorporating a quaternary ammonium monomer dimethylaminododecyl methacrylate (DMADDM) into a commercial orthodontic cement, and to investigate the effects on microcosm biofilm response and enamel bond strength. DMADDM, a recently-synthetized antibacterial monomer, was incorporated into orthodontic cement at 0%, 1.5%, 3% and 5% mass fractions. Bond strength of brackets to enamel was measured. A microcosm biofilm model was used to measure metabolic activity, lactic acid production, and colony-forming units (CFU) on orthodontic cements. Shear bond strength was not reduced at 3% DAMDDM (p > 0.1), but was slightly reduced at 5% DMADDM, compared to 0% DMADDM. Biofilm viability was substantially inhibited when in contact with orthodontic cement containing 3% DMADDM. Biofilm metabolic activity, lactic acid production, and CFU were much lower on orthodontic cement containing DMADDM than control cement (p orthodontic cement containing 3% DMADDM inhibited oral biofilms without compromising the enamel bond strength, and is promising to reduce or eliminate demineralization in enamel around orthodontic brackets. PMID:25035230

  4. Synthesis of Molecularly Imprinted Polymers for Amino Acid Derivates by Using Different Functional Monomers

    Directory of Open Access Journals (Sweden)

    Sonia Scorrano

    2011-03-01

    Full Text Available Fmoc-3-nitrotyrosine (Fmoc-3-NT molecularly imprinted polymers (MIPs were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA, methacrylic acid (MAA, methacrylamide (MAM, 2-vinylpyridine (2-VP, 4-vinylpyridine (4-VP, have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1 was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

  5. Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Dongdong [Physical; Wu, Zhigang [School; Song, Miao [Physical; Chun, Jaehun [Physical; Schenter, Gregory K. [Physical; Li, Dongsheng [Physical

    2018-01-11

    Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to lack of direct observation. Using an in-situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in aqueous solution through both classical monomer-by-monomer addition and non-classical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars formed via both oriented and non-oriented attachment. Our calculations, along with dynamics of the observed attachment, showed that van der Waals force overcame hydrodynamic and friction forces and drove the particles toward each other. During classical growth, an anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on {001} surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag+ near the surface and the diffusion of Ag+ from bulk to surface.

  6. Preparation of a Bis-GMA-Free Dental Resin System with Synthesized Fluorinated Dimethacrylate Monomers

    Directory of Open Access Journals (Sweden)

    Shuzhen Luo

    2016-12-01

    Full Text Available With the aim of reducing human exposure to Bisphenol A (BPA derivatives in dentistry, a fluorinated dimethacrylate monomer was synthesized to replace 2,2-bis[4-(2-hydroxy-3-methacryloy-loxypropyl-phenyl]propane (Bis-GMA as the base monomer of dental resin. After mixing with reactive diluent triethyleneglycol dimethacrylate (TEGDMA, fluorinated dimethacrylate (FDMA/TEGDMA was prepared and compared with Bis-GMA/TEGDMA in physicochemical properties, such as double bond conversion (DC, volumetric shrinkage (VS, water sorption (WS and solubility (WSL, flexural strength (FS and modulus (FM. The results showed that, when compared with Bis-GMA based resin, FDMA-based resin had several advantages, such as higher DC, lower VS, lower WS, and higher FS after water immersion. All of these revealed that FDMA had potential to be used as a substitute for Bis-GMA. Of course, many more studies, such as biocompatibility testing, should be undertaken to prove whether FDMA could be applied in clinic.

  7. Final report of the safety assessment of methacrylate ester monomers used in nail enhancement products.

    Science.gov (United States)

    2005-01-01

    Methacrylate ester monomers are used in as artificial nail builders in nail enhancement products. They undergo rapid polymerization to form a hard material on the nail that is then shaped. While Ethyl Methacrylate is the primary monomer used in nail enhancement products, other methacrylate esters are also used. This safety assessment addresses 22 other methacrylate esters reported by industry to be present in small percentages as artificial nail builders in cosmetic products. They function to speed up polymerization and/or form cross-links. Only Tetrahydrofurfuryl Methacrylate was reported to the FDA to be in current use. The polymerization rates of these methacrylate esters are within the same range as Ethyl Methacrylate. While data are not available on all of these methacrylate esters, the available data demonstrated little acute oral, dermal, or i.p. toxicity. In a 28-day inhalation study on rats, Butyl Methacrylate caused upper airway irritation; the NOAEL was 1801 mg/m3. In a 28-day oral toxicity study on rats, t-Butyl Methacrylate had a NOAEL of 20 mg/kg/day. Beagle dogs dosed with 0.2 to 2.0 g/kg/day of C12 to C18 methacrylate monomers for 13 weeks exhibited effects only in the highest dose group: weight loss, emesis, diarrhea, mucoid feces, or salivation were observed. Butyl Methacrylate (0.1 M) and Isobutyl Methacrylate (0.1 M) are mildly irritating to the rabbit eye. HEMA is corrosive when instilled in the rabbit eye, while PEG-4 Dimethacrylate and Trimethylolpropane Trimethacrylate are minimally irritating to the eye. Dermal irritation caused by methacrylates is documented in guinea pigs and rabbits. In guinea pigs, HEMA, Isopropylidenediphenyl Bisglycidyl Methacrylate, Lauryl Methacrylate, and Trimethylolpropane Trimethacrylate are strong sensitizers; Butyl Methacrylate, Cyclohexyl Methacrylate, Hexyl Methacrylate, and Urethane Methacrylate are moderate sensitizers; Hydroxypropyl Methacrylate is a weak sensitizer; and PEG-4 Dimethacrylate and

  8. Process for recovering oil from subterranean formations

    International Nuclear Information System (INIS)

    Knight, B.; Gogarty, W.B.

    1978-01-01

    Improved flooding of oil-bearing formations is obtained by injecting and displacing through the formation a saline solution containing a water-soluble, substantially linear, high molecular weight polymer obtained by irradiating an aqueous solution of an ethylenically unsaturated monomer and a water-soluble salt under controlled conditions of concentration, radiation intensity, conversion, and total radiation dose. The saline water can contain at least 15,000 ppm of TDS (total dissolved solids) and at least 50 ppm and preferably 300 ppm of polyvalent cations. (Auth.)

  9. pKa value and buffering capacity of acidic monomers commonly used in self-etching primers.

    Science.gov (United States)

    Salz, Ulrich; Mücke, Angela; Zimmermann, Jörg; Tay, Franklin R; Pashley, David H

    2006-06-01

    The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4-(dihydroxyphosphoryl)-2-ox-abutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/l NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated bythe corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. For all the investigated acidic monomers, pKal values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKal values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0

  10. Cycling performance of lithium polymer cells assembled by in situ polymerization of a non-flammable ionic liquid monomer

    International Nuclear Information System (INIS)

    Lee, Yoon-Sung; Kim, Dong-Won

    2013-01-01

    Highlights: • Gel polymer electrolytes were synthesized by in situ polymerization of ionic liquid in the lithium polymer cells. • Flammability of the electrolyte was significantly reduced by polymerizing electrolyte containing a non-flammable ionic liquid monomer. • The cells assembled with polymeric ionic liquid-based electrolytes exhibited reversible cycling behavior with good capacity retention. -- Abstract: Lithium polymer cells composed of a lithium negative electrode and a LiCoO 2 positive electrode were assembled with a gel polymer electrolyte obtained by in situ polymerization of an electrolyte solution containing an ionic liquid monomer with vinyl groups. The polymerization of the electrolyte solution containing the non-flammable ionic liquid monomer resulted in a significant reduction of the flammability of the gel polymer electrolytes. The lithium polymer cell assembled with the stable gel polymer electrolyte delivered a discharge capacity of 134.3 mAh g −1 at ambient temperature and exhibited good capacity retention

  11. The role of monomer fraction data in association theories—Can we improve the performance for phase equilibrium calculations?

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Bøgh, David; Karakatsani, Eirini

    2014-01-01

    with different ethanol content as inhibitor. There are some differences in the performance of CPA with the two sets but on average the results are similar. This may indicate that monomer fraction data are not very useful in this case or that ethanol monomer fraction data are not accurate and both possibilities...... accurate and how useful are such data today and how successful is their use in the context of association models? In this work we attempt to answer these questions in the case of the CPA model and for ethanol. CPA has been already successfully used to describe thermodynamic properties of many ethanol...... containing mixtures, using an ethanol parameter set that was adjusted to experimental vapor pressure and liquid density data. We present in this work a new parameter set for ethanol which is estimated using experimental vapor pressure, liquid density data as well as the experimental monomer fractions...

  12. Microwave plasma initiated graft copolymerization modification of monomers onto PTFE surface

    International Nuclear Information System (INIS)

    Guan Weishu; Wen Yunjian; Fang Yan; Yin Yongxiang

    1996-02-01

    A graft copolymerization modification technique of monomers onto polytetrafluoroethylene (PTFE) surface initiated by a 2.45 GHz non-equilibrium microwave plasma has been investigated. Standard X-Ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (sEM) and wetting techniques were used for examination and analysis of samples. Considerable changes in chemical structure, composition and in morphology of grafted surface of PTFE were found. Results showed the occurrence of noticeable defluorination and cross-linked structure on grafted surface, and indicated that different kinds and contents of oxygen-containing functional groups were introduced into the surface of PTFE. Wetting and adhesion experiment of the sample proved that significant improvements in hydrophilicity and adhesion of surface were exhibited. These results confirmed the success of grafting. (8 refs., 7 figs., 1 tab.)

  13. Lurgi MegaMethanol technology. Delivering the building blocks for the future fuel and monomer demand

    Energy Technology Data Exchange (ETDEWEB)

    Wurzel, T. [Lurgi AG, Frankfurt/Main (Germany)

    2006-07-01

    The paper describes the central role of methanol within a changing environment with respect to feedstock availability as well as steadily growing demand in fuel and monomer demand. The current large-scale production facilities are described with respect to the technological challenges in order to ensure the availability of sufficient methanol for down-stream applications. Different down-stream applications are described which clearly confirm that methanol is the dominant C1-building block due to its chemical flexibility. It is concluded that by means of the implementation of two MTP (Methanol to Propylene) projects in China initiated the era of ''down-stream methanol'' has begun in the industry. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Theodorakis, P E [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Avgeropoulos, A [Department of Materials Science and Engineering, University of Ioannina, 45110 Ioannina (Greece); Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Universidad Nacional de Educacion a Distancia, Facultad de Ciencias, Senda del Rey 9, 28040 Madrid (Spain); Kosmas, M [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece); Vlahos, C [Department of Chemistry, University of Ioannina, 45110 Ioannina (Greece)

    2007-11-21

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

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

    Science.gov (United States)

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

    2007-11-01

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

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  17. Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

    International Nuclear Information System (INIS)

    Grishin, D.F.; Mojkin, A.A.

    1996-01-01

    When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

  18. A method for polymerizing insaturated monomers through irradiation in the presence of a salt

    International Nuclear Information System (INIS)

    Phalangas, C.J.; Restaino, A.J.; Yun, Hanbo.

    1975-01-01

    The method consists in irradiating an aqueous solution with a pH between about 2 and 12, comprising from 10 to 40% about an ethylene-insaturated monomer or of mixtures thereof with vinyl-sulfonic acid, an alkaline metal salt of said acid or acrylamide diacetone and at least 3% of a potassium, sodium, lithium, ammonium or aluminium salt, by means of highly powerful radiations, e.g. gamma rays, the radiation intensity being between 1000 and 200000 rads per hour and the overall radiation dose being in the 1000-30000 rads. The obtained product is a polymer aqueous solution either in the liquid state or in the form of a gel [fr

  19. Progress of research in treatment of hyperlipidemia by monomer or compound recipe of Chinese herbal medicine.

    Science.gov (United States)

    Dou, Xiao-bing; Wo, Xing-de; Fan, Chun-lei

    2008-03-01

    Hyperlipidemia (HLP) is the No.1 risk factor for patients with atherosclerosis (AS) and is directly related to the occurrence of coronary artery disease (CAD) and cerebrovascular disease. Therefore, prevention and treatment of AS is of great importance and of practical significance in controlling the incidence and mortality of CAD. With its peculiar syndrome-dependent therapy, traditional Chinese medicine (TCM) has accumulated abundant practical experiences in this field and good clinical effects have been achieved. Chinese herbal medicine, with its particularly unique advantages and high potentials yet to be tapped, displays its huge strength in HLP prevention and treatment. The progress of studies concerning prevention and treatment of HLP by Chinese herbal medicines, in the form of monomers or compound recipes, is reviewed in this paper.

  20. Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings

    Science.gov (United States)

    Segalman, Rachel

    Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.

  1. Vanadate monomers and dimers both inhibit the human prostatic acid phosphatase.

    Science.gov (United States)

    Crans, D C; Simone, C M; Saha, A K; Glew, R H

    1989-11-30

    A combination of enzyme kinetics and 51V NMR spectroscopy was used to identify the species of vanadate that inhibits acid phosphatases. Monomeric vanadate was shown to inhibit wheat germ and potato acid phosphatases. At pH 5.5, the vanadate dimer inhibits the human prostatic acid phosphatase whereas at pH 7.0 it is the vanadate monomer that inhibits this enzyme. The pH-dependent shift in the affinity of the prostatic phosphatase for vanadate is presumably due to deprotonation of an amino acid side chain in or near the binding site resulting in a conformational change in the protein. pH may be a subtle effector of the insulin-like vanadate activity in biological systems and may explain some of the differences in selectivity observed with the protein phosphatases.

  2. Solvent polarity scale on the fluorescence spectra of a dansyl monomer copolymerizable in aqueous media

    Science.gov (United States)

    Ren, Biye; Gao, Feng; Tong, Zhen; Yan, Yu

    1999-06-01

    A copolymerizable fluorescent monomer N-[2-[[[5-(N,N-dimethylamino)-1-naphthalenyl]sulfonyl]-amino]ethyl]-2-propenamide (DANSAEP) was synthesized, which exhibits dual fluorescence due to the twisted intramolecular charge transfer in the excited state. The emission maximum λem shifts from 463.3 nm in n-hexane to 530.0 nm in water, showing solvent polarity dependence. The relations between λem and the conventional solvent polarity parameters ET(30) or Z are linear, dividing solvents into protic and aprotic groups. Kamlet's linear solvation energy relationship gives a good description for λem as a solvent polarity scale. The increment of dipole moment Δ μ at the excited state was estimated as 5.09 D with the solvatochromic analysis.

  3. Radiation curing of mixture of diallylphthalate prepolymer and vinyl monomer, 11

    International Nuclear Information System (INIS)

    Gotoda, Masao; Yagi, Toshiaki; Yoshizawa, Iwao; Okugawa, Hideo.

    1975-01-01

    Preparation of Wood-Polymer Composite (WPC) piled plywood for flooring, was attempted by electron beam irradiation of American Hemlock veneer, impregnated with low molecular weight diallylphthalate prepolymer (DAPsub(p).L)/vinyl monomer mixtures, in comparison with that by thermal curing reported previously. For the improvement of the mechanical properties of WPC piled plywood, 5-15 parts of low molecular weight polyvinylacetate (PVAc) was added to DAPsub(p).L/methyl acrylate/hydroxyethyl acrylate/benzoyl peroxide (50/40/10/2) mixture. The addition of PVAc did not give much influence to the degree of impregnation in the veneer and to the curability by electron beam irradiation. As to the resistance to hot and cold cycle test, WPC piled plywood, prepared by the resin containing 5 parts of PVAc gave the best results. As a general conclusion, due to the superior mechanical properties, the WPC piled plywood processed by electron beam irradiation is suitable for flooring use. (author)

  4. HMI design of MIRROR PLANT for Safe Operation and Application to Vinyl Acetate Monomer Process

    International Nuclear Information System (INIS)

    Hatsugai, Emiko; Nakaya, Makoto

    2014-01-01

    Dynamic plant simulators have always been used off-line for operator training and control loop design prior to the plant construction phase. Here, we propose on-line use of a dynamic simulator for the development of new plant operation. The developed MIRROR PLANT is an on-line dynamic plant simulator that can perfectly simulate dynamic plant behavior, and can also be used to forecast future plant behavior by making the computer run the simulation faster than real-time. Using the estimated and forecast data, the plant operator can detect abnormal situations in the plant. Before activating an alarm from the conventional control system, the operator will be able to perform proactive operation to maintain safety. In this paper, we propose a new human-machine interface (HMI) design to realize proactive operation and discuss application of the HMI to the vinyl acetate monomer process as an example of MIRROR PLANT

  5. Synthesis and electrochemical analysis of polyaniline/TiO2 composites prepared with various molar ratios between aniline monomer and para-toluenesulfonic acid

    International Nuclear Information System (INIS)

    Oh, Misoon; Kim, Seok

    2012-01-01

    Graphical abstract: Polyaniline (PANI)/TiO 2 composites were prepared by in situ polymerization using para-toluenesulfonic acid (p-TSA). The composites showed different morphology and specific capacitances as a function of aniline concentration, which are related to the morphology (shape or size) of particles. Scheme of the formation of composites consisting of PANI film and the micelle structures is shown. Highlights: ► PANI/TiO 2 composite were prepared with a different concentration of monomer and dopant. ► Aniline/acid ratio influenced the morphological and electrochemical properties. ► The composites showed different capacitances as a function of aniline concentrations. ► Aniline/acid ratio could influence on the dispersion and surface roughness of particles. - Abstract: Polyaniline (PANI)/titanium dioxide (TiO 2 ) composites were prepared with a chemical oxidation polymerization of aniline monomer (ANI) with various molar ratios between ANI and para toluenesulfonic acid (p-TSA). To find an effect of the [ANI]:[p-TSA] molar ratio on the electrochemical properties of the prepared PANI/TiO 2 composites, the composites were synthesized under same conditions except the p-TSA concentrations. The prepared composite films had more homogeneous TiO 2 dispersion with changing [ANI]:[p-TSA] molar ratios from 6:1 to 1:1. p-TSA surfactant-like doping acid helped the dispersion of TiO 2 particles in the PANI matrix. PANI covering the TiO 2 surfaces was confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Prepared PANI films on the TiO 2 particles had the smoothest surface when the ANI and p-TSA had 1:1 molar ratio in the reaction solution. The composite prepared with molar ratio [ANI]:[p-TSA] of 3:1 had the highest capacitance (800 F g −1 ) among the prepared composites.

  6. Effect of microwave postpolymerization treatment on residual monomer content and the flexural strength of autopolymerizing reline resin

    Directory of Open Access Journals (Sweden)

    Patil Padmakar

    2009-01-01

    Full Text Available Background : Microwave postpolymerization has been suggested as a method to improve the flexural strength of an autopolymerizing denture reline resin. However, the effect of microwave postpolymerization on the residual monomer content and its influence on flexural strength have not been investigated. Objectives : This study analyzed the effect of microwave postpolymerization on the residual monomer content and its influence on the flexural strength of an autopolymerizing reline resin (Denture Liner. Materials and Methods : A total of 70 specimens (64 Χ 10 Χ 3.3 mm were polymerized according to the manufacturer′s instructions and divided into 7 groups (n = 10. Control group specimens were not subjectedto any further processing. Before testing, the specimens were subjected to postpolymerization in a microwave oven using different power (550 and 650 W and time (3, 4, and 5 min settings. Two specimens of each group were then manually ground into fine powder and samples extracted from the specimens using reflux method. The samples were then subjected to gas chromatography for residual monomer determination in area%. Eight specimens were subjected to a three-point bending device with a span of 50 mm and crosshead speed of 5 mm/min, and the flexural strength was determined in MPa. Data analyses included Student′s t-test and one-way analysis of variance. Results : For the Denture Liner reline resin, the residual monomer content decreased and the flexural strength increased significantly with the application of microwave irradiation using different time/power combinations. The specimens with the lowest residual monomer content were the similar specimens which presented with the highest flexural strength. Conclusion : Microwave postpolymerization irradiation can be an effective method for increasing the flexural strength of denture liner (at 650 W for 5 min by reducing the residual monomer content by further polymerization at free radical sites.

  7. Computational studies at the density functional theory (DFT) level about the surface functionalization of hexagonal monolayers by chitosan monomer

    Science.gov (United States)

    Ebrahimi, Javad; Ahangari, Morteza Ghorbanzadeh; Jahanshahi, Mohsen

    2018-05-01

    Theoretical investigations based on density functional theory have been carried out to understand the underlying interactions between the chitosan monomer and several types of hexagonal monolayers consisting of pristine and defected graphene and boron-nitride nanosheets. Based on the obtained results, it was found that the type of the interaction for all the systems is of non-covalent nature and the chitosan monomer physically interacts with the surface of mentioned nanostructures. The interaction strength was evaluated by calculating the adsorption energies for the considered systems and it was found that the adsorption of chitosan monomer accompanies by the release of about -0.67 and -0.66 eV energy for pristine graphene and h-BN monolayer, respectively. The role of structural defect has also been considered by embedding a Stone-Wales defect within the structure of mentioned monolayers and it was found that the introduced defect enhances the interactions between the chitosan monomer and nanostructures. The role of dispersion interactions has also been taken into account and it was found that these long-range interactions play the dominating role in the attachment of chitosan monomer onto the graphene sheet, while having strong contribution together with the electrostatic interactions for the stabilization of chitosan onto the surface of h-BN monolayer. For all the cases, the adsorption of chitosan monomer did not change the inherent electronic properties of the nanostructures based on the results of charge transfer analysis and energy gap calculations. The findings of the present work would be very useful in future investigations to explore the potential applications of these hybrid materials in materials science and bio-related fields.

  8. Pseudomonas syringae evades host immunity by degrading flagellin monomers with alkaline protease AprA.

    Science.gov (United States)

    Pel, Michiel J C; van Dijken, Anja J H; Bardoel, Bart W; Seidl, Michael F; van der Ent, Sjoerd; van Strijp, Jos A G; Pieterse, Corné M J

    2014-07-01

    Bacterial flagellin molecules are strong inducers of innate immune responses in both mammals and plants. The opportunistic pathogen Pseudomonas aeruginosa secretes an alkaline protease called AprA that degrades flagellin monomers. Here, we show that AprA is widespread among a wide variety of bacterial species. In addition, we investigated the role of AprA in virulence of the bacterial plant pathogen P. syringae pv. tomato DC3000. The AprA-deficient DC3000 ΔaprA knockout mutant was significantly less virulent on both tomato and Arabidopsis thaliana. Moreover, infiltration of A. thaliana Col-0 leaves with DC3000 ΔaprA evoked a significantly higher level of expression of the defense-related genes FRK1 and PR-1 than did wild-type DC3000. In the flagellin receptor mutant fls2, pathogen virulence and defense-related gene activation did not differ between DC3000 and DC3000 ΔaprA. Together,