WorldWideScience

Sample records for monomer units metal

  1. Papain-Catalyzed Synthesis of Polyglutamate Containing a Nylon Monomer Unit

    OpenAIRE

    Kenjiro Yazawa; Keiji Numata

    2016-01-01

    Peptides have the potential to serve as an alternative for petroleum-based polymers to support a sustainable society. However, they lack thermoplasticity, owing to their strong intermolecular interactions. In contrast, nylon is famous for its thermoplasticity and chemical resistance. Here, we synthesized peptides containing a nylon unit to modify their thermal properties by using papain-catalyzed chemoenzymatic polymerization. We used l-glutamic acid alkyl ester as the amino acid monomer and ...

  2. Efficiency of light-emitting diode and halogen units in reducing residual monomers

    Science.gov (United States)

    de Assis Ribeiro Carvalho, Felipe; Almeida, Rhita C.; Almeida, Marco Antonio; Cevidanes, Lucia H. S.; Leite, Marcia C. Amorim M.

    2011-01-01

    Introduction In this in-vitro study, we aimed to compare the residual monomers in composites beneath brackets bonded to enamel, using a light-emitting diode (LED) or a halogen unit, and to compare the residual monomers in the central to the peripheral areas of the composite. Methods Twenty bovine teeth preserved in 0.1% thymol were used in this study. Ten teeth were used to standardize the thickness of the composite film, since different thicknesses would cause different absorbance of light. Brackets were bonded to 10 bovine incisors, with the halogen light (n = 5) and the LED (n = 5). The brackets were debonded, and the remaining composite on the enamel surface was sectioned in 2 regions: peripheral (0.8 mm) and central, resulting in 2 subgroups per group: central halogen (n = 5), peripheral halogen (n = 5), central LED (n = 5), and peripheral LED (n = 5). The spectrometric analysis in the infrared region was used to measure the free monomers with the attenuated total reflectance method. Results Normal distribution was tested by using the Kolmogorov-Smirnov test. Data were compared by 2-way analysis of variance (ANOVA) at P <0.05. The LED group showed fewer residual monomers than did the halogen group (P = 0.014). No differences were found among the regions (P = 0.354), and there were no interactions between light type and region (P = 0.368). Conclusions LED leaves less residual monomer than does the halogen light, even with half of the irradiation time; there were no differences between the central and peripheral regions, and no interaction between light type and region. PMID:21055603

  3. 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

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

    Science.gov (United States)

    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 (0.063-0.088s(-1)) were lower than those determined in the monomer combinations (0.116-0.158s(-1)) incorporating phosphate diacrylate (11wt.%), BisGMA (33wt.%), TEGDMA (10wt.%), UDMA (10wt.%) and HEMA (15wt.%), the degree of conversion varying between 63.4 and 74.5%. The formed copolymers showed high values for water sorption (18.65-57.02μg/mm(3)) and water solubility (3.51-13.38μg/mm(3)), and the contact angle was dependent on the presence of CO-DAP (θF1: 66.67°), TMP-DAP (θF2: 55.05°) or AMP-P (θF3: 52.90°) in the photocrosslinked specimens compared to the sample without phosphate monomer (θF4: 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 20s 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 (1wt.%) 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.

  5. Synthesis of fluorinated poly(arylene ether)s with dibenzodioxin and spirobisindane units from new bis(pentafluorophenyl)- and bis(nonafluorobiphenyl)-containing monomers

    DEFF Research Database (Denmark)

    Tkachenko, Ihor M.; Belov, Nikolay A.; Kobzar, Yaroslav L.

    2017-01-01

    -substituted compounds were synthesised. Fluorinated poly(arylene ether)s having perfluorinated aromatic units as well as both rigid dibenzodioxin and spirobisindane fragments were successfully obtained by interaction of the synthesized core-fluorinated monomers with 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1......(nonafluorophenyl)-containing monomers have higher average molecular masses (Mw) in the range 47,000–88,300 and are able to form robust, solvent-cast films. Good thermal stabilities in air (up to 350 °C) were observed in all fluorinated polymers. The Brunauer–Emmett–Teller specific surface area and the pore size of polymers can...

  6. 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.

  7. 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.

  8. A monomer is the minimum functional unit required for channel and ATPase activity of the cystic fibrosis transmembrane conductance regulator.

    Science.gov (United States)

    Ramjeesingh, M; Li, C; Kogan, I; Wang, Y; Huan, L J; Bear, C E

    2001-09-04

    The cystic fibrosis transmembrane conductance regulator (CFTR) normally functions as a phosphorylation-regulated chloride channel on the apical surface of epithelial cells, and lack of this function is the primary cause for the fatal disease cystic fibrosis (CF). Previous studies showed that purified, reconstituted CFTR can function as a chloride channel and, further, that its intrinsic ATPase activity is required to regulate opening and closing of the channel gate. However, these previous studies did not identify the quaternary structure required to mediate conduction and catalysis. Our present studies show that CFTR molecules may self-associate in CHO and Sf9 membranes, as complexes close to the predicted size of CFTR dimers can be captured by chemical cross-linking reagents and detected using nondissociative PAGE. However, CFTR function does not require a multimeric complex for function as we determined that purified, reconstituted CFTR monomers are sufficient to mediate regulated chloride conduction and ATPase activity.

  9. STUDY ON THE IMMOBILIZATION OF PAPAIN WITH A MACROPOROUS BEAD CARRIER OF COPOLYMER CONTAINING MONOMER UNITS OF N-AMINOETHYL ACRYLAMIDE AND VINYL ALCOHOL

    Institute of Scientific and Technical Information of China (English)

    Yan-feng Li; Jun-rong Li; Lian-di Fu; Yao-zeng Li

    2000-01-01

    A kind of macroporous bead carrier of copolymer containing monomer units ofN-aminoethyl acrylamide and vinyl alcohol was synthesized, i.e. the MR-AA carrier. Papain was immobilized on the carrier using glutaraldehyde as the coupling agent. The enzymatic activity of the immobilized papain was compared with free papain using casein as a substrate, and the effects of glutaraldehyde concentration, pH, temperature, time and papain amount added on the activity recovery were also investigated. The results show that the MR-AA carrier contains reactive primary amine groups, hydrophilic amido links and hydroxyl groups, as well as macroporous structures based on its matrix (MR-AV matrix), furthermore, the activity recovery of papain in the immobilization could reach 48%~58%. In comparison with free papain, the resulting immobilized papain exhibits a remarkable thermostability and better reusability.

  10. Bax monomers form dimer units in the membrane that further self-assemble into multiple oligomeric species

    Science.gov (United States)

    Subburaj, Yamunadevi; Cosentino, Katia; Axmann, Markus; Pedrueza-Villalmanzo, Esteban; Hermann, Eduard; Bleicken, Stephanie; Spatz, Joachim; García-Sáez, Ana J.

    2015-08-01

    Bax is a key regulator of apoptosis that mediates the release of cytochrome c to the cytosol via oligomerization in the outer mitochondrial membrane before pore formation. However, the molecular mechanism of Bax assembly and regulation by other Bcl-2 members remains obscure. Here, by analysing the stoichiometry of Bax oligomers at the single-molecule level, we find that Bax binds to the membrane in a monomeric state and then self-assembles in Bax does not exist in a unique oligomeric state, but as several different species based on dimer units. Moreover, we show that cBid activates Bax without affecting its assembly, while Bcl-xL induces the dissociation of Bax oligomers. On the basis of our experimental data and theoretical modelling, we propose a new mechanism for the molecular pathway of Bax assembly to form the apoptotic pore.

  11. Poly[N-(2-aminoethyl)ethyleneimine] as a New Non-Viral Gene Delivery Carrier : The Effect of Two Protonatable Nitrogens in the Monomer Unit on Gene Delivery Efficiency

    NARCIS (Netherlands)

    Khazaie, Yahya; Novo, Luis; van Gaal, Ethlinn; Fassihi, Afshin; Mirahmadi-Zareh, Seyedeh Zohreh; Esfahani, Mohammad Hossein Nasr; van Nostrum, Cornelus F.; Hennink, Wim E.; Dorkoosh, Farid

    2014-01-01

    Purpose. The aim of this study was to investigate the in vitro gene delivery efficiency of poly[N-(2-aminoethyl)ethylene-imine](PAEEI), a polymer with a linear Polyethyleneimine (LPEI) backbone and with aminoethyl side groups that has two protonatable nitrogen atoms per monomer unit instead of one a

  12. Design of a new, multi-purpose, light-curing adhesive comprising a silane coupling agent, acidic adhesive monomers and dithiooctanoate monomers for bonding to varied metal and dental ceramic materials.

    Science.gov (United States)

    Ikemura, Kunio; Tanaka, Hisaki; Fujii, Toshihide; Deguchi, Mikito; Negoro, Noriyuki; Endo, Takeshi; Kadoma, Yoshinori

    2011-01-01

    A newly designed, light-curing adhesive was investigated for its bonding effectiveness to porcelain, alumina, zirconia, Au, Au alloy, Ag alloy, Au-Ag-Pd alloy, and Ni-Cr alloy. Four experimental adhesives were prepared using varying contents of the following: a silane coupling agent [3-methacryloyloxypropyltriethoxysilane (3-MPTES)], acidic adhesive monomers [6-methacryloyloxyhexyl phosphonoacetate(6-MHPA),6-methacryloyloxyhexyl3-phosphonopropionate(6-MHPP)and 4-methacryloyloxyethoxycarbonylphthalic acid (4-MET)], and dithiooctanoate monomers [6-methacryloyloxyhexyl 6,8-dithiooctanoate (6-MHDT) and 10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT)]. After all adherend surfaces were sandblasted and applied with an experimental adhesive, shear bond strengths (SBSs) of a light-curing resin composite (Beautifil II, Shofu Inc., Kyoto, Japan) to the adherend materials after 2,000 times of thermal cycling were measured. For the experimental adhesive which contained 3-MPTES (30.0 wt%), 6-MHPA (1.0 wt%), 6-MHPP (1.0 wt%), 4-MET (1.0 wt%), 6-MHDT (0.5 wt%) and 10-MDDT (0.5 wt%), it consistently yielded the highest SBS for all adherend surfaces in the range of 20.8 (4.8)-30.3 (7.9) MPa, with no significant differences among all the adherend materials (p>0.05). Therefore, the newly designed, multi-purpose, light-curing adhesive was able to deliver high SBS to all the adherend materials tested.

  13. Recovery of olefin monomers

    Science.gov (United States)

    Golden, Timothy Christoph; Weist, Jr., Edward Landis; Johnson, Charles Henry

    2004-03-16

    In a process for the production of a polyolefin, an olefin monomer is polymerised said polyolefin and residual monomer is recovered. A gas stream comprising the monomer and nitrogen is subjected to a PSA process in which said monomer is adsorbed on a periodically regenerated silica gel or alumina adsorbent to recover a purified gas stream containing said olefin and a nitrogen rich stream containing no less than 99% nitrogen and containing no less than 50% of the nitrogen content of the gas feed to the PSA process.

  14. New radiation sensor embedded in a metal detection unit

    Energy Technology Data Exchange (ETDEWEB)

    Osovizky, A.; Cohen-Zada, I.; Vulasky, E.; Ginzburg, D.; Manor, A.; Ankry, N.; Pushkarsky, V.; Lefevre, M. [Health Physics Instrumentation Department, Rotem Industries Ltd. (Israel); Ghelman, M.; Marcus, E.; Kadmon, Y.; Cohen, Y. [Electronics and Control Laboratories, Nuclear Research Center - Negev, Beer-Sheva (Israel)

    2009-07-01

    This work introduces the embedment of a radiation detection unit within a metal detector. The radiation sensor, based on the Silicon Photomultiplier (SiPM) coupled to a scintillation crystal, was successfully incorporated into a common metal detection unit. The results for sensitivity are presented. The study also shows that SiPM is not affected by microphone noises (which make PIN-diodes improper to some applications) and by the alternating type of the voltage supply (which means that SiPM can be used either in portable or in stationary applications)

  15. Synthesis and photoactivity of phenylazonaphthalene peptide nucleic acid monomers

    Institute of Scientific and Technical Information of China (English)

    Jin Du Li; Miao Chen; Sheng Liu; Hao Bo Zhang; Zhi Lu Liu

    2008-01-01

    Phenylazonaphthalene peptide nucleic acid (PNA) monomers were successfully synthesized,and their photoisomerization was examined.The new PNA monomers showed reversible trans-cis isomerization with UV and visible light irradiation,which might be the foundation of photo-regulating the hybridization between PNA containing phenylazonaphthalene unit and DNA.Simultaneously,the fluorescence of the new PNA monomers might make them especially useful as structural probes.

  16. Metal prices in the United States through 2010

    Science.gov (United States)

    ,

    2013-01-01

    This report, which updates and revises the U.S. Geological Survey (USGS) (1999) publication, “Metal Prices in the United States Through 1998,” presents an extended price history for a wide range of metals available in a single document. Such information can be useful for the analysis of mineral commodity issues, as well as for other purposes. The chapter for each mineral commodity includes a graph of annual current and constant dollar prices for 1970 through 2010, where available; a list of significant events that affected prices; a brief discussion of the metal and its history; and one or more tables that list current dollar prices. In some cases, the metal prices presented herein are for some alternative form of an element or, instead of a price, a value, such as the value for an import as appraised by the U.S. Customs Service. Also included are the prices for steel, steel scrap, and iron ore—steel because of its importance to the elements used to alloy with it, and steel scrap and iron ore because of their use in steelmaking. A few minor metals, such as calcium, potassium, sodium, strontium, and thorium, for which price histories were insufficient, were excluded. The annual prices given may be averages for the year, yearend prices, or some other price as appropriate for a particular commodity. Certain trade journals have been the source of much of this price information—American Metal Market, ICIS Chemical Business, Engineering and Mining Journal, Industrial Minerals, Metal Bulletin, Mining Journal, Platts Metals Week, Roskill Information Services Ltd. commodity reports, and Ryan’s Notes. Price information also is available in minerals information publications of the USGS (1880–1925, 1996–present) and the U.S. Bureau of Mines (1926–95), such as Mineral Commodity Summaries, Mineral Facts and Problems, Mineral Industry Surveys, and Minerals Yearbook. In addition to prices themselves, these journals and publications contain information relevant to

  17. A review of the developments of multi-purpose primers and adhesives comprising novel dithiooctanoate monomers and phosphonic acid monomers.

    Science.gov (United States)

    Ikemura, Kunio; Endo, Takeshi; Kadoma, Yoshinori

    2012-02-03

    This paper reviews the developments of dithiooctanoate monomers and acidic adhesive monomers, and their roles in multi-purpose primers and adhesives in promoting adhesion to multiple substrate materials. Novel dithiooctanoate monomers exhibited excellent bonding to precious metals and alloys when compared against conventional sulfur-containing monomers. Newly developed phosphonic acid monomers, endowed with a water-soluble nature, enabled sufficient demineralization of dental hard tissues and thus improved bonding to both ground enamel and dentin. The optimal combination for bonding to dental hard tissues and precious and non-precious metals and alloys was 5.0 wt% 10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT) and 1.0 wt% 6-methacryloyloxyhexyl phosphonoacetate (6-MHPA). For bonding to dental porcelain, alumina, zirconia, and gold (Au) alloy, a ternary combination of silane coupling agent, acidic adhesive monomers, and dithiooctanoate monomers seemed promising. The latest development was a single-bottle, multi-purpose, self-etching adhesive which contained only acidic adhesive monomers and dithiooctanoate monomers but which produced strong adhesion to ground enamel and dentin, sandblasted zirconia, and Au alloy.

  18. Study on the efficiency of the different units for removing metallic ...

    African Journals Online (AJOL)

    ... of the different units for removing metallic ions in Isfahan water treatment plant. ... In this study, removal efficiency of heavy metals such as iron, manganese, ... the water treatment plant exceeded the EPA drinking water standard (50 µg l-1).

  19. A Macrocyclic 1,4-Diketone Enables the Synthesis of a p-Phenylene Ring That Is More Strained than a Monomer Unit of [4]Cycloparaphenylene.

    Science.gov (United States)

    Mitra, Nirmal K; Corzo, Hector H; Merner, Bradley L

    2016-07-01

    The synthesis of a p-terphenyl-based macrocycle, containing a p-phenylene unit with 42.6 kcal/mol of strain energy (SE), is reported. The conversion of a macrocyclic 1,4-diketone to a highly strained arene system takes place over five synthetic steps, featuring iterative dehydrative reactions in the aromatization protocol. Spectroscopic data of the deformed benzenoid macrocycle are in excellent agreement with other homologues that have been reported, indicating that the central p-phenylene ring of 9 is aromatic.

  20. Heterogeneity within a Mesoporous Metal-Organic Framework with Three Distinct Metal-Containing Building Units.

    Science.gov (United States)

    Tu, Binbin; Pang, Qingqing; Ning, Erlong; Yan, Wenqing; Qi, Yi; Wu, Doufeng; Li, Qiaowei

    2015-10-28

    Materials built from multiple constituents have revealed emerging properties that are beyond linear integration of those from single components. We report a mesoporous metal-organic framework made from three geometrically distinct metal-containing secondary building units (SBUs) as a result of topological induction. The combinations of the Cu-based triangular, Zn-based octahedral, and Zn-based square pyramidal SBUs have created four types of cages in the network, despite that only one organic linker pyrazolecarboxylate was used. The longest distance for molecules maneuvering inside the largest cage is 5.2 nm. Furthermore, the complex and diversified pore environments allow the installation of various new functionalities in the framework as well as the expedited Ag nanoparticle formation in the pores. As presented in the molecule movement diagram, the crystal has provided specific arrangements of cages and apertures with distinct chemical features for guests transporting between the pores.

  1. Monomer Migration and Annihilation Processes

    Institute of Scientific and Technical Information of China (English)

    KE Jian-Hong; LIN Zhen-Quan; ZHUANG You-Yi

    2005-01-01

    We propose a two-species monomer migration-annihilation model, in which monomer migration reactions occur between any two aggregates of the same species and monomer annihilation reactions occur between two different species. Based on the mean-field rate equations, we investigate the evolution behaviors of the processes. For the case with an annihilation rate kernel proportional to the sizes of the reactants, the aggregation size distribution of either species approaches the modified scaling form in the symmetrical initial case, while for the asymmetrical initial case the heavy species with a large initial data scales according to the conventional form and the light one does not scale. Moreover,at most one species can survive finally. For the case with aconstant annihilation rate kernel, both species may scale according to the conventional scaling law in the symmetrical case and survive together at the end.

  2. A diethyl phosphonate containing oxazoline: Synthesis and characterization of monomer and homopolymer

    Energy Technology Data Exchange (ETDEWEB)

    Hermes, R.E.; Thompson, R.D.; Valdez, L.S.

    1995-05-01

    A diethyl phosphonate oxazoline monomer and its polymer have been synthesized. The monomer appears to polymerize via a ring-opening mechanism giving the expected polyethyleneimine backbone with pendant carbonyl groups. Two distinct molecular weights were produced during polymerization suggesting two mechanisms of chain growth. Studies are underway to elucidate the reasons for this. This polymer has potential as a metal-chelating agent.

  3. GENERAL: Cluster Growth Through Monomer Adsorption Processes

    Science.gov (United States)

    Ke, Jian-Hong; Lin, Zhen-Quan; Chen, Xiao-Shuang

    2010-02-01

    We propose a monomer adsorption model, in which only the monomers are allowed to diffuse and adsorb onto other clusters. By means of the generalized rate equation we investigate the kinetic behavior of the system with a special rate kernel. For the system without monomer input, the concentration aj(t) of the Aj clusters (j > 1) asymptotically retains a nonzero quantity, while for the system with monomer input, it decays with time and vanishes finally. We also investigate the kinetics of an interesting model with fixed-rate monomer adsorption. For the case without monomer source, the evolution of the system will halt at a finite time; while the system evolves infinitely in time in the case with monomer source. Finally, we also suggest a connection between the fixed-rate monomer adsorption systems and growing networks.

  4. Reaction of sulfur-containing structural units of transition metals

    Institute of Scientific and Technical Information of China (English)

    陈忠宁; 康北笙; 童叶翔; 张华新; 苏成勇; 林璋; 洪茂椿; 郁开北

    1997-01-01

    Two tri-n-butylphosphme-participated ( PBu3n) nickel (Ⅱ) complexes of 2-mercaptophenol(H2mp),i.e,Ni2Ru(mp)3(Hmp)(PBu3n)3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear "synthon",[HNEt3] [Ni(mp) (Hmp) (PBu3n)] 1 were synthesized and characterized by X-crystallography and 1H NMR,FAB-MS and cyclic valtammogram measurements.The nickel(Ⅱ) center in 1 has a square-planar geometry For 3,the ruthenium(Ⅲ) atom is in a distorted octahedral environment and the two mckel(Ⅱ) atoms exhibit square-planar and rare triangle-planar geometries,respectively.The Ni (1)-Ru-Ni(2 ) arrangement is severely asymmetric with the distances 0.254 and 0.394 nm,respectively,for Ni(1)-Ru and Ni(2)-Ru.The structural regularities of relevant complexes are summarized in relation to the structural as well as spectra data.

  5. United abominations: Density functional studies of heavy metal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Schoendorff, George [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    Carbonyl and nitrile addition to uranyl (UO22+) are studied. The competition between nitrile and water ligands in the formation of uranyl complexes is investigated. The possibility of hypercoordinated uranyl with acetone ligands is examined. Uranyl is studied with diactone alcohol ligands as a means to explain the apparent hypercoordinated uranyl. A discussion of the formation of mesityl oxide ligands is also included. A joint theory/experimental study of reactions of zwitterionic boratoiridium(I) complexes with oxazoline-based scorpionate ligands is reported. A computational study was done of the catalytic hydroamination/cyclization of aminoalkenes with zirconium-based catalysts. Techniques are surveyed for programming for graphical processing units (GPUs) using Fortran.

  6. Fingerprinting sedimentary and soil units by their natural metal contents: a new approach to assess metal contamination.

    Science.gov (United States)

    Amorosi, Alessandro; Guermandi, Marina; Marchi, Nazaria; Sammartino, Irene

    2014-12-01

    One of the major issues when assessing soil contamination by inorganic substances is reliable determination of natural metal concentrations. Through integrated sedimentological, pedological and geochemical analyses of 1414 (topsoil/subsoil) samples from 707 sampling stations in the southern Po Plain (Italy), we document that the natural distribution of five potentially toxic metals (Cr, Ni, Cu, Zn and Pb) can be spatially predicted as a function of three major factors: source-rock composition, grain size variability and degree of soil weathering. Thirteen genetic and functional soil units (GFUs), each reflecting a unique combination of these three variables, are fingerprinted by distinctive geochemical signatures. Where sediment is supplied by ultramafic (ophiolite-rich) sources, the natural contents of Cr and Ni in soils almost invariably exceed the Italian threshold limits designated for contaminated lands (150 mg/kg and 120 mg/kg, respectively), with median values around twice the maximum permissible levels (345 mg/kg for Cr and 207 mg/kg for Ni in GFU B5). The original provenance signal is commonly confounded by soil texture, with general tendency toward higher metal concentrations in the finest-grained fractions. Once reliable natural metal concentrations in soils are established, the anthropogenic contribution can be promptly assessed by calculating metal enrichments in topsoil samples. The use of combined sedimentological and pedological criteria to fingerprint GFU geochemical composition is presented here as a new approach to enhance predictability of natural metal contents, with obvious positive feedbacks for legislative purposes and environmental protection. Particularly, natural metal concentrations inferred directly from a new type of pedogeochemical map, built according to the international guideline ISO 19258, are proposed as an efficient alternative to the pre-determined threshold values for soil contamination commonly established by the national

  7. Polymer as a function of monomer: Analytical quantum modeling

    CERN Document Server

    Nakhaee, Mohammad

    2016-01-01

    To identify an analytical relation between the properties of polymers and their's monomer a Metal-Molecule-Metal (MMM) junction has been presented as an interesting and widely used object of research in which the molecule is a polymer which is able to conduct charge. The method used in this study is based on the Green's function approach in the tight-binding approximation using basic properties of matrices. For a polymer base MMM system, transmission, density of states (DOS) and local density of states (LDOS) have been calculated as a function of the hamiltonian of the monomer. After that, we have obtained a frequency for LDOS variations in pass from a subunit to the next one which is a function of energy.

  8. Intense generation of respirable metal nanoparticles from a low-power soldering unit

    Energy Technology Data Exchange (ETDEWEB)

    Gómez, Virginia [Department of Chemical Engineering, Nanoscience Institute of Aragon (INA), 50018 Zaragoza (Spain); Irusta, Silvia [Department of Chemical Engineering, Nanoscience Institute of Aragon (INA), 50018 Zaragoza (Spain); Networking Biomedical Research Center of Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), 50018 Zaragoza (Spain); Balas, Francisco [Networking Biomedical Research Center of Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), 50018 Zaragoza (Spain); Instituto de Carboquímica – Consejo Superior de Investigaciones Científicas (ICB-CSIC), 50018 Zaragoza (Spain); Santamaria, Jesus, E-mail: Jesus.Santamaria@unizar.es [Department of Chemical Engineering, Nanoscience Institute of Aragon (INA), 50018 Zaragoza (Spain); Networking Biomedical Research Center of Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN), 50018 Zaragoza (Spain)

    2013-07-15

    Highlights: • Intense generation of nanoparticles in the breathing range from a flux-soldering unit is detected. • Coagulation in the aerosol phase leads to 200-nm respirable nanoparticles up to 30 min after operation. • Nanoparticle concentration in the working environment depends on the presence of ambient air. • Metal-containing nanoparticles are collected in TEM grids and filters in the hundreds of nanometer range. -- Abstract: Evidence of intense nanoparticle generation from a low power (45 W) flux soldering unit is presented. This is a familiar device often used in daily life, including home repairs and school electronic laboratories. We demonstrate that metal-containing nanoparticles may reach high concentrations (ca. 10{sup 6} particles/cm{sup 3}) within the breathing range of the operator, with initial size distributions centered at 35–60 nm The morphological and chemical analysis of nanoparticle agglomerates collected on TEM grids and filters confirms their multiparticle structure and the presence of metals.

  9. 以乙烯基吡咯烷酮为功能单体的金属配合印迹聚合物的制备及水相识别%Preparation and Aqueous Recognition of Metal Complex Imprinted Polymer Using N-vinyl-2-pyrrolidone as Functional Monomer

    Institute of Scientific and Technical Information of China (English)

    王学军; 许振良; 邴乃慈; 杨座国

    2007-01-01

    Using nickel( Ⅱ ) acetate-2,2'-dipyridyl complex as template and N-vinyl-2-pyrrolidone (NVP) as coordinate functional monomer, a new kind of metal-complexing template molecularly imprinted polymer (MIP) was prepared. The results of equilibrium binding experiments in aqueous solution showed that the MIP had higher binding capacity for nickel( Ⅱ )-2,2'-dipyridyl than the non-imprinted polymer with the same chemical composition. The influences of metal ions and pH of solution on the recognition performance of MIP were investigated. The binding characteristics of MIP were evaluated by the Scatchard analysis with one-site and two-site binding equations, respectively. The results on substrate selectivity of imprinted polymer revealed that MIP had better binding affinity for template among the tested compounds.

  10. Development of a new toxic-unit model for the bioassessment of metals in streams

    Science.gov (United States)

    Schmidt, T.S.; Clements, W.H.; Mitchell, K.A.; Church, S.E.; Wanty, R.B.; Fey, D.L.; Verplanck, P.L.; San, Juan C.A.

    2010-01-01

    Two toxic-unit models that estimate the toxicity of trace-metal mixtures to benthic communities were compared. The chronic criterion accumulation ratio (CCAR), a modification of biotic ligand model (BLM) outputs for use as a toxic-unit model, accounts for the modifying and competitive influences of major cations (Ca2+, Mg2+, Na+, K+, H+), anions (HCO3−, CO32−,SO42−, Cl−, S2−) and dissolved organic carbon (DOC) in determining the free metal ion available for accumulation on the biotic ligand. The cumulative criterion unit (CCU) model, an empirical statistical model of trace-metal toxicity, considers only the ameliorative properties of Ca2+ and Mg2+ (hardness) in determining the toxicity of total dissolved trace metals. Differences in the contribution of a metal (e.g., Cu, Cd, Zn) to toxic units as determined by CCAR or CCU were observed and attributed to how each model incorporates the influences of DOC, pH, and alkalinity. Akaike information criteria demonstrate that CCAR is an improved predictor of benthic macroinvertebrate community metrics as compared with CCU. Piecewise models depict great declines (thresholds) in benthic macroinvertebrate communities at CCAR of 1 or more, while negative changes in benthic communities were detected at a CCAR of less than 1. We observed a 7% reduction in total taxa richness and a 43% decrease in Heptageniid abundance between background (CCAR = 0.1) and the threshold of chronic toxicity on the basis of continuous chronic criteria (CCAR = 1). In this first application of the BLM as a toxic-unit model, we found it superior to CCU.

  11. 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.

  12. Comparison of discharge silver concentrations from electrolytic plating and metallic replacement silver recovery units.

    Science.gov (United States)

    Harper, Martin; Siegel, Julie M

    2003-04-01

    Silver-based photographic X-ray film is made of solid crystals of silver chloride or silver bromide suspended in a gelatin and then coated on a film. During the X-ray developing process, the image is processed and the nonimage areas containing solid silver chloride or silver bromide crystals are removed in a solution called the fixer. There may be local environmental regulations that regulate the amount of silver discharged from a facility. To meet these regulations, many facilities have added silver recovery units to their processes. Two different types of recovery processes are in use in a large hospital and three clinics under study. All of the units were claimed by their respective manufacturers to be able to recover silver down to concentrations of 5 mg/L. This concentration would ensure that the building that houses each unit would meet the local county limit of 0.5 mg/L silver for total building silver discharge. The hypothesis for this research is that one system, newer and more expensive, consisting of so-called electrolytic plating units (EPUs) (which are followed by so-called metallic replacement units [MRUs] as a backup), will have better silver recovery than MRUs alone. A total of six units were sampled, three EPUs (in combination with MRUs) and three MRUs. The units were sampled once or twice a day for 10 days for a total of 17 samples from each. The samples then were analyzed by inductively coupled plasma spectroscopy, and an analysis of variance was performed on the results. The range for the electrolytic plating unit/metallic replacement unit combinations was 0.20-99.9 mg/L (mean of 35.15 mg/L; median of 33.8 mg/L). The range for the MRUs alone was 7.2-1112 mg/L (mean of 565.5 mg/L; median of 720 mg/L). Many individual results exceeded 5 mg/L, such that extensive dilution would be required to ensure the building effluent did not exceed 0.5 mg/L. It is suggested that the metallic replacement units be changed to EPUs (with metallic replacement backup

  13. Cutin and suberin monomers are membrane perturbants.

    Science.gov (United States)

    Douliez, Jean-Paul

    2004-03-15

    The interaction between cutin and suberin monomers, i.e., omega -hydroxylpalmitic acid, alpha, omega -hexadecanedioic acid, alpha, omega --hexadecanediol, 12-hydroxylstearic acid, and phospholipid vesicles biomimicking the lipid structure of plant cell membranes has been studied by optical and transmission electron microscopy, quasielastic light scattering, differential scanning calorimetry, and (31)P solid-state NMR. Monomers were shown to penetrate model membranes until a molar ratio of 30%, modulating their gel to fluid-phase transition, after which monomer crystals also formed in solution. These monomers induced a decrease of the phospholipid vesicle size from several micrometers to about 300 nm. The biological implications of these findings are discussed.

  14. Glassy dynamics of model colloidal polymers: The effect of "monomer" size

    Science.gov (United States)

    Li, Jian; Zhang, Bo-kai; Li, Hui-shu; Chen, Kang; Tian, Wen-de; Tong, Pei-qing

    2016-05-01

    In recent years, attempts have been made to assemble colloidal particles into chains, which are termed "colloidal polymers." An apparent difference between molecular and colloidal polymers is the "monomer" size. Here, we propose a model to represent the variation from molecular polymer to colloidal polymer and study the quantitative differences in their glassy dynamics. For chains, two incompatible local length scales, i.e., monomer size and bond length, are manifested in the radial distribution function and intramolecular correlation function. The mean square displacement of monomers exhibits Rouse-like sub-diffusion at intermediate time/length scale and the corresponding exponent depends on the volume fraction and the monomer size. We find that the threshold volume fraction at which the caging regime emerges can be used as a rescaling unit so that the data of localization length versus volume fraction for different monomer sizes can gather close to an exponential curve. The increase of monomer size effectively increases the hardness of monomers and thus makes the colloidal polymers vitrify at lower volume fraction. Static and dynamic equivalences between colloidal polymers of different monomer sizes have been discussed. In the case of having the same peak time of the non-Gaussian parameter, the motion of monomers of larger size is much less non-Gaussian. The mode-coupling critical exponents for colloidal polymers are in agreement with that of flexible bead-spring chains.

  15. Development of high performance vinyl acetate monomer (VAM) catalysts

    OpenAIRE

    2009-01-01

    The focus of this study was to develop high performance catalysts for the synthesis of vinyl acetate monomer (VAM). By systematic variation of different preparation parameters a multitude of shell catalysts consisting of PdAu nanoparticles supported on a bentonite carrier was explored. In order to investigate the influence of these alterations on catalytic performance, a catalyst classification was accomplished in a high-throughput Temkin test unit by comparison with a highly efficient commer...

  16. Polyelectrolyte properties of proteoglycan monomers

    Science.gov (United States)

    Li, Xiao; Reed, Wayne F.

    1991-03-01

    Light scattering measurements were made on proteoglycan monomers (PGM) over a wide range of ionic strengths Cs, and proteoglycan concentrations [PG]. At low Cs there were clear peaks in the angular scattering intensity curve I(q), which moved towards higher scattering wave numbers q, as [PG]1/3. This differs from the square root dependence of scattering peaks found by neutron scattering from more concentrated polyelectrolyte solutions. The peaks remained roughly fixed as Cs increased, but diminished in height, and superposed I(q) curves yielded a sort of isosbestic point. Under certain assumptions the static structure factor S(q) could be extracted from the measured I(q), and was found to retain a peak. A simple hypothesis concerning coexisting disordered and liquidlike correlated states is presented, which qualitatively accounts for the most salient features of the peaks. There was evidence of a double component scattering autocorrelation decay at low Cs, which, when resolved into two apparent diffusion coefficients, gave the appearance of simultaneous ``ordinary'' and ``extraordinary'' phases. The extraordinary phase was ``removable,'' however, by filtering. At higher Cs the proteoglycans appear to behave as random nonfree draining polyelectrolyte coils, with a near constant ratio of 0.67 between hydrodynamic radius and radius of gyration. The apparent persistence length varied as roughly the -0.50 power of ionic strength, similar to various linear synthetic and biological polyelectrolytes. Electrostatic excluded volume theory accounted well for the dependence of A2 on Cs.

  17. Overview of flow studies for recycling metal commodities in the United States

    Science.gov (United States)

    Sibley, Scott F.

    2011-01-01

    Metal supply consists of primary material from a mining operation and secondary material, which is composed of new and old scrap. Recycling, which is the use of secondary material, can contribute significantly to metal production, sometimes accounting for more than 50 percent of raw material supply. From 2001 to 2011, U.S. Geological Survey (USGS) scientists studied 26 metals to ascertain the status and magnitude of their recycling industries. The results were published in chapters A-Z of USGS Circular 1196, entitled, "Flow Studies for Recycling Metal Commodities in the United States." These metals were aluminum (chapter W), antimony (Q), beryllium (P), cadmium (O), chromium (C), cobalt (M), columbium (niobium) (I), copper (X), germanium (V), gold (A), iron and steel (G), lead (F), magnesium (E), manganese (H), mercury (U), molybdenum (L), nickel (Z), platinum (B), selenium (T), silver (N), tantalum (J), tin (K), titanium (Y), tungsten (R), vanadium (S), and zinc (D). Each metal commodity was assigned to a single year: chapters A-M have recycling data for 1998; chapters N-R and U-W have data for 2000, and chapters S, T, and X-Z have data for 2004. This 27th chapter of Circular 1196 is called AA; it includes salient data from each study described in chapters A-Z, along with an analysis of overall trends of metals recycling in the United States during 1998 through 2004 and additional up-to-date reviews of selected metal recycling industries from 1991 through 2008. In the United States for these metals in 1998, 2000, and 2004 (each metal commodity assigned to a single year), 84 million metric tons (Mt) of old scrap was generated. Unrecovered old scrap totaled 43 Mt (about 51 percent of old scrap generated, OSG), old scrap consumed was 38 Mt (about 45 percent of OSG), and net old scrap exports were 3.3 Mt (about 4 percent of OSG). Therefore, there was significant potential for increased recovery from scrap. The total old scrap supply was 88 Mt, and the overall new

  18. Controlling monomer-sequence using supramolecular templates

    OpenAIRE

    ten Brummelhuis, Niels

    2014-01-01

    The transcription and translation of information contained in nucleic acids that has been perfected by nature serves as inspiration for chemists to devise strategies for the creation of polymers with welldefined monomer sequences. In this review the various approaches in which templates (either biopolymers or synthetic ones) are used to influence the monomer-sequence are discussed.

  19. Critical load analysis in hazard assessment of metals using a Unit World Model.

    Science.gov (United States)

    Gandhi, Nilima; Bhavsar, Satyendra P; Diamond, Miriam L

    2011-09-01

    A Unit World approach has been used extensively to rank chemicals for their hazards and to understand differences in chemical behavior. Whereas the fate and effects of an organic chemical in a Unit World Model (UWM) analysis vary systematically according to one variable (fraction of organic carbon), and the chemicals have a singular ranking regardless of environmental characteristics, metals can change their hazard ranking according to freshwater chemistry, notably pH and dissolved organic carbon (DOC). Consequently, developing a UWM approach for metals requires selecting a series of representative freshwater chemistries, based on an understanding of the sensitivity of model results to this chemistry. Here we analyze results from a UWM for metals with the goal of informing the selection of appropriate freshwater chemistries for a UWM. The UWM loosely couples the biotic ligand model (BLM) to a geochemical speciation model (Windermere Humic Adsorption Model [WHAM]) and then to the multi-species fate transport-speciation (Transpec) model. The UWM is applied to estimate the critical load (CL) of cationic metals Cd, Cu, Ni, Pb, and Zn, using three lake chemistries that vary in trophic status, pH, and other parameters. The model results indicated a difference of four orders of magnitude in particle-to-total dissolved partitioning (K(d)) that translated into minimal differences in fate because of the short water residence time used. However, a maximum 300-fold difference was calculated in Cu toxicity among the three chemistries and three aquatic organisms. Critical loads were lowest (greatest hazard) in the oligotrophic water chemistry and highest (least hazard) in the eutrophic water chemistry, despite the highest fraction of free metal ion as a function of total metal occurring in the mesotrophic system, where toxicity was ameliorated by competing cations. Water hardness, DOC, and pH had the greatest influence on CL, because of the influence of these factors on aquatic

  20. Determination of Heavy Metals Concentration in Traditional Herbs Commonly Consumed in the United Arab Emirates

    Directory of Open Access Journals (Sweden)

    Rania Dghaim

    2015-01-01

    Full Text Available Herbs are extensively consumed in the United Arab Emirates for their flavoring and medicinal properties. This study aimed at determining the concentration of heavy metals in selected traditional herbs consumed in the United Arab Emirates (UAE. A total of 81 samples of seven herbs, parsley (Petroselinum crispum, basil (Ocimum basilicum, sage (Salvia officinalis, oregano (Origanum vulgare, mint (Mentha spicata, thyme (Thymus vulgaris, and chamomile (Matricaria chamomilla, were purchased from the local market in Dubai and analyzed for their cadmium, lead, copper, iron, and zinc contents. Microwave-assisted digestion was applied for the dissolution of the samples and heavy metals concentration was determined using Atomic Absorption Spectrometry (AAS. Metals were found to be present in varied concentrations in the herb samples. The concentration ranges were found as follows: less than 0.1–1.11 mg·kg−1 for cadmium, less than 1.0–23.52 mg·kg−1 for lead, 1.44–156.24 mg·kg−1 for copper, 12.65–146.67 mg·kg−1 for zinc, and 81.25–1101.22 mg·kg−1 for iron. The findings of the study suggest that most of the analyzed herbs contained unsafe levels of heavy metals that exceeded the World Health Organization (WHO permissible limits (PL.

  1. 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.

  2. Cyclic Polymer with Alternating Monomer Sequence.

    Science.gov (United States)

    Zhu, Wen; Li, Zi; Zhao, Youliang; Zhang, Ke

    2015-11-01

    Cyclic polymers with alternating monomer sequence are synthesized for the first time based on the ring-closure strategy. Well-defined telechelic alternating polymers are synthesized by reversible addition-fragmentation chain transfer polymerization by copolymerizing the electron acceptor monomer of N-benzylmaleimide and donor monomer of styrene with a feed ratio of 1 between them. The corresponding cyclic alternating polymers are then produced by the UV-induced Diels-Alder click reaction to ring-close the linear alternating polymer precursors under highly diluted reaction solution.

  3. Titanium recycling in the United States in 2004, chap. Y of Sibley, S.F., ed., Flow studies for recycling metal commodities in the United States

    Science.gov (United States)

    Goonan, Thomas G.

    2010-01-01

    As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the titanium metal fraction of the titanium economy, which generates and uses titanium metal scrap in its operations. Data for 2004 were selected to demonstrate the titanium flows associated with these operations. This report includes a description of titanium metal supply and demand in the United States to illustrate the extent of titanium recycling and to identify recycling trends. In 2004, U.S. apparent consumption of titanium metal (contained in various titanium-bearing products) was 45,000 metric tons (t) of titanium, which was distributed as follows: 25,000 t of titanium recovered as new scrap, 9,000 t of titanium as titanium metal and titanium alloy products delivered to the U.S. titanium products reservoir, 7,000 t of titanium consumed by steelmaking and other industries, and 4,000 t of titanium contained in unwrought and wrought products exported. Titanium recycling is concentrated within the titanium metals sector of the total titanium market. The titanium market is otherwise dominated by pigment (titanium oxide) products, which generate dissipative losses instead of recyclable scrap. In 2004, scrap (predominantly new scrap) was the source of roughly 54 percent of the titanium metal content of U.S.-produced titanium metal products.

  4. Advances in metals classification under the United Nations globally harmonized system of classification and labeling.

    Science.gov (United States)

    Skeaff, James; Adams, William J; Rodriguez, Patricio; Brouwers, Tony; Waeterschoot, Hugo

    2011-10-01

    This article shows how regulatory obligations mandated for metal substances can be met with a laboratory-based transformation/dissolution (T/D) method for deriving relevant hazard classification outcomes, which can then be linked to attendant environmental protection management decisions. We report the results of a ring-test at 3 laboratories conducted to determine the interlaboratory precision of the United Nations T/D Protocol (T/DP) in generating data for classifying 4 metal-bearing substances for acute and chronic toxicity under the United Nations Globally Harmonized System of Classification and Labelling (GHS) criteria with respect to the aquatic environment. The test substances were Ni metal powder, cuprous oxide (Cu(2) O) powder, tricobalt tetroxide (Co(3) O(4) ) powder, and cuttings of a NILO K Ni-Co-Fe alloy. Following GHS Annex 10 guidelines, we tested 3 loadings (1, 10, and 100 mg/L) of each substance at pH 6 and 8 for 7 or 28 d to yield T/D data for acute and chronic classification, respectively. We compared the T/DP results (dissolved metal in aqueous media) against acute and chronic ecotoxicity reference values (ERVs) for each substance to assess GHS classification outcomes. For dissolved metal ions, the respective acute and chronic ERVs established at the time of the T/D testing were: 29 and 8 µg/L for Cu; 185 and 1.5 µg/L for Co; and 13.3 and 1.0 mg/L for Fe. The acute ERVs for Ni were pH-dependent: 120 and 68 µg/L at pH 6 and 8, respectively, whereas the chronic ERV for Ni was 2.4 µg/L. The acute classification outcomes were consistent among 3 laboratories: cuprous oxide, Acute 1; Ni metal powder, Acute 3; Co(3) O(4) and the NILO K alloy, no classification. We obtained similar consistent results in chronic classifications: Cu(2) O, Ni metal powder, and Co(3) O(4) , Chronic 4; and the NILO K alloy, no classification. However, we observed equivocal results only in 2 of a possible 48 cases where the coefficient of variation of final T

  5. Local and systemic effects of unpolymerised monomers

    Directory of Open Access Journals (Sweden)

    Sulekha Siddharth Gosavi

    2010-01-01

    Full Text Available Methyl methacrylate (MMA, a widely used monomer in dentistry and medicine has been reported to cause abnormalities or lesions in several organs. Experimental and clinical studies have documented that monomers may cause a wide range of adverse health effects such as irritation to skin, eyes, and mucous membranes, allergic dermatitis, stomatitis, asthma, neuropathy, disturbances of the central nervous system, liver toxicity, and fertility disturbances.

  6. Occupational and Qualification Structures in the Field of Environmental Protection in the Metal and Chemical Industries in the United Kingdom.

    Science.gov (United States)

    European Centre for the Development of Vocational Training, Berlin (Germany).

    A study analyzed the occupational structure and qualifications associated with the field of environmental protection in the metal and chemical industries in the United Kingdom. The analysis included nine case studies based on interviews with firms in the chemicals and metals sectors. Information was gathered within an analytical framework that…

  7. 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.

  8. Computational design of metal-organic frameworks with paddlewheel-type secondary building units

    Science.gov (United States)

    Schwingenschlogl, Udo; Peskov, Maxim V.; Masghouni, Nejib

    We employ the TOPOS package to study 697 coordination polymers containing paddlewheel-type secondary building units. The underlying nets are analyzed and 3 novel nets are chosen as potential topologies for paddlewheel-type metal organic frameworks (MOFs). Dicarboxylate linkers are used to build basic structures for novel isoreticular MOF series, aiming at relatively compact structures with a low number of atoms per unit cell. The structures are optimized using density functional theory. Afterwards the Grand Canonical Monte Carlo approach is employed to generate adsorption isotherms for CO2, CO, and CH4 molecules. We utilize the universal forcefield for simulating the interaction between the molecules and hosting MOF. The diffusion behavior of the molecules inside the MOFs is analyzed by molecular dynamics simulations.

  9. Design and simulation of an activated sludge unit associated to a continuous reactor to remove heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    D`Avila, J.S.; Nascimento, R.R. [Ambientec Consultoria Ltda., Aracaju, SE (Brazil)

    1993-12-31

    A software was developed to design and simulate an activated sludge unit associated to a new technology to remove heavy metals from wastewater. In this process, a continuous high efficiency biphasic reactor operates by using particles of activated peat in conjugation with the sludge unit. The results obtained may be useful to increase the efficiency or to reduce the design and operational costs involved in a activated sludge unit. (author). 5 refs., 2 tabs.

  10. Tandem ring-opening/ring-closing metathesis polymerization: relationship between monomer structure and reactivity.

    Science.gov (United States)

    Park, Hyeon; Lee, Ho-Keun; Choi, Tae-Lim

    2013-07-24

    Monomers containing either cycloalkenes with low ring strain or 1-alkynes are poor monomers for olefin metathesis polymerization. Ironically, keeping two inactive functional groups in proximity within one molecule can make it an excellent monomer for metathesis polymerization. Recently, we demonstrated that monomer 1 having cyclohexene and propargyl moieties underwent rapid tandem ring-opening/ring-closing metathesis (RO/RCM) polymerization via relay-type mechanism. Furthermore, living polymerization was achieved when a third-generation Grubbs catalyst was used. Here, we present a full account on this tandem polymerization by investigating how various structural modifications of the monomers affected the reactivity of the tandem polymerization. We observed that changing the ring size of the cycloalkene moieties, the length of the alkynes, and linker units influenced not only the polymerization rates but also the reactivities of Diels-Alder reaction, which is a post-modification reaction of the resulting polymers. Also, the mechanism of tandem polymerization was studied by conducting end-group analysis using (1)H NMR analysis, thereby concluding that the polymerization occurred by the alkyne-first pathway. With this mechanistic conclusion, factors responsible for the dramatic structure-reactivity relationship were proposed. Lastly, tandem RO/RCM polymerization of monomers containing sterically challenging trisubstituted cycloalkenes was successfully carried out to give polymer repeat units having tetrasubstituted cycloalkenes.

  11. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.

    1992-10-01

    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  12. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.

    1992-10-01

    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  13. Expanded organic building units for the construction of highly porous metal-organic frameworks.

    Science.gov (United States)

    Kong, Guo-Qiang; Han, Zhi-Da; He, Yabing; Ou, Sha; Zhou, Wei; Yildirim, Taner; Krishna, Rajamani; Zou, Chao; Chen, Banglin; Wu, Chuan-De

    2013-10-25

    Two new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST-1. Because the organic linkers in ZJU-35 and ZJU-36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST-1 to 14.4 Å in ZJU-35 and 16.5 Å in ZJU-36, thus leading to their higher porosities with Brunauer-Emmett-Teller (BET) surface areas of 2899 and 4014 m(2) g(-1) for ZJU-35 and ZJU-36, respectively. High-pressure gas-sorption isotherms indicate that both ZJU-35 and ZJU-36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high-pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU-35 and ZJU-36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self-assembled from organic tetra- and hexacarboxylates that contain m-benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self-assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra- and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated

  14. 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 tempera...

  15. Producing monomers and polymers from plant oils

    Science.gov (United States)

    The integration of biobased industrial products into existing markets, where petrochemically-derived materials currently dominate, is a worthy objective. This chapter reviews some technologies that have been developed including olefins of various chain lengths, photo-curable polymers, vinyl monomers...

  16. A Homochiral Multifunctional Metal-Organic Framework with Rod-Shaped Secondary Building Units

    Directory of Open Access Journals (Sweden)

    Kun Cai

    2017-04-01

    Full Text Available A new homochiral multifunctional metal-organic framework, [Zn2(CTBA2·H2O] (JUC-112, was synthesized under solvothermal conditions, through the design of chiral ligand 4-(3-carboxy-2,2,3-trimethylcyclopentanecarboxamido benzoic acid (H2CTBA based on camphoric acid as building block. The crystal structure of the new material is a 2-dimensional (2D chiral layer packed with infinite rod-shaped secondary building units (SBUs. The homochiral framework was identified by circular dichroism (CD spectrum. Thermogravimetric measurement indicates its high thermal stability up to 450 °C. In addition, JUC-112 exhibits the capability of separating water from alcohols, second-order nonlinear optical effect, and photoluminescence.

  17. A Homochiral Multifunctional Metal-Organic Framework with Rod-Shaped Secondary Building Units

    Science.gov (United States)

    Cai, Kun; Zhao, Nian; Zhang, Ning; Sun, Fu-Xing; Zhao, Qing; Zhu, Guang-Shan

    2017-01-01

    A new homochiral multifunctional metal-organic framework, [Zn2(CTBA)2·H2O] (JUC-112), was synthesized under solvothermal conditions, through the design of chiral ligand 4-(3-carboxy-2,2,3-trimethylcyclopentanecarboxamido) benzoic acid (H2CTBA) based on camphoric acid as building block. The crystal structure of the new material is a 2-dimensional (2D) chiral layer packed with infinite rod-shaped secondary building units (SBUs). The homochiral framework was identified by circular dichroism (CD) spectrum. Thermogravimetric measurement indicates its high thermal stability up to 450 °C. In addition, JUC-112 exhibits the capability of separating water from alcohols, second-order nonlinear optical effect, and photoluminescence. PMID:28430135

  18. Release of monomers from composite dust.

    Science.gov (United States)

    Cokic, S M; Duca, R C; Godderis, L; Hoet, P H; Seo, J W; Van Meerbeek, B; Van Landuyt, K L

    2017-05-01

    Dental personnel are more at risk to develop asthmatic disease, but the exact reason is so far unknown. During abrasive procedures, dental personnel are exposed to nano-sized dust particles released from dental composite. The aim of this study was to investigate whether respirable composite dust may also release monomers. Respirable (composite dust was collected and the release of methacrylate monomers and Bisphenol A (BPA) in water and ethanol was evaluated by liquid chromatography/mass spectroscopy (LC-MS/MS). The dust was ultra-morphologically and chemically analyzed by transmission electron microscopy and energy-dispersive X-ray spectroscopy (TEM-EDS). LC-MS/MS analysis revealed that, irrespective of the type of composite, the respirable fraction of composite dust may release relatively high concentrations of unpolymerized methacrylate monomers, both in water and ethanol. Higher release was observed in ethanol. The endocrine disruptor BPA also emanated from the composite dust particles. TEM showed that most particles were nano-sized, although particle size ranged between 6nm and 5μm with a mode value between 12 and 39nm. Most particles consisted of several filler particles in resin matrix, although single nano-filler particles could also be observed. Elemental analysis by TEM-EDS proved that the particles collected on the filters originated from the dental composites. Theoretically, composite dust may function as a vehicle to transport monomers deeply into the respiratory system. The results of this study may shed another light on the increasing incidence of respiratory disease among dental personnel, and more care should be taken to prevent inhalation of composite dust. Special care should be taken to prevent inhalation of composite dust, as the dust particles may release methacrylate monomers. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Trace metal concentrations and lead isotopic composition in surface waters of the Northeast Pacific along the United States - Mexico boundary

    Energy Technology Data Exchange (ETDEWEB)

    Sanudo-Wilhelmy, S. (Inst. of Marine Science, Santa Cruz, CA (United States))

    1990-01-09

    To evaluate the magnitude of heavy metal contamination along the United States - Mexico boundary, trace metal concentrations (Pb, Cd, Mn, Fe, and Zn) and lead isotopic composition ([sup 204]Pb, [sup 206]Pb, [sup 207]Pb, and [sup 208]Pb) were measured along four surface water transects across the continental shelf off the Baja California Coast. The stations were located between 2 to 45 km offshore, including both coastal and open ocean locations. All the metal distributions along the transects were characterized by offshore concentration gradients. The highest trace metal concentrations occurred in coastal waters in association with high salinities and nutrient concentrations. There was also a longshore gradient in trace metal concentrations. Trace element concentrations were lower in the southern locations than along the United States - Mexico boundary, and were comparable to typical open ocean values. The relative enrichment of metals in surface waters off the northern part of Baja California was primarily associated with advection/upwelling processes, not with anthropogenic inputs. Mass balance calculations indicated that about 1% of Cd and 13% of Zn were from urban discharges. The low metal levels measured in coastal waters off the central part of Baja California were attributed to the intrusion of open ocean waters, based on hydrographic data, satellite images and lead isotopic compositions.

  20. 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.

  1. Functionalization of nanodiamond with epoxy monomer

    Institute of Scientific and Technical Information of China (English)

    Huan Huan Zhang; Ya Ting Liu; Rong Wang; Xiao Yan Yu; Xiong Wei Qu; Qing Xin Zhang

    2011-01-01

    A novel nanodiamond-epoxy derivative (ND-EP) was synthesized by grafting epoxy monomers onto the surface of nanodiamond (ND), and characterized by FTIR and TGA. The ratio of grafted epoxy groups was determined to be 32.5 wt% by TGA. The developed methodology provides an efficient method for the functionalization of nanodiamond material, which enables a variety of advanced engineering and biomedical applications of ND.

  2. Quantifying missing annual emission sources of heavy metals in the United Kingdom with an atmospheric transport model

    Energy Technology Data Exchange (ETDEWEB)

    Dore, Anthony J., E-mail: todo@ceh.ac.uk [Centre for Ecology and Hydrology (United Kingdom); Hallsworth, Stephen [Centre for Ecology and Hydrology (United Kingdom); McDonald, Alan G. [Scottish Environment Protection Agency (United Kingdom); Werner, Małgorzata; Kryza, Maciej [Department of Climatology and Atmosphere Protection, University of Wrocław (Poland); Abbot, John [Ricardo-AEA, Didcot (United Kingdom); Nemitz, Eiko [Centre for Ecology and Hydrology (United Kingdom); Dore, Christopher J. [Aether Ltd., Oxford (United Kingdom); Malcolm, Heath; Vieno, Massimo; Reis, Stefan; Fowler, David [Centre for Ecology and Hydrology (United Kingdom)

    2014-05-01

    An atmospheric chemical transport model was adapted to simulate the concentration and deposition of heavy metals (arsenic, cadmium, chromium, copper, lead, nickel, selenium, vanadium, and zinc) in the United Kingdom. The model showed that wet deposition was the most important process for the transfer of metals from the atmosphere to the land surface. The model achieved a good correlation with annually averaged measurements of metal concentrations in air. The correlation with measurements of wet deposition was less strong due to the complexity of the atmospheric processes involved in the washout of particulate matter which were not fully captured by the model. The measured wet deposition and air concentration of heavy metals were significantly underestimated by the model for all metals (except vanadium) by factors between 2 and 10. These results suggest major missing sources of annual heavy metal emissions which are currently not included in the official inventory. Primary emissions were able to account for only 9%, 21%, 29%, 21%, 36%, 7% and 23% of the measured concentrations for As, Cd, Cr, Cu, Ni, Pb and Zn. A likely additional contribution to atmospheric heavy metal concentrations is the wind driven re-suspension of surface dust still present in the environment from the legacy of much higher historic emissions. Inclusion of two independent estimates of emissions from re-suspension in the model was found to give an improved agreement with measurements. However, an accurate estimate of the magnitude of re-suspended emissions is restricted by the lack of measurements of metal concentrations in the re-suspended surface dust layer. - Highlights: • Concentrations and deposition of 9 heavy metals in the UK were simulated. • Modelled data were well correlated to measured concentrations and deposition. • The model greatly underestimated metal deposition and air concentrations. • Under-estimation was attributed to wind-driven re-suspension of surface dust.

  3. 40 CFR Table 3 to Subpart Uuu of... - Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continous Monitoring Systems for Metal... Units Pt. 63, Subpt. UUU, Table 3 Table 3 to Subpart UUU of Part 63—Continous Monitoring Systems for... CFR 60.102 a. Over 20,000 barrels per day fresh feed capacity Electrostatic precipitator Continuous...

  4. Ab Initio Study of the Adsorption of Small Molecules on Metal-Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion.

    Science.gov (United States)

    Mavrandonakis, Andreas; Vogiatzis, Konstantinos D; Boese, A Daniel; Fink, Karin; Heine, Thomas; Klopper, Wim

    2015-09-08

    The interactions of H2, CO, CO2, and H2O with the undercoordinated metal centers of the trimetallic oxo-centered M3(III)(μ3-O)(X) (COO)6 moiety are studied by means of wave function and density functional theory. This trimetallic oxo-centered cluster is a common building unit in several metal-organic frameworks (MOFs) such as MIL-100, MIL-101, and MIL-127 (also referred to as soc-MOF). A combinatorial computational screening is performed for a large variety of trimetallic oxo-centered units M3(III)O (M = Al(3+), Sc(3+), V(3+), Cr(3+), Fe(3+), Ga(3+), Rh(3+), In(3+), Ir(3+)) interacting with H2O, H2, CO, and CO2. The screening addresses interaction energies, adsorption enthalpies, and vibrational properties. The results show that the Rh and Ir analogues are very promising materials for gas storage and separations.

  5. A Metal-Organic Framework Containing Unusual Eight-Connected Zr–-Oxo Secondary Building Units and Orthogonal Carboxylic Acids for Ultra-sensitive Metal Detection

    Energy Technology Data Exchange (ETDEWEB)

    Carboni, Michaël; Lin, Zekai; Abney, Carter W.; Zhang, Teng; Lin, Wenbin (UC)

    2015-08-21

    Two metal-organic frameworks (MOFs) with Zr-oxo secondary building units (SBUs) were prepared by using p,p'-terphenyldicarboxylate (TPDC) bridging ligands pre-functionalized with orthogonal succinic acid (MOF-1) and maleic acid groups (MOF-2). Single-crystal X-ray structure analysis of MOF-1 provides the first direct evidence for eight-connected SBUs in UiO-type MOFs. In contrast, MOF-2 contains twelve-connected SBUs as seen in the traditional UiO MOF topology. These structural assignments were confirmed by extended X-ray absorption fine structure (EXAFS) analysis. The highly porous MOF-1 is an excellent fluorescence sensor for metal ions with the detection limit of <0.5 ppb for Mn2+ and three to four orders of magnitude greater sensitivity for metal ions than previously reported luminescent MOFs.

  6. Induced DNA damage by dental resin monomers in somatic cells.

    Science.gov (United States)

    Arossi, Guilherme Anziliero; Lehmann, Mauricio; Dihl, Rafael Rodrigues; Reguly, Maria Luiza; de Andrade, Heloisa Helena Rodrigues

    2010-02-01

    The present in vivo study investigated the genotoxicity of four dental resin monomers: triethyleneglycoldimethacrylate (TEGDMA), hydroxyethylmethacrylate (HEMA), urethanedimethacrylate (UDMA) and bisphenol A-glycidylmethacrylate (BisGMA). The Somatic Mutation and Recombination Test (SMART) in Drosophila melanogaster was applied to analyse their genotoxicity expressed as homologous mitotic recombination, point and chromosomal mutation. SMART detects the loss of heterozygosity of marker genes expressed phenotypically on the fly's wings. This fruit fly has an extensive genetic homology to mammalians, which makes it a suitable model organism for genotoxic investigations. The present findings provide evidence that the mechanistic basis underlying the genotoxicity of UDMA and TEGDMA is related to homologous recombination and gene/chromosomal mutation. A genotoxic pattern can correspondingly be discerned for both UDMA and TEGDMA: their genotoxicity is attributed respectively to 49% and 44% of mitotic recombination, as well as 51% and 56% of mutational events, including point and chromosomal alterations. The monomer UDMA is 1.6 times more active than TEGDMA to induce mutant clones per treatment unit. BisGMA and HEMA had no statistically significant effect on total spot frequencies - suggesting no genotoxic action in the SMART assay. The clinical significance of these observations has to be interpreted for data obtained in other bioassays.

  7. Interactions of univalent counterions with headgroups of monomers and dimers of an anionic surfactant.

    Science.gov (United States)

    Jakubowska, Anna

    2015-03-24

    Specific ion effects in solution are related to the hydrated ion size and ion hydration, electrostatic interactions, dispersion forces, ion effects on water structure, and ion modification of surface tension. In this study, we tried to identify which factor determines the ion specificity observed. The preference and energy of metal cations binding with the headgroups of dodecylsulfate (DS) monomers and dimers were determined by mass spectrometry. In the gas phase, cation binding to DS dimer headgroups depends strongly on the cation radius. On the other hand, the interactions between DS monomer headgroups and chaotropic ions depend on the cation polarizability, and the binding of kosmotropic cations to DS monomer headgroups strongly depends on the Gibbs free energies of ion hydration. DS dimers are related to surfactants having doubly charged headgroups, and DS monomers are related to surfactants with singly charged headgroups. Our spectrometric study of the strength of counterion binding to free monomers of a surfactant provides insight into surfactant-counterion interactions at micellar interfaces in bulk solution.

  8. 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...

  9. Comparison of Bond Strength of Metal and Ceramic Brackets Bonded with Conventional and High-Power LED Light Curing Units

    Science.gov (United States)

    Chalipa, Javad; Jalali, Yasamin Farajzadeh; Gorjizadeh, Fatemeh; Baghaeian, Pedram; Hoseini, Mohammad Hashem

    2016-01-01

    Objectives: The aim of this study was to evaluate the effect of conventional and high-power light emitting diode (LED) light curing units on shear bond strength (SBS) of metal and ceramic brackets to tooth surface. Materials and Methods: Forty sound bovine maxillary central incisors were used for the study. The teeth were divided into four groups (n=10). Teeth surfaces were etched with 37% phosphoric acid for 20 seconds. After applying a uniform layer of adhesive primer on the etched enamel, composite was placed on the base of brackets. The samples were light cured according to the manufacturer’s instructions and thermocycled. The SBS was measured. The failure mode was scored using the adhesive remnant index (ARI). Results: The mean SBS of samples in groups A (high-power LED, metal bracket), B (high-power LED, ceramic bracket), C (conventional LED, metal bracket) and D (conventional LED, ceramic bracket) was 23.1±3.69, 10.7±2.06, 24.92±6.37 and 10.74±3.18MPa, respectively. The interaction effect of type of LED unit (high-power/conventional) and bracket type on SBS was not statistically significant (P=0.483). In general, type of LED unit did not affect SBS. Type of bracket significantly affected SBS (P<0.001). The ARI score was not significantly influenced by the interaction between the type of LED unit and bracket. Conclusions: The obtained SBS is the same for both bracket types by use of high-power and conventional LED light curing units. Regardless of the type of LED unit, SBS of ceramic brackets was significantly lower than that of metal brackets.

  10. A review of our development of dental adhesives--effects of radical polymerization initiators and adhesive monomers on adhesion.

    Science.gov (United States)

    Ikemura, Kunio; Endo, Takeshi

    2010-03-01

    This paper reviews the development of dental adhesives by collating information of related studies from original scientific papers, reviews, and patent literatures. Through our development, novel radical polymerization initiators, adhesive monomers, and microcapsules were synthesized, and their effects on adhesion were investigated. It was found that 5-monosubstituted barbituric acid (5-MSBA)-containing ternary initiators in conjunction with adhesive monomers contributed to effective adhesion with good polymerization reactivity. Several kinds of novel adhesive monomers bearing carboxyl group, phosphonic acid group or sulfur-containing group were synthesized, and investigated their multi-purpose bonding functions. It was suggested that the flexible methylene chain in the structure of adhesive monomers played a pivotal role in their enhanced bonding durability. It was found that the combination of acidic monomers with sulfur-containing monomer markedly improved adhesion to enamel, dentin, porcelain, alumina, zirconia, non-precious metals and precious metals. A new poly(methyl methacrylate) (PMMA)-type adhesive resin comprising microencapsulated polymerization initiators was also found to exhibit both good formulation stability and excellent adhesive property.

  11. 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.

  12. Static and dynamical critical behavior of the monomer-monomer reaction model with desorption

    Science.gov (United States)

    da Costa, E. C.; Rusch, Flávio Roberto

    2016-06-01

    We studied in this work the monomer-monomer reaction model on a linear chain. The model is described by the following reaction: A + B → AB, where A and B are two monomers that arrive at the surface with probabilities yA and yB, respectively, and we have considered desorption of the monomer B with probability α. The model is studied in the adsorption controlled limit where the reaction rate is infinitely larger than the adsorption rate. We employ site and pair mean-field approximations as well as static and dynamical Monte Carlo simulations. We show that the model exhibits a continuous phase transition between an active steady state and an A-absorbing state, when the parameter yA is varied through a critical value, which depends on the value of α. Monte Carlo simulations and finite-size scaling analysis near the critical point are used to determine the static critical exponents β and ν⊥ and the dynamical critical exponents ν∥ and z. The results found for the monomer-monomer reaction model with B desorption, in the linear chain, are different from those found by E. V. Albano (Albano, 1992) and are in accordance with the values obtained by Jun Zhuo and Sidney Redner (Zhuo and Redner, 1993), and endorse the conjecture of Grassberger, which states that any system undergoing a continuous phase transition from an active steady state to a single absorbing state, exhibits the same critical behavior of the directed percolation universality class.

  13. An unprecedented Co(II) cuboctahedron as the secondary building unit in a Co-based metal-organic framework.

    Science.gov (United States)

    Holmberg, Rebecca J; Kay, Marika; Korobkov, Ilia; Kadantsev, Eugene; Boyd, Peter G; Aharen, Tomoko; Desgreniers, Serge; Woo, Tom K; Murugesu, Muralee

    2014-05-25

    A cubic metal-organic framework with an unprecedented octanuclear secondary building unit (SBU) was isolated. The obtained SBU is composed of 8 Co(II) ions at each vertex, 6 μ4-OH groups at each face, and 12 cpt(-) ligands framing the metal core. The cuboctahedra arrange in a ubt framework topology, eliciting a highly symmetrical MOF structure. Magnetic measurements as well as DFT calculations on this crystalline MOF reveal intramolecular antiferromagnetic coupling between Co(II) ions in the octanuclear SBU.

  14. The effect of sprue design and alloy type on the fit of three-unit metal/ceramic bridges.

    Science.gov (United States)

    Johnson, A

    1995-12-01

    This study was designed to compare the effect of three sprue designs and three types of metal alloy/ceramic on the accuracy of fit of three unit bridges. A sprue design which has straight sprues attached directly to the pattern but does not have a button of excess metal connecting the sprues together after casting, produced the best marginal accuracy, irrespective of the alloy type used. Of the three alloys used (gold, palladium and nickel/chromium based alloys) the gold alloy produced better fitting bridges with each sprue design used.

  15. Close-packed polymer crystals from two-monomer-connected precursors

    Science.gov (United States)

    Lee, Hong-Joon; Jo, Yong-Ryun; Kumar, Santosh; Yoo, Seung Jo; Kim, Jin-Gyu; Kim, Youn-Joong; Kim, Bong-Joong; Lee, Jae-Suk

    2016-09-01

    The design of crystalline polymers is intellectually stimulating and synthetically challenging, especially when the polymerization of any monomer occurs in a linear dimension. Such linear growth often leads to entropically driven chain entanglements and thus is detrimental to attempts to realize the full potential of conjugated molecular structures. Here we report the polymerization of two-monomer-connected precursors (TMCPs) in which two pyrrole units are linked through a connector, yielding highly crystalline polymers. The simultaneous growth of the TMCP results in a close-packed crystal in polypyrrole (PPy) at the molecular scale with either a hexagonal close-packed or face-centred cubic structure, as confirmed by high-voltage electron microscopy, and the structure that formed could be controlled by simply changing the connector. The electrical conductivity of the TMCP-based PPy is almost 35 times that of single-monomer-based PPy, demonstrating its promise for application in diverse fields.

  16. Differences in aerosol trace metals between the northern Caribbean and southeastern United States.

    Science.gov (United States)

    Miller, R. C.

    2002-12-01

    Five Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring stations in the southeastern United States and the U.S. Virgin Islands (U.S.V.I.), clearly show the metals in aerosols are derived from two different sources. The aerosols are collected by IMPROVE samplers and passed through a series of filter cassettes that are analyzed at University of California, Davis laboratories. Teflon, nylon and quartz filters were used to collect fine particles, PM2.5, while a fourth filter of Teflon collected PM10 particles. The Teflon filters that collected PM10 particles were analyzed using gravimetric analysis. The second Teflon filter was used to measure elements and mass; Particle Induced X-Ray Emission (PIXE) and X-Ray Fluorescence (XRF) were used to measure the concentrations of the elements from sodium to lead while Proton Elastic Scattering Analysis (PESA) was used to measure hydrogen concentrations. Nylon filters were used to measure nitrate, sulfate and chloride concentrations by ion chromatography. The average yearly concentrations in η g m-3 of copper, iron, potassium and zinc, one of the elemental groups tested by IMPROVE, in the U.S.V.I. aerosols are 0.20 η g m-3, 176.49 η g m-3, 89.32 η g m-3and 1.61 η g m-3. In Sipsy Wilderness, Alabama the concentrations are 1.37 η g m-3, 50.06 η g m-3, 61.03 η g m-3and 9.86 η g m-3respectively. Statistical analysis of the data indicates that the composition of the aerosols at the more northern sites of Sipsy Wilderness, Alabama, Okefenokee National Wildlife Reserve, Georgia and Chassahowitzka Wildlife Refuge, Florida are distinctly different than the Everglades National Park (E.N.P.), Florida and the U.S.V.I. Correlations of elements at the U.S.V.I. and E.N.P. sites are similar and the correlation coefficients are strong (> 0.75) for elements considered to be of terrestrial source. At the northern sites, there is no relation among the metals. Examination of the annual data with cluster analysis

  17. 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

  18. Effect of the microhardness difference between base metal and bionic coupling unit on wear resistance of gray cast iron

    Science.gov (United States)

    Pang, Zuobo; Zhou, Hong; Chang, Fang; Zhang, Peng; Cong, Dalong; Meng, Chao; Wang, Chuanwei; Ren, Luquan

    2015-12-01

    In order to improve the wear resistance of gray cast iron guide rail, the samples with different microhardness difference between bionic coupling units and base metal were manufactured by laser surface remelting. Wear behavior of gray cast iron with bionic coupling units has been studied under dry sliding condition at room temperature using a homemade liner reciprocating wear testing machine. The wear resistance was evaluated by means of weight loss measurement and wear morphology. The results indicated that when the microhardness difference is 561 HV0.2, the wear resistance of sample is the best.

  19. Quantifying missing annual emission sources of heavy metals in the United Kingdom with an atmospheric transport model.

    Science.gov (United States)

    Dore, Anthony J; Hallsworth, Stephen; McDonald, Alan G; Werner, Małgorzata; Kryza, Maciej; Abbot, John; Nemitz, Eiko; Dore, Christopher J; Malcolm, Heath; Vieno, Massimo; Reis, Stefan; Fowler, David

    2014-05-01

    An atmospheric chemical transport model was adapted to simulate the concentration and deposition of heavy metals (arsenic, cadmium, chromium, copper, lead, nickel, selenium, vanadium, and zinc) in the United Kingdom. The model showed that wet deposition was the most important process for the transfer of metals from the atmosphere to the land surface. The model achieved a good correlation with annually averaged measurements of metal concentrations in air. The correlation with measurements of wet deposition was less strong due to the complexity of the atmospheric processes involved in the washout of particulate matter which were not fully captured by the model. The measured wet deposition and air concentration of heavy metals were significantly underestimated by the model for all metals (except vanadium) by factors between 2 and 10. These results suggest major missing sources of annual heavy metal emissions which are currently not included in the official inventory. Primary emissions were able to account for only 9%, 21%, 29%, 21%, 36%, 7% and 23% of the measured concentrations for As, Cd, Cr, Cu, Ni, Pb and Zn. A likely additional contribution to atmospheric heavy metal concentrations is the wind driven re-suspension of surface dust still present in the environment from the legacy of much higher historic emissions. Inclusion of two independent estimates of emissions from re-suspension in the model was found to give an improved agreement with measurements. However, an accurate estimate of the magnitude of re-suspended emissions is restricted by the lack of measurements of metal concentrations in the re-suspended surface dust layer.

  20. Distribution of heavy metal concentrations in surface sediments in Dubai Creeks, United Arab Emirates.

    Science.gov (United States)

    Howari, Fares M

    2005-01-01

    Dubai is developing rapidly and many developmental activities are concentrated around its Creek. The present study reports the lateral distribution of heavy metals and compares it with local historical record of heavy metal concentrations. For this purpose surface sediment samples were collected and analyzed for metal contents, total organic carbon content (TOC), mineralogy and grain size. The percentages of the different grain size fraction of the collected sediments were as follow 65% for sand size, 15% for silt size fraction, and the rest accounted for clay size fraction. The microscopic analyses indicate that the sediment composed mainly from carbonate and quartz with traces of rock fragments. Such mineral composition is not believed to be a potential source of heavy metal. The study found that the average recorded heavy metal concentrations in the collected sediment samples were 87, 96, 127, 38.5, and 279 ppm for Cr, Cu, Ni, Pb, and Zn, respectively. Those values were slightly higher than metal concentrations recoded in 2001 with 1.22 (Cr), 2.5 (Cu), 2.87 (Ni), 0.69 (Pb), and 2.1 (Zn) folds. However, in 2001 and 2003 the measured metal contents, along the creek, were lower than those of the average earth crust. Along the Creek most metals recorded the highest concentrations in the upper reach of the Creek. The distribution of the measured heavy metals was not affected significantly with the TOC values. The present study also documented obvious related point sources of pollution.

  1. 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 

  2. Synthesis and characterization of nitroaromatic peptoids: fine tuning peptoid secondary structure through monomer position and functionality.

    Science.gov (United States)

    Fowler, Sarah A; Luechapanichkul, Rinrada; Blackwell, Helen E

    2009-02-20

    N-substituted glycine oligomers, or peptoids, have emerged as an important class of foldamers for the study of biomolecular interactions and for potential use as therapeutic agents. However, the design of peptoids with well-defined conformations a priori remains a formidable challenge. New approaches are required to address this problem, and the systematic study of the role of individual monomer units in the global peptoid folding process represents one strategy. Here, we report our efforts toward this approach through the design, synthesis, and characterization of peptoids containing nitroaromatic monomer units. This work required the synthesis of a new chiral amine building block, (S)-1-(2-nitrophenyl)ethanamine (s2ne), which could be readily installed into peptoids using standard solid-phase peptoid synthesis techniques. We designed a series of peptoid nonamers that allowed us to probe the effects of this relatively electron-deficient and sterically encumbered alpha-chiral side chain on peptoid structure, namely, the peptoid threaded loop and helix. Circular dichroism spectroscopy of the peptoids revealed that the nitroaromatic monomer has a significant effect on peptoid secondary structure. Specifically, the threaded loop structure was disrupted in a nonamer containing alternating N-(S)-1-phenylethylglycine (Nspe) and Ns2ne monomers, and the major conformation was helical instead. Indeed, placement of a single Ns2ne at the N-terminal position of (Nspe)(9) resulted in a destabilized form of the threaded loop structure relative to the homononamer (Nspe)(9). Conversely, we observed that incorporation of N-(S)-1-(4-nitrophenyl)ethylglycine (Nsnp, a p-nitro monomer) at the N-terminal position stabilized the threaded loop structure relative to (Nspe)(9). Additional experiments revealed that nitroaromatic side chains can influence peptoid nonamer folding by modulating the strength of key intramolecular hydrogen bonds in the peptoid threaded loop structure. Steric

  3. The practice of using Phenol inhibitors in obtaining monomers

    Energy Technology Data Exchange (ETDEWEB)

    Kurbatov, V.A.; Kirpichnikov, P.A.; Likumovich, A.G.

    1983-01-01

    Phenol antioxidants are promising stabilizers for the industrial production of monomers. Their potential may be considerably improved by searching for optimum compositions and conditions of application.

  4. Can the hydrophilicity of functional monomers affect chemical interaction?

    Science.gov (United States)

    Feitosa, V P; Ogliari, F A; Van Meerbeek, B; Watson, T F; Yoshihara, K; Ogliari, A O; Sinhoreti, M A; Correr, A B; Cama, G; Sauro, S

    2014-02-01

    The number of carbon atoms and/or ester/polyether groups in spacer chains may influence the interaction of functional monomers with calcium and dentin. The present study assessed the chemical interaction and bond strength of 5 standard-synthesized phosphoric-acid ester functional monomers with different spacer chain characteristics, by atomic absorption spectroscopy (AAS), ATR-FTIR, thin-film x-ray diffraction (TF-XRD), scanning electron microscopy (SEM), and microtensile bond strength (μTBS). The tested functional monomers were 2-MEP (two-carbon spacer chain), 10-MDP (10-carbon), 12-MDDP (12-carbon), MTEP (more hydrophilic polyether spacer chain), and CAP-P (intermediate hydrophilicity ester spacer). The intensity of monomer-calcium salt formation measured by AAS differed in the order of 12-MDDP=10-MDP>CAP-P>MTEP>2-MEP. FTIR and SEM analyses of monomer-treated dentin surfaces showed resistance to rinsing for all monomer-dentin bonds, except with 2-MEP. TF-XRD confirmed the weaker interaction of 2-MEP. Highest µTBS was observed for 12-MDDP and 10-MDP. A shorter spacer chain (2-MEP) of phosphate functional monomers induced formation of unstable monomer-calcium salts, and lower chemical interaction and dentin bond strength. The presence of ester or ether groups within longer spacer carbon chains (CAP-P and MTEP) may affect the hydrophilicity, μTBS, and also the formation of monomer-calcium salts.

  5. 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.

  6. The electrochemical and spectroelectrochemical properties of metal free and metallophthalocyanines containing triazole/piperazine units

    Science.gov (United States)

    Demirbaş, Ümit; Akyüz, Duygu; Mermer, Arif; Akçay, Hakkı Türker; Demirbaş, Neslihan; Koca, Atıf; Kantekin, Halit

    2016-01-01

    The synthesis and characterization of novel peripherally tetra [1,2,4]-triazole substituted metal-free phthalocyanine and its metal complexes (Zn(II), Ni(II), Pb(II), Cu(II) and Fe(II)) and the investigation of electrochemical and spectroelectrochemical properties of metal-free, Zn(II), Pb(II), Fe(II) phthalocyanines were performed for the first time in this study. Electrochemical characterizations of the complexes were performed with voltammetric and in situ spectroelectrochemical measurements. Voltammetric responses of the complexes supported the proposed structures, since complexes bearing redox inactive Pc ring metal centers just gave Pc based electron transfer reactions, while iron phthalocyanine went to metal based electron transfer reaction in addition to the Pc based ones. Electron withdrawing nature of [1,2,4]-triazole substituents shifted the redox processes toward the positive potentials. All complexes were electropolymerized during the oxidation reactions in dichloromethane (DCM) solvent. Types of the metal center of the complexes altered the electropolymerization reactions of the complexes. Spectra and colors of the electrogenerated redox species of the complexes were also determined with in situ spectroelectrochemical and in situ electrocolorimetric measurements.

  7. Supplementary dataset for child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States

    National Research Council Canada - National Science Library

    Angela L. Perez; Melanie Nembhard; Andrew Monnot; Daniel Bator; Elizabeth Madonick; Shannon H. Gaffney

    2017-01-01

    ... cosmetics sold in the United States" [1]. This article describes the concentration of metals and metalloids contained in various cosmetic products such as body paint, lipstick and eye shadow, the relative percent deviation of two analyses...

  8. Unbiased charge oscillations in DNA monomer-polymers and dimer-polymers

    CERN Document Server

    Lambropoulos, Konstantinos; Morphis, Andreas; Kaklamanis, Konstantinos; Theodorakou, Marina; Simserides, Constantinos

    2015-01-01

    We call {\\it monomer} a B-DNA base-pair and examine, analytically and numerically, electron or hole oscillations in monomer- and dimer-polymers, i.e., periodic sequences with repetition unit made of one or two monomers. We employ a tight-binding (TB) approach at the base-pair level to readily determine the spatiotemporal evolution of a single extra carrier along a $N$ base-pair polymer. We study HOMO and LUMO eigenspectra as well as the mean over time probabilities to find the carrier at a particular monomer. We use the pure mean transfer rate $k$ to evaluate the easiness of charge transfer. The inverse decay length $\\beta$ for exponential fits $k(d)$, where $d$ is the charge transfer distance, and the exponent $\\eta$ for power law fits $k(N)$ are computed; generally power law fits are better. We illustrate that increasing the number of different parameters involved in the TB description, the fall of $k(d)$ or $k(N)$ becomes steeper and show the range covered by $\\beta$ and $\\eta$. Finally, both for the time-...

  9. Plasma-Enhanced Copolymerization of Amino Acid and Synthetic Monomers

    Science.gov (United States)

    2011-12-16

    end cap containing a second inlet for the liquid monomer delivery (Scheme 1). The solid L-tyrosine monomer was placed in a resistively heated tantalum ...microroughness, which is indicative of uniform cross-linking and wetting of the deposits of all components. These films are free of pinhole defects as well

  10. 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...

  11. Monomer-dimer tatami tilings of square regions

    CERN Document Server

    Erickson, Alejandro

    2011-01-01

    We prove that the number of monomer-dimer tilings of an $n\\times n$ square grid, with $mmonomers in which no four tiles meet at any point is $m2^m+(m+1)2^{m+1}$, when $m$ and $n$ have the same parity. In addition, we present a new proof of the result that there are $n2^{n-1}$ such tilings with $n$ monomers, which divides the tilings into $n$ classes of size $2^{n-1}$. The sum of these tilings over all monomer counts has the closed form $2^{n-1}(3n-4)+2$ and, curiously, this is equal to the sum of the squares of all parts in all compositions of $n$. We also describe two algorithms and a Gray code ordering for generating the $n2^{n-1}$ tilings with $n$ monomers, which are both based on our new proof.

  12. Copolymerization of Propylene and Polar Monomers Using Pd/IzQO Catalysts.

    Science.gov (United States)

    Nakano, Ryo; Nozaki, Kyoko

    2015-09-02

    Palladium catalysts bearing imidazo[1,5-a]quinolin-9-olate-1-ylidene (IzQO) ligands polymerize α-olefins while incorporating polar monomers. The steric environment provided by N-heterocyclic-carbene (NHC) enables regioselective insertion of α-olefins and polar monomers, yielding polypropylene, propylene/allyl carboxylate copolymers, and propylene/methyl acrylate copolymer. Known polymerization catalysts bearing NHC-based ligands decompose rapidly, whereas the present catalyst is durable because of structural confinement, wherein the NHC-plane is coplanar to the metal square plane. The present catalyst system enables facile access to a new class of functionalized polyolefins and helps conceive a new fundamental principle for designing NHC-based ligands.

  13. The status of metal levels in common loons (Gavia immer) in the northeast United states

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — From 1989-1993, 178 common loons found dead or moribund throughout the northeastern United States were examined by personnel from Tufts University School of...

  14. Nanocluster metal films as thermoelectric material for radioisotope mini battery unit

    Science.gov (United States)

    Borisyuk, P. V.; Krasavin, A. V.; Tkalya, E. V.; Lebedinskii, Yu. Yu.; Vasiliev, O. S.; Yakovlev, V. P.; Kozlova, T. I.; Fetisov, V. V.

    2016-10-01

    The paper is devoted to studying the thermoelectric and structural properties of films based on metal nanoclusters (Au, Pd, Pt). The experimental results of the study of single nanoclusters' tunneling conductance obtained with scanning tunneling spectroscopy are presented. The obtained data allowed us to evaluate the thermoelectric power of thin film consisting of densely packed individual nanoclusters. It is shown that such thin films can operate as highly efficient thermoelectric materials. A scheme of miniature thermoelectric radioisotope power source based on the thorium-228 isotope is proposed. The efficiency of the radioisotope battery using thermoelectric converters based on nanocluster metal films is shown to reach values up to 1.3%. The estimated characteristics of the device are comparable with the parameters of up-to-date radioisotope batteries based on nickel-63.

  15. Study on the preirradiation polymerization of vinyl monomers

    Science.gov (United States)

    Yu-Ming, Liu; Yue-Qi, Yang; Zue-Teh, Ma

    This paper presents mainly the polymerization, copolymerization and crosslinking of monomers off-source induced by peroxides which are formed by high energy irradiation of vinyl monomers such as styrene (St), acrylonitrile (AN), methylmethacrylate (MMA), vinyl acetate (VAc) and 2-hydroxyethyl methacrylate (HEMA). The peroxides produced by irradiation of the above-mentioned monomers can not only induce the monomers themselves, but also another non-irradiated monomer to carry out copolymerization efficiently. The activation energy of peroxide formation, the apparent activation energy of polymerization and the activation energy of peroxide initiation by irradiation of vinyl monomers are: Ef(MMA) = 11, Ef(St) = 9.6, Ef(AN) = 8.5, EMMA = EVA = 11.4, Ei(MMA) = Ei(VA) = 13 kcal/mol. The rate of decomposition of monomer peroxides is smoother than that of BPO during the polymerization and so a smooth kinetic progress is obtained. The initiating ability of forming peroxides by irradiation of the vinyl monomers depends mainly on the chemical structure of the monomers. For instance, the main structure of peroxides formed during preirradiation MMA are: alternating peroxy-copolymer ? and random peroxy-copolymer ? Owing to the peroxy-bond which is unstable and in which homolytic breakage easily occurs to yield a pair of radicals, RO . is formed within the above-mentioned structural compounds, so that they possess stronger initiating reactivity. It is quite evident that the initiating reactivity of AN peroxide will be greatly reduced because of the conjugate double bond. In other words, the initiating ability of AN peroxide is lower than MMA peroxide and St peroxide.

  16. 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 pat...... the required LNA monomers. © Georg Thieme Verlag....

  17. 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.

  18. An evaluation of marginal fit of three-unit fixed dental prostheses fabricated by direct metal laser sintering system.

    Science.gov (United States)

    Kim, Ki-Baek; Kim, Woong-Chul; Kim, Hae-Young; Kim, Ji-Hwan

    2013-07-01

    This in vitro study aimed to evaluate and compare marginal fit of three-unit fixed dental prostheses (FDPs) fabricated using a newly developed direct metal laser sintering (DMLS) system with that of three-unit FDPs by a conventional lost wax technique (LW) method. Ten cobalt-chromium alloy three-unit FDPs using DMLS system and another ten nickel-chromium alloy FDPs using LW method were fabricated. Marginal fit was examined using a light-body silicone. After setting, the silicon film was cut into four parts and the thickness of silicon layer was measured at 160× magnification using a digital microscope to measure absolute marginal discrepancy (AMD), marginal gap (MG) and internal gap (IG). A repeated measure ANOVA for statistical analysis was performed using the SPSS statistical package version 12.0 (α=0.05). The mean values of AMD, MG, and IG were significantly larger in the DMLS group than in the LW group (p0.05). The marginal fit of the DMLS system appeared significantly inferior compared to that of the conventional LW method and slightly larger than the acceptable range. For clinical application further improvement of DMLS system may be required. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  19. CFA-1: the first chiral metal-organic framework containing Kuratowski-type secondary building units.

    Science.gov (United States)

    Schmieder, Phillip; Denysenko, Dmytro; Grzywa, Maciej; Baumgärtner, Benjamin; Senkovska, Irena; Kaskel, Stefan; Sastre, German; van Wüllen, Leo; Volkmer, Dirk

    2013-08-14

    The novel homochiral metal-organic framework CFA-1 (Coordination Framework Augsburg-1), [Zn5(OAc)4(bibta)3], containing the achiral linker {H2-bibta = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole}, has been synthesised. The reaction of H2-bibta and Zn(OAc)2·2H2O in N-methylformamide (NMF) (90 °C, 3 d) yields CFA-1 as trigonal prismatic single crystals. CFA-1 serves as a convenient precursor for the synthesis of isostructural frameworks with redox-active metal centres, which is demonstrated by the postsynthetic exchange of Zn(2+) by Co(2+) ions. The framework is robust to solvent removal and has been structurally characterized by synchrotron single-crystal X-ray diffraction and solid state NMR measurements ((13)C MAS- and (1)H MAS-NMR at 10 kHz). Results from MAS-NMR and IR spectroscopy studies are corroborated by cluster and periodic DFT calculations performed on CFA-1 cluster fragments.

  20. Performance Assessment of Sintered Metal Fiber Filters in Fluid Catalytic Cracking Unit

    Directory of Open Access Journals (Sweden)

    Liang Yang

    2014-01-01

    Full Text Available A long-term test was performed in a fluid catalytic cracking (FCC hot gas filtration facility using sintered metal candle filters. The operating temperature and pressure were maximum 55°C and 0.28 MPa, respectively. Specific particle sampling systems were used to measure the particle size and concentration directly at high temperature. The range of inlet particle concentration is from 150 to 165 mg/Nm3. The outlet particle concentration is in the range of 0.71–2.77 mg/Nm3 in stable operation. The filtration efficiency is from 98.23% to 99.55%. The inlet volume median diameter and the outlet volume median diameter of the particle are about 1 μm and 2.2 μm, respectively. The cake thickness is calculated based on the equation of Carman-Kozeny. The effects of operating parameters including face velocity, gas cleaning pressure, pulse duration, and maximum pressure drop were investigated. The optimal operating conditions and cleaning strategies were determined. The results show that sintered metal fiber filters are suitable for industrial application due to the good performance and high efficiency observed.

  1. 21 CFR 864.7300 - Fibrin monomer paracoagulation test.

    Science.gov (United States)

    2010-04-01

    ... to detect fibrin monomer in the diagnosis of disseminated intravascular coagulation (nonlocalized clotting within a blood vessel) or in the differential diagnosis between disseminated intravascular coagulation and primary fibrinolysis (dissolution of the fibrin in a blood clot). (b) Classification. Class...

  2. PHOTOINDUCED GRAFTING OF ACRYLIC AND ALLYL MONOMERS ON POLYETHYLENE SURFACE

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhenfeng; HU Xingzhou; YAN Qing

    1995-01-01

    Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.

  3. PREPARATION AND SURFACE PROPERTIES OF ACRYLIC COPOLYMERS CONTAINING FLUORINATED MONOMERS

    Institute of Scientific and Technical Information of China (English)

    Tai-jiang Gui; Hao Wei; Ying Zhao; Xiu-lin Wang; Du-jin Wang; Duan-fu Xu

    2006-01-01

    A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray (EDAX) show that the length and content ofperfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.

  4. Composition of amino acids, fatty acids and dietary fibre monomers ...

    African Journals Online (AJOL)

    Composition of amino acids, fatty acids and dietary fibre monomers in kernels of ... Nuts are rich in protein and essential amino acids, and have a high energy value ... of protein, especially when combined with foods with high lysine content.

  5. Synthesis of Functional Polyethylene Copolymers via Reactive Monomer

    Institute of Scientific and Technical Information of China (English)

    Hua-yi Li; Shu-qing Zhang; Ling-zhi Wang; You-liang Hu

    2005-01-01

    @@ 1Introduction Polyolefins are used widely due to their good performance and low price, but the poor compatibility and adhesion with other materials limits their applications in broader areas. Reactive monomer approach is effective to synthesize functional polyolefins[1]. In this case, olefin is copolymerized with a reactive comonomer to produce reactive intermediary which is then converted to functional group or initiator to initiate graft-from polymerization of polar monomer.

  6. 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.

  7. Two Principles of Reticular Chemistry Uncovered in a Metal-Organic Framework of Heterotritopic Linkers and Infinite Secondary Building Units.

    Science.gov (United States)

    Catarineu, Noelle R; Schoedel, Alexander; Urban, Philipp; Morla, Maureen B; Trickett, Christopher A; Yaghi, Omar M

    2016-08-31

    Structural diversity of metal-organic frameworks (MOFs) has been largely limited to linkers with at most two different types of coordinating groups. MOFs constructed from linkers with three or more nonidentical coordinating groups have not been explored. Here, we report a robust and porous crystalline MOF, Zn3(PBSP)2 or MOF-910, constructed from a novel linker PBSP (phenylyne-1-benzoate, 3-benzosemiquinonate, 5-oxidopyridine) bearing three distinct types of coordinative functionality. The MOF adopts a complex and previously unreported topology termed tto. Our study suggests that simple, symmetric linkers are not a necessity for formation of crystalline extended structures and that new, more complex topologies are attainable with irregular, heterotopic linkers. This work illustrates two principles of reticular chemistry: first, selectivity for helical over straight rod secondary building units (SBUs) is achievable with polyheterotopic linkers, and second, the pitch of the resulting helical SBUs may be fine-tuned based on the metrics of the polyheterotopic linker.

  8. Approaching two-dimensional copolymers: photoirradiation of anthracene- and diaza-anthracene-bearing monomers in Langmuir monolayers.

    Science.gov (United States)

    Payamyar, Payam; Servalli, Marco; Hungerland, Tim; Schütz, Andri P; Zheng, Zhikun; Borgschulte, Andreas; Schlüter, A Dieter

    2015-01-01

    By using structurally similar amphiphilic monomers, it is shown that compressed monolayers of varying amounts of such monomers at the air/water interface can be converted by photo-irradiation into the corresponding covalently connected monolayer sheets. Since one of the monomers carries three anthracene units and the other three 1,8-diaza-anthracene units, the growth reaction is proposed to take place through photochemically achieved [4+4]-cycloaddition between pairs of these units that are co-facially (face-to-face) arranged, to furnish the corresponding covalent dimers. While evidence for both homodimers is amply available, the existence of the heterodimer needs to be established with the help of a model reaction to support the conceptual aspect of this work, copolymerization in two dimensions. The sheet copolymers exhibit substantial robustness in that they can be spanned over 20 × 20 μm(2)-sized holes without rupturing under their own weight. X-ray photoelectron spectroscopy (XPS) studies reveal that the monomers are incorporated into the sheet copolymers according to feed. These results establish existence of the first covalent sheet copolymer, which is considered a step ahead towards novel 2D materials.

  9. Supplementary dataset for child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States.

    Science.gov (United States)

    Perez, Angela L; Nembhard, Melanie; Monnot, Andrew; Bator, Daniel; Madonick, Elizabeth; Gaffney, Shannon H

    2017-08-01

    The data presented in this article are related to the research article entitled "Child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States" [1]. This article describes the concentration of metals and metalloids contained in various cosmetic products such as body paint, lipstick and eye shadow, the relative percent deviation of two analyses performed on the products and the physico-chemico properties of the metals and metalloids used in the SkinPerm model presented in the aforementioned article.

  10. Supplementary dataset for child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States

    Directory of Open Access Journals (Sweden)

    Angela L. Perez

    2017-08-01

    Full Text Available The data presented in this article are related to the research article entitled "Child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States" [1]. This article describes the concentration of metals and metalloids contained in various cosmetic products such as body paint, lipstick and eye shadow, the relative percent deviation of two analyses performed on the products and the physico-chemico properties of the metals and metalloids used in the SkinPerm model presented in the aforementioned article.

  11. Transition metal complexes supported by a neutral tetraamine ligand containing N,N-dimethylaniline units.

    Science.gov (United States)

    Chu, Lei; Hardcastle, Kenneth I; MacBeth, Cora E

    2010-08-16

    First-row transition metal-halide complexes of tris(2-dimethylaminophenyl)amine, L(Me), have been synthesized and characterized. X-ray crystallographic studies on [Co(L(Me))Br]BPh(4), [Ni(L(Me))Cl]BPh(4), [Fe(L(Me))Cl]BPh(4), and [Cu(L(Me))Cl]BF(4) have been performed, and in all cases the ligand produces five-coordinate complexes with distorted trigonal bipyramidal coordination geometries. Where possible, comparisons have been made to the structures of related neutral tripodal ligands. Spectroscopic and magnetic studies of these complexes are also described. The Cu(I)-carbonyl complexes [Cu(L(Me))(CO)]PF(6) and [Cu(Me(6)tren)(CO)]PF(6) (Me(6)tren = tris(N,N-dimethylaminoethyl)amine) have also been prepared. Infrared spectroscopic investigations of these carbonyl complexes confirm that L(Me) is a less electron donating ligand than Me(6)tren and indicate that L(Me) can impart a different coordination number in the solid-state.

  12. Monomers of cutin biopolymer: sorption and esterification on montmorillonite surfaces

    Science.gov (United States)

    Olshansky, Yaniv; Polubesova, Tamara; Chefetz, Benny

    2013-04-01

    One of the important precursors for soil organic matter is plant cuticle, a thin layer of predominantly lipids that cover all primary aerial surfaces of vascular plants. In most plant species cutin biopolymer is the major component of the cuticle (30-85% weight). Therefore cutin is the third most abundant plant biopolymer (after lignin and cellulose). Cutin is an insoluble, high molecular weight bio-polyester, which is constructed of inter-esterified cross linked hydroxy-fatty acids and hydroxyepoxy-fatty acids. The most common building blocks of the cutin are derivatives of palmitic acid, among them 9(10),16 dihydroxy palmitic acid (diHPA) is the main component. These fatty acids and their esters are commonly found in major organo-mineral soil fraction-humin. Hence, the complexes of cutin monomers with minerals may serve as model of humin. Both cutin and humin act as adsorption efficient domains for organic contaminants. However, only scarce information is available about the interactions of cutin with soil mineral surfaces, in particular with common soil mineral montmorillonite. The main hypothesize of the study is that adsorbed cutin monomers will be reconstituted on montmorillonite surface due to esterification and oligomerization, and that interactions of cutin monomers with montmorillonite will be affected by the type of exchangeable cation. Cutin monomers were obtained from the fruits of tomato (Lycopersicon esculentum). Adsorption of monomers was measured for crude Wyoming montmorillonites and montmorillonites saturated with Fe3+ and Ca2+. To understand the mechanism of monomer-clay interactions and to evaluate esterification on the clay surface, XRD and FTIR analyses of the montmorillonite-monomers complexes were performed. Our results demonstrated that the interactions of cutin monomers with montmorillonite are affected by the type of exchangeable cation. Isotherms of adsorption of cutin monomers on montmorillonites were fitted by a dual mode model of

  13. Polyimides derived from non-aromatic monomers

    Energy Technology Data Exchange (ETDEWEB)

    Volksen, W.; Sanchez, M.I.; Cha, Hyuk-Jin; Yoon, D.Y. [IBM Almaden Research Center, San Jose, CA (United States)

    1995-12-01

    In recent years the shift in emphasis on high performance polymers, such as polyimides for microelectronic applications, has led to the search for other potential applications utilizing the unique properties of this class of polymers. In this context, polyimides incorporating non-aromatic units in the polymer backbone have been shown to exhibit excellent optical properties as well as significantly lower refractive indices. This lowering in the refractive index, of course, is also reflected in a lower dielectric constant of the material. For this reason, we have initiated a study of new polyimides, in which the traditional aromatic character is diluted with cycloaliphatic structures. One such example is the polyimide derived from hexafluoroisopropylidene diphthalic anhydride (6FDA) and 1,4-diaminocyclohexane (DACH). Preliminary data with respect to the preparation and solution behavior of the polyimide precursor as well as the characterization of relevant physical properties of the final polyimide will be presented.

  14. Molecular weight recognition in the multiple-stranded helix of a synthetic polymer without specific monomer-monomer interaction.

    Science.gov (United States)

    Kumaki, Jiro; Kawauchi, Takehiro; Ute, Koichi; Kitayama, Tatsuki; Yashima, Eiji

    2008-05-21

    Stereoregular isotactic and syndiotactic poly(methyl methacrylate)s (it- and st-PMMAs) are known to form a multiple-stranded complementary helix, so-called stereocomplex (SC) through van der Waals interactions, which is a rare example of helical supramolecular structures formed by a commodity polymer. In this study, we prepared SCs by using uniform it- and st-PMMAs and those with a narrow molecular weight distribution having different molecular weights and investigated their structures in detail using high-resolution atomic force microscopy as a function of the molecular weight and molecular weight distribution of the component PMMAs. We found that complementary it- and st-PMMAs with the longer molecular length determine the total length of the SC, and molecules of the shorter component associate until they fill up or cover the longer component. These observations support a supramolecular triple-stranded helical structure of the SCs composed of a double-stranded helix of two intertwined it-PMMA chains included in a single helix of st-PMMA, and this triple-stranded helix model of the SCs appears to be applicable to the it- and st-PMMAs having a wide range of molecular weights we employed in this study. In homogeneous double-stranded helices of it-PMMA, it has been found that, in mixtures of two it-PMMAs with different molecular weights, chains of the same molecular weight selectively form a double-stranded it-PMMA helix, or recognize the molecular weights of each other ("molecular sorting"). We thus demonstrate that molecular weight recognition is possible, without any specific interaction between monomer units, through the formation of a topological multiple-stranded helical structure based upon van der Waals interaction.

  15. Trace metals in soils of the main geomorphological units in the southwestern part of Western Siberia

    Science.gov (United States)

    Konstantinova, E. Yu

    2016-09-01

    Total concentrations of Ti, Cr, Mn, Ni, Cu, Zn, Rb, Sr, and Pb as well as soil granulometric texture were studied for three plot sites representing different geomorphologic units of the southwestern part of Western Siberia: periphery of the upland Tobolsky Mainland, Ishim plain, Turinskaya plain. Interregional difference in the relationship by and among the content of trace elements and particle size distribution of soil horizons is established. Thus, for the soils of Turinskaya plain such interrelations are not observed. For the soils of Ishim Plain moderate negative correlation between Pb concentrations and medium silt, as well as average positive correlations between Zn and fine sand, coarse sand and Pb are found. For the soils of the high terraces of the Irtish and periphery of Tobolsky Mainland interface zone moderate positive correlations between contents of Ti, Zn, Sr and fine sand, weak positive ones between Rb and medium sand, moderate negative ones between Zn and clay, Ti, Ni, Cu, Zn, Rb, Sr, and fine dust, Ti, Cu, Zn, Rb, Sr and medium silt are observed. Consequently, properties and genesis of local parent rocks are significant factors for distribution and accumulation of trace elements in the soils of the southern taiga; at the same time, the processes of bioaccumulation in thick humus horizons of dark gray soils and chernozems apparently play an important part in accumulation and migration of trace elements in forest-steppe soils of Ishim and Turinskaya plains.

  16. Comparative study on adhesive performance of functional monomers.

    Science.gov (United States)

    Yoshida, Y; Nagakane, K; Fukuda, R; Nakayama, Y; Okazaki, M; Shintani, H; Inoue, S; Tagawa, Y; Suzuki, K; De Munck, J; Van Meerbeek, B

    2004-06-01

    Mild self-etch adhesives demineralize dentin only partially, leaving hydroxyapatite around collagen within a submicron hybrid layer. We hypothesized that this residual hydroxyapatite may serve as a receptor for chemical interaction with the functional monomer and, subsequently, contribute to adhesive performance in addition to micro-mechanical hybridization. We therefore chemically characterized the adhesive interaction of 3 functional monomers with synthetic hydroxyapatite, using x-ray photoelectron spectroscopy and atomic absorption spectrophotometry. We further characterized their interaction with dentin ultra-morphologically, using transmission electron microscopy. The monomer 10-methacryloxydecyl dihydrogen phosphate (10-MDP) readily adhered to hydroxyapatite. This bond appeared very stable, as confirmed by the low dissolution rate of its calcium salt in water. The bonding potential of 4-methacryloxyethyl trimellitic acid (4-MET) was substantially lower. The monomer 2-methacryloxyethyl phenyl hydrogen phosphate (phenyl-P) and its bond to hydroxyapatite did not appear to be hydrolytically stable. Besides self-etching dentin, specific functional monomers have additional chemical bonding efficacy that is expected to contribute to their adhesive potential to tooth tissue.

  17. Polyethylene imine-metal salt solid electrolyte

    Science.gov (United States)

    Davis, G. T.; Chiang, C. K.; Takahashi, T.

    1985-02-01

    This research pertains to the development of new solid battery electrolytes. An object of this invention is to provide polymeric electrolytes using a wider variety of metal salts. These and other objects of this invention are accomplished by providing: (1) a solid polymer electrolyte comprising: a matrix of linear poly(ethylene amine) having the formula (-CH2CH2NH-)n; and (2) a metal salt which is LiI, LiClO4, NaI, NaBr, KI, CsSCN, AgNO3, CuCl1, CoCl2, or Mg(ClO4)2, wherein the salt is dissolved in and distributed throughout the poly(ethylene amine) matrix and from more than zero to 0.10 moles of salt are used per mole of monomer repeat unit, (-CH2CH2NH-).

  18. Organic-Inorganic Thermoelectrics from Single Monomers to Polymer Devices

    Science.gov (United States)

    Chang, William Bee

    Waste heat recovery from the human body provides opportunities to power electronics with a source that is cheap and readily available. Thermoelectrics utilize the Seebeck effect to recover useable electrical energy from this waste heat, but are limited due to material parameters being inversely coupled in the bulk. We investigate the role of novel physics at interfaces in order to develop new fundamental understanding of thermoelectrics. The goal is to discover systems where the Seebeck coefficient and the electrical conductivity are not inversely correlated. We investigate thermoelectric transport in organic-organic systems such as scanning tunneling microscope molecular break junctions on the nanoscale, gold nanocrystal arrays on the mesoscale and polymeric ion and mixed conductors at the macroscale. The STM molecular junctions studied in this work can provide design rules to positively couple the Seebeck coefficient and the electrical conductance. Since STM molecular junctions are one-dimensional systems, by minimizing the gap between the molecular orbital energy level and the electrode Fermi energy, the power factor S2? can be optimized. I built a toolbox of chemical structures by first understanding the role of the interface coupling to alkylthiol binding groups of thiophene-based molecules. With this understanding, I designed small molecules based on the monomer unit of donor-acceptor polymers and other conductive polymers. Molecules with very high HOMO levels or low LUMO levels were studied, and the corresponding energy levels were examined using spectroscopic techniques. I then present our work on scaling these molecular junctions to the macroscale using ligand-exchanged gold nanocrystal arrays. Beginning with a model system of alkanethiols and alkanedithiols, I show that the electrical conductivity scales with ligand length exactly as observed in single molecule junctions, and the Seebeck coefficient follows a similar trend. By showing that gold

  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

    units, respectively. Raman spectroscopy gives valuable knowledge on lignin and has a large potential for further developments. Thus in the present work we show how the use of electronic structure theory can support the study of environmental effects on lignin Raman bands. Raman spectra of the lignin...... 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. The limits of precision monomer placement in chain growth polymerization

    Science.gov (United States)

    Gody, Guillaume; Zetterlund, Per B.; Perrier, Sébastien; Harrisson, Simon

    2016-02-01

    Precise control over the location of monomers in a polymer chain has been described as the `Holy Grail' of polymer synthesis. Controlled chain growth polymerization techniques have brought this goal closer, allowing the preparation of multiblock copolymers with ordered sequences of functional monomers. Such structures have promising applications ranging from medicine to materials engineering. Here we show, however, that the statistical nature of chain growth polymerization places strong limits on the control that can be obtained. We demonstrate that monomer locations are distributed according to surprisingly simple laws related to the Poisson or beta distributions. The degree of control is quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. This analysis establishes experimental requirements for the design of polymeric chains with controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis.

  1. Biosynthesis of Polyhydroxyalkanoates Consisting of Short-chain-length Monomers and Medium-chain-length Monomers by Pseudomonas YS1

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    A strain capable of producing polyhydroxyalkanoates (PHAs) consisting of short- and medium-chain-length monomers was identified as Pseudomonas sp.coded as YS1.The strain synthesized PHAs containing monomers of hydroxybutyrate(HB or C4) and/or hydroxyoctanoate (HO or C8) and/or hydroxydecanoate (HD or C10) when grown in various substrates including glucose, raw sugar, molasses and various fatty acids.It was found that growth temperature affected the HB and HO monomer contents in the PHA.HB content in PHA increased from mole fraction 69% at 26℃ to mole fraction 85% at 37℃ while HO content decreased from mole fraction 29% at 26℃ to mole fraction 12% at 37℃.The temperature effect provides a simple and effective way to control the PHA composition and hence control the PHA mechanical and other physical properties.Also, the fermentor experiment indicated that PHB formation was growth associated and HO monomer production was in fact promoted by N-limitation.This conclusion was further supported by the fact that the formation of PHB only polyester was observed only when C/N molar ratio was smaller than 20.Higher C/N ratio led to the formation of HO monomers in the polyesters.

  2. Monomer release from nanofilled and microhybrid dental composites after bleaching.

    Directory of Open Access Journals (Sweden)

    Masumeh Hasani Tabatabaee

    2014-02-01

    Full Text Available The aim of this study was to assess the effect of bleaching on elution of monomers from nanofilled and microhybrid composites.80 samples (5mm diameter and 3mm thickness of each composite were prepared. After curing, half of them were randomly polished. Each group was divided into 8 subgroups and immersed in water or 10%, 20% and 30% H2O2 for 3 or 8 hours. Eluted Bis-GMA (Bis-phenol A Glycidyl Dimethacrylate, TEGDMA (Triethyleneglycol Dimethacrylate, UDMA (Urethane Dimethacrylate and BisEMA (Bis-phenol A ethoxylate Dimethacrylate were quantified by high performance liquid chromatography and the results were analyzed by univariate ANOVA and t-test (P<0.05.Bleach significantly increased the overall release of monomers (P<0.001; TEGDMA was released more than Bis-GMA (P<0.001. Supreme released more TEGDMA compared to Z250 (P<0.001. Bleaching increased the release of this monomer (P<0.001. Increasing both the concentration of H2O2, and the immersion time, increased the release of TEGDMA (P<0.001. Polishing had no effect on release of this monomer (P=0.952. Supreme released more Bis-GMA than Z250 (P=0.000. The more concentrated H2O2 caused more elution of Bis-GMA (P= 0.003; while the effect of immersion time was not significant (P=0.824. Polishing increased the release of Bis-GMA (P=0.001. Neither the type of composite nor Bleaching had any effect on release of UDMA (P=0.972 and (P=0.811 respectively. Immersion duration increased the release of UDMA (P=0.002, as well as polishing (P=0.024.Bleaching increased the release of monomers. Nanofilled composites released more monomer than the microfilled.

  3. The study on mechanism of holographic recording in photopolymer with dual monomer

    Science.gov (United States)

    Zhai, Qianli; Tao, Shiquan; Wang, Dayong

    2010-06-01

    In this paper we study the dynamics of refractive index modulation in a dual-monomer photopolymer through grating growth under different experiment stages. By using different sets of parameters for vinyl monomers (NVC) and acrylate monomers (POEA) respectively, a composite dual-monomer model, extended from the uniform post-exposure (UPE) model for single monomer photopolymer, is proposed and fitted with the experiment data very well. Further discussions indicate that the dominant contribution to the total index modulation is made by NVC monomers, and a brief explanation of the function of POEA monomers is given.

  4. PMR polyimide composites for aerospace applications. [Polymerization of Monomer Reactants

    Science.gov (United States)

    Serafini, T. T.

    1984-01-01

    A novel class of addition-type polyimides has been developed in response to the need for high temperature polymers with improved processability. The new plastic materials are known as PMR (for in situ polymerization of monomer reactants) polyimides. The highly processable PMR polyimides have made it possible to realize much of the potential of high temperature resistant polymers. Monomer reactant combinations for several PMR polyimides have been identified. The present investigation is concerned with a review of the current status of PMR polyimides. Attention is given to details of PMR polyimide chemistry, the processing of composites and their properties, and aerospace applications of PMR-15 polyimide composites.

  5. Cationically polymerizable monomers derived from renewable sources. Annual performance report

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.

    1992-10-01

    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year`s research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  6. [Influence Factors on Monomer Conversion of Dental Composite Resin].

    Science.gov (United States)

    Wang, Shuang; Gao, Yan; Wang, Jing; Zhang, Yan; Zhang, Yuntao; Wang, Fanghui; Wang, Qingshan

    2015-04-01

    Dental composite resin is a kind of material which has been widely used in dental restoration. Research has found that the influence of residual monomer on the material mechanical, chemical and biological properties cannot be ignored. This paper elaborates these harms of residual monomers. The effects of resin matrix, inorganic filler and initiating system, illumination, secondarily treatment on the degree of conversion were also analyzed. The paper also discusses the effective measures to increase the conversion, and offers theoretical basis for the clinical application and development of composite resin.

  7. 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......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...

  8. Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    Science.gov (United States)

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-05-03

    A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  9. Morphology Control of Metal-Organic Frameworks Based on Paddle-Wheel Units on Ion-Doped Polymer Substrate Using an Interfacial Growth Approach.

    Science.gov (United States)

    Tsuruoka, Takaaki; Mantani, Koji; Miyanaga, Ayumi; Matsuyama, Tetsuhiro; Ohhashi, Takashi; Takashima, Yohei; Akamatsu, Kensuke

    2016-06-21

    A three-dimensional metal-organic framework (MOF) consisting of pillared square-grid nets based on paddle-wheel units was synthesized by interfacial self-assembly of the frameworks on a metal-ion-doped polymer substrate. Although this type of Cu-based MOF is typically synthesized by a two-step solvothermal method, the utilization of a metal-ion-doped polymer substrate as a metal source for the framework allowed for the one-pot growth of MOF crystals on the substrate. The morphology of the obtained MOF crystals could be controlled from tetragonal to elongated tetragonal with different aspect ratios by changing the concentrations of the dicarboxylate layer ligands and diamine pillar ligands. The present approach provides a new route for the design and synthesis of MOF crystals and thin films for future applications such as gas membranes, catalysts, and electronic devices.

  10. Design of new phosphonic acid monomers for dental adhesives--synthesis of (meth) acryloxyalkyl 3-phosphonopropionates and evaluation of their adhesion-promoting functions.

    Science.gov (United States)

    Ikemura, Kunio; Tay, Franklin R; Nishiyama, Nonrihiro; Pashley, David H; Endo, Takeshi

    2006-09-01

    The aims of this study were to synthesize new phosphonic acid monomers, and to examine their bonding performance. Four kinds of newly designed phosphonic acid monomers were synthesized, and seven experimental composite-type adhesive resins comprising the synthesized monomers (3 wt%), with BPO/DEPT/BPBA initiator were prepared. Tensile bond strengths of the adhesive resins to enamel and metal were measured with a universal testing machine at a crosshead speed of 1.0 mm/ min. The synthesized adhesive monomers were light yellow viscous liquids with 32.5%-49.3% yields, and identified by 1H NMR, IR and elemental analysis to be (meth)acryloxyalkyl 3-phosphonopropionates [R-P(=O) (OH)2] (5-MPPP, 6-MHPP, 6-AHPP, 10-MDPP). It was found that the newly developed phosphonic acid monomers with BPO/DEPT/BPBA initiator attained strong adhesion to both unetched, ground enamel and sandblasted Ni-Cr alloy with good durability. They exhibited significantly higher bond strengths than conventional phosphorous-containing monomers such as MEPP and VBPA (p adhesive resins have potential prosthodontic and orthodontic applications, especially as self-etching, non-rinsing orthodontic adhesive resins.

  11. 40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

    Science.gov (United States)

    2010-07-01

    ... concentration in the catalytic cracking unit catalyst regenerator flue gas as measured by Method 29 in appendix... emissions from catalytic cracking units? 63.1564 Section 63.1564 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Catalytic Cracking...

  12. WH2 domain: a small, versatile adapter for actin monomers.

    Science.gov (United States)

    Paunola, Eija; Mattila, Pieta K; Lappalainen, Pekka

    2002-02-20

    The actin cytoskeleton plays a central role in many cell biological processes. The structure and dynamics of the actin cytoskeleton are regulated by numerous actin-binding proteins that usually contain one of the few known actin-binding motifs. WH2 domain (WASP homology domain-2) is a approximately 35 residue actin monomer-binding motif, that is found in many different regulators of the actin cytoskeleton, including the beta-thymosins, ciboulot, WASP (Wiskott Aldrich syndrome protein), verprolin/WIP (WASP-interacting protein), Srv2/CAP (adenylyl cyclase-associated protein) and several uncharacterized proteins. The most highly conserved residues in the WH2 domain are important in beta-thymosin's interactions with actin monomers, suggesting that all WH2 domains may interact with actin monomers through similar interfaces. Our sequence database searches did not reveal any WH2 domain-containing proteins in plants. However, we found three classes of these proteins: WASP, Srv2/CAP and verprolin/WIP in yeast and animals. This suggests that the WH2 domain is an ancient actin monomer-binding motif that existed before the divergence of fungal and animal lineages.

  13. Microstructure Control in the emulsion polymerization of fluorinated monomers

    Energy Technology Data Exchange (ETDEWEB)

    Apostolo, Marco [Ausimont R and D, Bollate (Italy); Morbidelli, Massimo [ETH Zentrum, Zuerich (Switzerland)

    1997-03-01

    In this paper a mathematical model able to evaluate the microstructure of fluorinated polymers is presented. The model uses the pseudo-homo polymerization approach to describe the kinetic evolution of polymerization reactions involving any number of monomer species. The molecular weight distribution is evaluated combining the classical leading moments method with a recently proposed model based on the numerical fractionation technique.

  14. Synthesis of a benzoxazine monomer containing maleimide and allyloxy groups

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A novel benzoxazine monomer 3-(4-allyloxy)phenyl-3,4-dihydro-2H-6-(N-maleimido)-1,3-benzoxazine (AMB) was synthesized and structure was confirmed by FT-IR, 1H NMR. Thermal analysis (DSC) of AMB showed the introduction of allyloxy group decreased melting point and exhibited a narrow and symmetric curing exothermic window.

  15. Influence of the Diene Monomer on Devulcanization of EPDM Rubber

    NARCIS (Netherlands)

    Verbruggen, M.A.L.; van der Does, L.; Noordermeer, Jacobus W.M.; van Duin, M.

    2008-01-01

    Ethylene–propylene–diene rubbers (EPDM) with 2-ethylidene-5-norbornene (ENB), dicyclopentadiene (DCPD), and 1,4-hexadiene (HD) as third monomers have been vulcanized with peroxide and with a conventional sulfur vulcanization recipe, and their devulcanization was subsequently investigated for

  16. Epoxy resin monomers with reduced skin sensitizing potency.

    Science.gov (United States)

    O'Boyle, Niamh M; Niklasson, Ida B; Tehrani-Bagha, Ali R; Delaine, Tamara; Holmberg, Krister; Luthman, Kristina; Karlberg, Ann-Therese

    2014-06-16

    Epoxy resin monomers (ERMs), especially diglycidyl ethers of bisphenol A and F (DGEBA and DGEBF), are extensively used as building blocks for thermosetting polymers. However, they are known to commonly cause skin allergy. This research describes a number of alternative ERMs, designed with the aim of reducing the skin sensitizing potency while maintaining the ability to form thermosetting polymers. The compounds were designed, synthesized, and assessed for sensitizing potency using the in vivo murine local lymph node assay (LLNA). All six epoxy resin monomers had decreased sensitizing potencies compared to those of DGEBA and DGEBF. With respect to the LLNA EC3 value, the best of the alternative monomers had a value approximately 2.5 times higher than those of DGEBA and DGEBF. The diepoxides were reacted with triethylenetetramine, and the polymers formed were tested for technical applicability using thermogravimetric analysis and differential scanning calorimetry. Four out of the six alternative ERMs gave polymers with a thermal stability comparable to that obtained with DGEBA and DGEBF. The use of improved epoxy resin monomers with less skin sensitizing effects is a direct way to tackle the problem of contact allergy to epoxy resin systems, particularly in occupational settings, resulting in a reduction in the incidence of allergic contact dermatitis.

  17. Aggregation processes with catalysis-driven monomer birth/death

    Institute of Scientific and Technical Information of China (English)

    Chen Yu; Han An-Jia; Ke Jian-Hong; Lin Zhen-Quan

    2006-01-01

    We propose two solvable cluster growth models, in which an irreversible aggregation spontaneously occurs between any two clusters of the same species; meanwhile, monomer birth or death of species A occurs with the help of species B. The system with the size-dependent monomer birth/death rate kernel K(i,j) = Jijv is then investigated by means of the mean-field rate equation. The results show that the kinetic scaling behaviour of species A depends crucially on the value of the index v. For the model with catalysis-driven monomer birth, the cluster-mass distribution of species A obeys the conventional scaling law in the v ≤ 0 case, while it satisfies a generalized scaling form in the v>0 case; moreover, the total mass of species A is a nonzero value in the v< 0 case while it grows continuously with time in the v>0 case. For the model with catalysis-driven monomer death, the cluster-mass distribution also approaches the conventional scaling form in the v < 0 case, while the conventional scaling description of the system breaks down in the v ≥ 0 case. Additionally, the total mass of species A retains a nonzero quantity in the v <0 case, but it decreases to zero with time in the v ≥ 0 case.

  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. Influence of the diene monomer on devulcanization of EPDM rubber

    NARCIS (Netherlands)

    Verbruggen, M.; Does, van der L.; Noordermeer, J.W.M.; Duin, van M.

    2008-01-01

    Ethylene–propylene–diene rubbers (EPDM) with 2-ethylidene-5-norbornene (ENB), dicyclopentadiene (DCPD), and 1,4-hexadiene (HD) as third monomers have been vulcanized with peroxide and with a conventional sulfur vulcanization recipe, and their devulcanization was subsequently investigated for recycli

  20. Characterization of metal oxide field-effect transistors for first helical tomotherapy Hi-Art II unit in India

    Directory of Open Access Journals (Sweden)

    Kinhikar Rajesh

    2009-01-01

    Full Text Available Purpose : To characterize metal oxide semiconductor field-effect transistors (MOSFETs for a 6-MV photon beam with a first helical tomotherapy Hi-Art II unit in India. Materials and Methods : Standard sensitivity MOSFETs were first calibrated and then characterized for reproducibility, field size dependence, angular dependence, fade effects, and temperature dependence. The detector sensitivity was estimated for static as well as rotational modes for three jaw settings (1.0 cm × 40 cm, 2.5 cm × 40 cm, and 5 cm × 40 cm at 1.5-cm depth with a source-to-axis distance (SAD of 85 cm in virtual water slabs. The A1SL ion chamber and thermoluminescence dosimeters (TLDs were used to compare the results. Results : No significant difference was found in the detector sensitivity for static and rotational procedures. The average detector sensitivity for static procedures was 1.10 mV/cGy (SD 0.02 while it was 1.12 mV/cGy (SD 0.02 for rotational procedures. The average detector sensitivity found was the same within the experimental uncertainty for static and rotational dose deliveries. The MOSFET reading was consistent and its reproducibility was excellent (+0.5% while there was no significant dependence of field size. The angular dependence of less than 1.0% was observed. There was negligible fading effect of the MOSFET. The MOSFET response was found independent of temperature in the range 18°-30°. The ion chamber readings were assumed to be a reference for the estimation of the MOSFET calibration factor. The ion chamber and the TLD were in good agreement (+2% with each other. Conclusion : This study deals only with the measurements and calibration performed on the surface of the phantom. MOSFET was calibrated and validated for phantom surface measurements for a 6-MV photon beam generated by a tomotherapy machine. The sensitivity of the detector was the same for both modes of treatment delivery with tomotherapy. The performance of the MOSFET was validated

  1. Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization.

    Science.gov (United States)

    Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M; Héroguel, Florent; Li, Yanding; Kim, Hoon; Meilan, Richard; Chapple, Clint; Ralph, John; Luterbacher, Jeremy S

    2016-10-21

    Practical, high-yield lignin depolymerization methods could greatly increase biorefinery productivity and profitability. However, development of these methods is limited by the presence of interunit carbon-carbon bonds within native lignin, and further by formation of such linkages during lignin extraction. We report that adding formaldehyde during biomass pretreatment produces a soluble lignin fraction that can be converted to guaiacyl and syringyl monomers at near theoretical yields during subsequent hydrogenolysis (47 mole % of Klason lignin for beech and 78 mole % for a high-syringyl transgenic poplar). These yields were three to seven times those obtained without formaldehyde, which prevented lignin condensation by forming 1,3-dioxane structures with lignin side-chain hydroxyl groups. By depolymerizing cellulose, hemicelluloses, and lignin separately, monomer yields were between 76 and 90 mole % for these three major biomass fractions. Copyright © 2016, American Association for the Advancement of Science.

  2. Dynamics of Aggregate Growth Through Monomer Birth and Death

    Institute of Scientific and Technical Information of China (English)

    KE Jian-Hong; LIN Zhen-Quan

    2004-01-01

    @@ We investigate the kinetic behaviour of the growth of aggregates through monomer birth and death and propose a simple model with the rate kernels K(k) ∝ ku and K′(k) ∝ kv at which the aggregate Ak of size k respectively yields and loses a monomer. For the symmetrical system with K(k) = K′(k), the aggregate size distribution approaches the conventional scaling form in the case of u < 2, while the system may undergo a gelation-like transition in the u > 2 case. Moreover, the typical aggregate size S(t) grows as t1/(2-u) in the u < 2 case and increases exponentially with time in the u = 2 case. We also investigate several solvable systems with asymmetrical rate kernels and find that the scaling of the aggregate size distribution may break down in most cases.

  3. Novel fluoro-carbon functional monomer for dental bonding.

    Science.gov (United States)

    Yoshihara, K; Yoshida, Y; Hayakawa, S; Nagaoka, N; Kamenoue, S; Okihara, T; Ogawa, T; Nakamura, M; Osaka, A; Van Meerbeek, B

    2014-02-01

    Among several functional monomers, 10-methacryloxydecyl dihydrogen phosphate (10-MDP) bonded most effectively to hydroxyapatite (HAp). However, more hydrolysis-resistant functional monomers are needed to improve bond durability. Here, we investigated the adhesive potential of the novel fluoro-carbon functional monomer 6-methacryloxy-2,2,3,3,4,4,5,5-octafluorohexyl dihydrogen phosphate (MF8P; Kuraray Noritake Dental Inc., Tokyo, Japan) by studying its molecular interaction with powder HAp using solid-state nuclear magnetic resonance ((1)H MAS NMR) and with dentin using x-ray diffraction (XRD) and by characterizing its interface ultrastructure at dentin using transmission electron microscopy (TEM). We further determined the dissolution rate of the MF8P_Ca salt, the hydrophobicity of MF8P, and the bond strength of an experimental MF8P-based adhesive to dentin. NMR confirmed chemical adsorption of MF8P onto HAp. XRD and TEM revealed MF8P_Ca salt formation and nano-layering at dentin. The MF8P_Ca salt was as stable as that of 10-MDP; MF8P was as hydrophobic as 10-MDP; a significantly higher bond strength was recorded for MF8P than for 10-MDP. In conclusion, MF8P chemically bonded to HAp. Despite its shorter size, MF8P possesses characteristics similar to those of 10-MDP, most likely to be associated with the strong chemical bond between fluorine and carbon. Since favorable bond strength to dentin was recorded, MF8P can be considered a good candidate functional monomer for bonding.

  4. Syntheses of New Functionalized Monomers for π-Conjugated Polymers

    Institute of Scientific and Technical Information of China (English)

    D.VYPRACHTICKY; V.CIMRO; P.PAVLKOVA; I.KMNEK

    2007-01-01

    1 Results Tailored monomers based on the activated esters of 2,5-dibromobenzoic (sulfonic) acid derivatives, the 3-substituted 2,5-dibromothiophenes, the 9-substituted 2,7-dibromocarbazoles, and on the brominated 1,10-phenanthrolines suitable for Suzuki, Yamamoto or Grignard metathesis (GRIM) coupling reactions were synthesized and characterized by melting point, elemental analysis, 1H NMR, FTIR and TLC. The Horner-Wadsworth-Emmons reaction mechanism was utilized for the preparation of the 3-[2-(pyren-1...

  5. Synthesis of a new aromatic dianhydride monomer and related polyimide

    Institute of Scientific and Technical Information of China (English)

    Yun Xia Wei; Ming Guang Ma; Guo Hu Zhao; Sheng Ying Li; Ming Kai Chen

    2009-01-01

    A novel aromatic dianhydride monomer,3,3'-oxybis[(3,4-dicarboxyphenoxy)phenol]dianhydride,was successfully synthe-sized in three steps using 3,3'-oxybis(phenol)as starting material,which was reacted with 4,4'-oxydianiline(ODA)via a conventional thermal or chemical imidization method to produce a new polyimide.The resulting polyimide exhibited excellent solubility,and film-forming capability.

  6. Phytotoxicity of floodplain soils contaminated with trace metals along the clark fork river, Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, United States

    Science.gov (United States)

    Rader, B.R.; Nimmo, D.W.R.; Chapman, P.L.

    1997-01-01

    Concentrations of metals in sediments and soils deposited along the floodplain of the Clark Fork River, within the Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, USA, have exceeded maximum background concentrations in the United States for most metals tested. As a result of mining and smelting activities, portions of the Deer Lodge Valley, including the Grant-Kohrs Ranch, have received National Priority List Designation under the Comprehensive Environmental Response, Compensation and Liability Act. Using a series of plant germination tests, pH measurements, and metal analyses, this study investigated the toxicity of soils from floodplain 'slicken' areas, bare spots devoid of vegetation, along the Clark Fork River. The slicken soils collected from the Grant-Kohrs Ranch were toxic to all four plant species tested. The most sensitive endpoint in the germination tests was root length and the least sensitive was emergence. Considering emergence, the most sensitive species was the resident grass species Agrostis gigantea. The sensitivities were reversed when root lengths were examined, with Echinochloa crusgalli showing the greatest sensitivity. Both elevated concentrations of metals and low pH were necessary to produce an acutely phytotoxic response in laboratory seed germination tests using slicken soils. Moreover, pH values on the Grant-Kohrs Ranch appear to be a better predictor of acutely phytotoxic conditions than total metal levels.

  7. 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.

  8. Thermally stable drilling fluid additive comprised of a copolymer of catechol-based monomer

    Energy Technology Data Exchange (ETDEWEB)

    Patel, A.D.

    1986-06-17

    A water soluble polymer is described having thermal stability and exhibiting utility as an aqueous drilling fluid additive comprising: (a) a major portion of a catechol based monomer; (b) a minor portion of a dicarboxylic acid monomer.

  9. SYNTHESIS AND CHARACTERIZATION OF A NOVEL STYRYLTHIOPHENE MONOMER AND CORRESPONDING POLYURETHANE FOR NLO MATERIALS

    Institute of Scientific and Technical Information of China (English)

    Jiang-hong Wang; Jian-feng Zhai; Jia-yun Zhou; Yu-xia Zhao; Yu-quan Shen

    1999-01-01

    A novel monomer,(trans)-7-[4-N,N-(di-β-hydroxyethyl) amino-benzene]-ethenyl-3,5-dinitro-thiophene (HBDT), was synthesized and characterized. The details of synthesizing the monomer and prepolymer, polyurethane with the monomer covalently incorporated are presented. The prepolymer and polyurethane exhibited good solubility in common organic solvents. Molecular nonlinear optical properties of the monomer (HBDT) substituted thiophene based stilbenes is presented.

  10. Near-ultraviolet tyrosyl circular dichroism of pig insulin monomers, dimers, and hexamers. Dipole-dipole coupling calculations in the monopole approximation.

    Science.gov (United States)

    Strickland, E H; Mercola, D

    1976-08-24

    The tyrosyl circular dichroism (CD) has been calculated using the conformation of pig insulin observed in rhombohedral crystals containing 2 zinc atoms per hexamer. These calculations predict that the tyrosyl CD at 275 nm will be enhanced disproportionally as monomers interact to form dimers and as dimers interact to form hexamers. This enhanced tyrosyl CD (delta epsilon per 5800 molecular weight) results from new coupling interactions generated in the regions of contact between monomers and between dimers. These calculations illustrate that a large CD enhancement may accompany aggregation even in the absence of a conformation change in eith monomer. The tyrosyl CD intensities calculated for monomers, dimers, and hexamers of 2-zinc pig insulin are compatible with the experimentally observed CD spectra which are enhanced about fourfold in the hexamer compared with the monomer. Zinc ions and other metals do not contribute directly to the tyrosyl CD but only influence the optical properties by promoting the hexameric state. The relation of the integrity of the molecule to dimer formation and the biological activity of the molecules are discussed. The largest calculated contributions to tryosyl CD arise from interactions with far-ultraviolet transitions of neighboring aromatic groups. In the hexamer, about half of the tyrosyl CD intensity is calculated to arise from Tyr-A14.

  11. High surface-area amidoxime-based polymer fibers co-grafted with various acid monomers yielding increased adsorption capacity for the extraction of uranium from seawater.

    Science.gov (United States)

    Oyola, Yatsandra; Dai, Sheng

    2016-06-07

    Uranium is dissolved in the ocean at a uniform concentration of 3.34 ppb, which translates to approximately 4-5 billion tons of uranium. The development of adsorbents that can extract uranium from seawater has been a long term goal, but the extremely dilute uranium concentration along with the competition of other metal salts (which are at higher concentrations) has hindered the development of an economical adsorption process. Several acid monomers were co-grafted with acrylonitrile (AN) to help increase the hydrophilicity of the adsorbent to improve access to the metal adsorption sites. Grafting various acid monomers on PE fibers was found to significantly affect the uranium adsorption in simulated seawater in the following order: acrylic acid (AA) uranium adsorption capacity significantly increased when Mohr's salt was added with acrylic acid, most likely due to the reduction of co-polymerization of the monomers. When testing under more realistic conditions, the acid-grafted PE fiber adsorbents were exposed to natural seawater (more dilute uranium), the uranium adsorption capacity increased in the following order: MAA uranium adsorption capacity with each acid monomer was related to higher grafting of AN and therefore a higher conversion to amidoxime (AO).

  12. [Migration of monomers and primary aromatic amines from nylon products].

    Science.gov (United States)

    Mutsuga, Motoh; Yamaguchi, Miku; Ohno, Hiroyuki; Kawamura, Yoko

    2010-01-01

    Migration of 2 kinds of monomer and 21 kinds of primary aromatic amines (PAAs) from 21 kinds of nylon products such as turners, ladles and wrap film were determined. Samples were classified as regards materials by mean of pyrolysis-GC/MS. One sample was classified as nylon 6, 15 samples as nylon 66 and three samples as nylon 6/66 copolymers, while two samples were laminate of nylon 6 with polyethylene or polypropylene. All of the nylon 66 samples contained a small amount of ε-caprolactam (CPL), which is the nylon 6 monomer. Migration levels of monomers and PAAs at 60°C for 30 min into 20% ethanol were measured by LC/MS/MS. CPL was detected at the level of 0.015-38 µg/mL from all samples, excluding one wrap film sample, and 1,6-hexamethylenediamine was detected at the level of 0.002-0.013 µg/mL from all nylon 66 samples and one nylon 6/66 sample. In addition, 0.006-4.3 µg/mL of 4,4'-diaminodiphenylmethane from three samples, 0.032-0.23 µg/mL of aniline from four samples, 0.001 µg/mL of 4-chloroaniline from two samples, and 0.002 µg/mL of 2-toluidine and 0.066 mg/mL of 1-naphthylamine from one sample each were detected. The migration levels at 95 or 121°C were about 3 and 10 times the 60°C levels, respectively.

  13. The relationship between elemental carbon and diesel particulate matter in underground metal/nonmetal mines in the United States and coal mines in Australia.

    Science.gov (United States)

    Noll, James; Gilles, Stewart; Wu, Hsin Wei; Rubinstein, Elaine

    2015-01-01

    In the United States, total carbon (TC) is used as a surrogate for determining diesel particulate matter (DPM) compliance exposures in underground metal/nonmetal mines. Since TC can be affected by interferences and elemental carbon (EC) is not, one method used to estimate the TC concentration is to multiply the EC concentration from the personal sample by a conversion factor to avoid the influence of potential interferences. Since there is no accepted single conversion factor for all metal/nonmetal mines, one is determined every time an exposure sample is taken by collecting an area sample that represents the TC/EC ratio in the miner's breathing zone and is away from potential interferences. As an alternative to this procedure, this article investigates the relationship between TC and EC from DPM samples to determine if a single conversion factor can be used for all metal/nonmetal mines. In addition, this article also investigates how well EC represents DPM concentrations in Australian coal mines since the recommended exposure limit for DPM in Australia is an EC value. When TC was predicted from EC values using a single conversion factor of 1.27 in 14 US metal/nonmetal mines, 95% of the predicted values were within 18% of the measured value, even at the permissible exposure limit (PEL) concentration of 160 μg/m(3) TC. A strong correlation between TC and EC was also found in nine underground coal mines in Australia.

  14. Recovery of Monomer from Nylon waste powder for its Recycling

    Directory of Open Access Journals (Sweden)

    Dilip B.Patil

    2014-03-01

    Full Text Available Recovery of monomer hexamethylene diamine(HMD in the form of dibenzoyl derivative of hexamethylene diamine (DBHMD from Nylon waste rope powder was carried out by degradation of Nylon waste powder of nylon rope waste.The molecular weight of nylon waste powder was found to be 26582.The minimum amount of nylon waste powder and hydrochloric acid required for maximum recovery of HMD and DBHMD was found to be 5g and 5N,50ml hydrochloric acid respectively. Further it was observed that the maximum time and temperature required for getting maximum yield of DBHMD was 120 minutes and 800C respectively.

  15. Unprecedented selectivity in molecular recognition of carbohydrates by a metal-organic framework.

    Science.gov (United States)

    Yabushita, Mizuho; Li, Peng; Bernales, Varinia; Kobayashi, Hirokazu; Fukuoka, Atsushi; Gagliardi, Laura; Farha, Omar K; Katz, Alexander

    2016-06-04

    Metal-organic framework (MOF) material NU-1000 adsorbs dimers cellobiose and lactose from aqueous solution, in amounts exceeding 1250 mg gNU-1000(-1) while completely excluding the adsorption of the monomer glucose, even in a competitive mode with cellobiose. The MOF also discriminates between dimers consisting of α and β linkages, showing no adsorption of maltose. Electronic structure calculations demonstrate that key to this selective molecular recognition is the number of favorable CH-π interactions made by the sugar with pyrene units of the MOF.

  16. Comparison of monofunctional and multifunctional monomers in phosphate binding molecularly imprinted polymers.

    Science.gov (United States)

    Wu, Xiangyang; Goswami, Kisholoy; Shimizu, Ken D

    2008-01-01

    In this study, molecularly imprinted polymers (MIPs) prepared using a multifunctional and a monofunctional monomer were compared with respect to their affinities, selectivities, and imprinting efficiencies for organophosphates. This is of interest because multifunctional monomers have higher affinities than traditional monofunctional monomers for their target analytes and thus should yield MIPs with higher affinities and selectivities. However, polymers containing multifunctional monomer may also have a higher number of unselective, non-templated binding sites. This increase in background binding sites could lead to a decrease in the magnitude of the imprinting effect and in the selectivity of the MIP. Therefore, phosphate selective imprinted and non-imprinted polymers (NIPs) were prepared using a novel multifunctional triurea monomer. The binding properties of these polymers were compared with polymers prepared using a monofunctional monourea monomer. The binding affinities and selectivities of the monomers, imprinted polymers, and NIPs were characterized by NMR titration, binding uptake studies, and binding isotherms. MIPs prepared with the triurea monomer showed higher binding affinity and selectivity for the diphenylphosphate anion in organic solvents than the MIPs prepared with the monofunctional monomer. Surprisingly, the binding properties of the NIPs revealed that the polymers prepared using the multifunctional and monofunctional monomers were very similar in affinity and selectivity. Thus, the multifunctional monomers increase not only the affinity of the MIP but also enhance the imprinting effect.

  17. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    Science.gov (United States)

    Cruz-Aguilar, A.; Herrera-González, A. M.; Vázquez-García, R. A.; Navarro-Rodríguez, D.; Coreño, J.

    2013-06-01

    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  18. Mechanism for controlling the monomer-dimer conversion of SARS coronavirus main protease.

    Science.gov (United States)

    Wu, Cheng Guo; Cheng, Shu Chun; Chen, Shiang Chuan; Li, Juo Yan; Fang, Yi Hsuan; Chen, Yau Hung; Chou, Chi Yuan

    2013-05-01

    The Severe acute respiratory syndrome coronavirus (SARS-CoV) main protease (M(pro)) cleaves two virion polyproteins (pp1a and pp1ab); this essential process represents an attractive target for the development of anti-SARS drugs. The functional unit of M(pro) is a homodimer and each subunit contains a His41/Cys145 catalytic dyad. Large amounts of biochemical and structural information are available on M(pro); nevertheless, the mechanism by which monomeric M(pro) is converted into a dimer during maturation still remains poorly understood. Previous studies have suggested that a C-terminal residue, Arg298, interacts with Ser123 of the other monomer in the dimer, and mutation of Arg298 results in a monomeric structure with a collapsed substrate-binding pocket. Interestingly, the R298A mutant of M(pro) shows a reversible substrate-induced dimerization that is essential for catalysis. Here, the conformational change that occurs during substrate-induced dimerization is delineated by X-ray crystallography. A dimer with a mutual orientation of the monomers that differs from that of the wild-type protease is present in the asymmetric unit. The presence of a complete substrate-binding pocket and oxyanion hole in both protomers suggests that they are both catalytically active, while the two domain IIIs show minor reorganization. This structural information offers valuable insights into the molecular mechanism associated with substrate-induced dimerization and has important implications with respect to the maturation of the enzyme.

  19. 单体米黄大理石矿粉对小麦产量及各器官重金属含量的影响%Effect of Monomer Yellow Marble Powder on Wheat Yield and Heavy Metals Contents in Wheat Organs

    Institute of Scientific and Technical Information of China (English)

    向元英; 吴国艳; 杨克燕

    2012-01-01

    采用盆栽法,研究大理石矿粉对小麦产量及对成熟期小麦根、茎叶、果实中重全属含量的影响。结果表明:添加大理石矿粉会显著影响小麦的生长及产量(P〈0.05),添加矿粉的量不大于60g/kg时,小麦的结实小穗数、穗粒数、千粒重和产量随添加量的增加而增加,而含量再继续增大时,对小麦产量的促进作用将减弱:低含量的大理石矿粉能缓解Ph、Cu、Zn对小麦的毒害,而高含量的对小麦的影响各异,小麦各器官中重金属Cd、Cr与添加大理石矿粉含量呈显著正相关;重金属对小麦各器官的影响排序,根:Cd〉Cr〉Pb〉Cu〉Zn,茎叶:Cd〉Cr〉Cu〉Pb〉Zn.果实:Cd〉Cr〉Pb〉Zn〉Cu。在大理石开采区应该采取一定的措施,避免大量的大理石矿粉散入周围的耕地。%The effect of marble powder on the wheat yield as well as the heavy metals contents in the roots, stem leaves and grains of wheat in the mature stage were studied using potted wheat. The results showed that addition of marble powder significantly affected the growth and yield of wheat ( P 〈 0. 05 ). When the addition of marble powder wasn't higher than 60g/kg, the wheat parameters such as the number of seed-setting spikelets, number of grains per spike, thousand seed weight and yield increased with the increasing marble powder; while when the addition became more than 60g/kg, the promoting function for wheat yield became weak. The marble powder with low content could alleviate toxicity of heavy metals such as Pb, Cu and Zn on wheat, while that with high content affected the wheat differently. Actually there were significantly positive correlation between the contents of heavy metals such as Cd and Cr in different wheat organs and the addition amount of marble powder. The ranks of heavy metals affecting the wheat organs were as follows : for roots as Cd 〉 Cr 〉 Pb 〉 Cu 〉 Zn, for stem and leaves as Cd 〉 Cr

  20. Theoretical Analysis of Unit Friction Force Working on the Metal Contact Surface with the Roll Change during Feedstock with Non-Uniform Temperature Distribution Rolling Process

    Directory of Open Access Journals (Sweden)

    Sygut P.

    2016-06-01

    Full Text Available The paper presents the results of theoretical studies influence of non-uniform temperature distribution along the feedstock length to the unit friction force working on the metal contact surface with the roll change during the round bars 70 mm in diameter continuous rolling process. This value is one of the major factors affecting the grooves wear during the rolling process. The studies were carried out based on the actual engineering data for 160 × 160 mm square cross-section feedstock of steel S355J0. Numerical modelling of the rolling process was performed using Forge2008®, a finite-element based computer program.

  1. Effects of acrylic resin monomers on porcine coronary artery reactivity.

    Science.gov (United States)

    Abebe, Worku; West, Daniel; Rueggeberg, Frederick A; Pashley, David; Mozaffari, Mahmood S

    2016-07-01

    The purpose of the present investigation was to assess the reactivity of porcine coronary arteries under in vitro conditions following their exposure to methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) monomers. Confirming previous studies using rat aortas, both MMA and HEMA induced acute/direct relaxation of coronary ring preparations, which was partly dependent on the endothelium. With prolonged tissue exposure, both monomers caused time- and concentration-dependent inhibition of receptor-mediated contraction of the vascular smooth muscle caused by prostaglandin F2∝ (PGF2∝), with HEMA causing more inhibition than MMA. Hydroxyethyl methacrylate, but not MMA, also produced impairment of non-receptor-mediated contraction of the coronary smooth muscle induced by KCl. On the other hand, neither HEMA nor MMA altered relaxation of the smooth muscle produced by the direct-acting pharmacological agent, sodium nitroprusside (SNP). While exposure to HEMA impaired endothelium-dependent vasorelaxation caused by bradykinin (BK), MMA markedly enhanced this endothelial-mediated response of the arteries. The enhanced endothelial response produced by MMA was linked to nitric oxide (NO) release. In conclusion, with prolonged tissue exposure, MMA causes less pronounced effects/adverse consequences on coronary smooth muscle function relative to the effect of HEMA, while enhancing vasorelaxation associated with release of NO from the endothelium. Accordingly, MMA-containing resin materials appear to be safer for human applications than materials containing HEMA.

  2. Wet air oxidation of epoxy acrylate monomer industrial wastewater.

    Science.gov (United States)

    Yang, Shaoxia; Liu, Zhengqian; Huang, Xiaohui; Zhang, Beiping

    2010-06-15

    Epoxy acrylate monomer industrial wastewater contained highly concentrated and toxic organic compounds. The wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were used to eliminate pollutants in order to examine the feasibility of the WAO/CWAO as a pre-treatment method for the industrial wastewater. The results showed that in the WAO 63% chemical oxygen demand (COD) and 41% total organic carbon (TOC) removals were achieved and biological oxygen demand (BOD(5))/COD ratio increased from 0.13 to 0.72 after 3h reaction at 250 degrees C, 3.5MPa and the initial concentration of 100g(COD)/L. Among homogenous catalysts (Cu(2+), Fe(2+), Fe(3+) and Mn(2+) salts), Cu(2+) salt exhibited better performance. CuO catalyst was used in the CWAO of the wastewater, COD and TOC conversion were 77 and 54%, and good biodegradability was achieved. The results proved that the CWAO was an effective pre-treatment method for the epoxy acrylate monomer industrial wastewater.

  3. 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.

  4. Effect of cationic monomer on properties of fluorinated acrylate latex

    Institute of Scientific and Technical Information of China (English)

    Li Jun Chen

    2012-01-01

    Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers.The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter.Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail.Results show that the particle size of the latex has the minimum value and the zeta potential of the latex is increased when the amount of DMDAAC is increased.In addition,the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%.However,the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%.The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%.Nevertheless,the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 25%.

  5. The Kinetics of Cellulose Grafting with Vinyl Acetate Monomer

    Directory of Open Access Journals (Sweden)

    Éva Borbély

    2005-11-01

    Full Text Available Cellulose is a natural raw material recurring in a great quantity. The demand touse it more and more widely is increasing. The production of cellulose derivates started asearly as the 19th century, however the modification of these materials meant the breakingup the fibrous structure, which made their use more difficult in paper industry. Themodified cellulose made by graft copolymerization, however, keeps its fibrous character,which provides a great advantage regarding its use. Grafting of industrial cellulose pulpwith vinyl-acetate allows for the production of grafted wood cellulose fibres that have athermoplastic layer on their surface. The binder fibre (fibrid produced in this way can beexcellently used for producing synthetic papers.In the first part of my experiments I dealt with choosing the parameters of graftcopolymerization which are best suited to various uses and after that I studied thedependence of graft reaction on the composition and properties of industrial celluloseapplied. The selection of the suitable reaction parameters was followed by the study ofreaction speed and activation energy. I have stated that the gross reaction of graftingindustrial cellulose with vinyl-acetate monomer is a second order reaction, which is provenby the fact that the invert of the momentary monomer concentration of the system plottedagainst time is a linear function. The rise of the curves, that is, the reaction speed increaseswhen the temperature in the range of 293–323 K is increasing, while the average activationenergy decreases.

  6. Microporous rod metal-organic frameworks with diverse Zn/Cd-triazolate ribbons as secondary building units for CO2 uptake and selective adsorption of hydrocarbons.

    Science.gov (United States)

    Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Zhai, Quan-Guo

    2017-01-17

    The synthetic design of new porous open-framework materials with pre-designed pore properties for desired applications such as gas adsorption and separation remains challenging. We proposed one such class of materials, rod metal-organic frameworks (rod MOFs), which can be tuned by using rod secondary building units (rod SBUs) with different geometrical and chemical features. Our approach takes advantage of the readily accessible metal-triazolate 1-D motifs as rod SBUs to combine with dicarboxylate ligands to prepare target rod MOFs. Herein we report three such metal-triazolate-dicarboxylate frameworks (SNNU-21, -22 and -23). During the formation of these three MOFs, Cd or Zn ions are firstly connected by 1,2,4-triazole through the N1,N2,N4-mode to form 1-D metal-organic ribbon-like rod SBUs, which further joint four adjacent rod SBUs via eight BDC linkers to give 3-D microporous frameworks. However, tuned by the different NH2 groups from metal-triazolate rod SBUs, different space groups, pore sizes and shapes are observed for SNNU-21-23. All of these rod MOFs show not only remarkable CO2 uptake capacity, but also high CO2 over CH4 and C2-hydrocarbons over CH4 selectivity under ambient conditions. Specially, SNNU-23 exhibits a very high isosteric heat of adsorption (Qst) for C2H2 (62.2 kJ mol(-1)), which outperforms the values of all MOF materials reported to date including the famous MOF-74-Co.

  7. Structure and magnetism of a porous three-dimensional metal-organic framework based on planar tetranuclear copper(Ⅱ) cluster units

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A porous three-dimensional copper(Ⅱ) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(Ⅱ) cluster units. The variable temperature magnetic susceptibility data in the range 2-280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of -31.3 cm-1, -30.8 cm-1, and 13.5 cm-1.

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

    Directory of Open Access Journals (Sweden)

    2007-06-01

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

  9. Sorption studies on Cr (VI) removal from aqueous solution using cellulose grafted with acrylonitrile monomer.

    Science.gov (United States)

    Hajeeth, T; Sudha, P N; Vijayalakshmi, K; Gomathi, T

    2014-05-01

    Graft copolymerization of acrylonitrile on to cellulosic material derived from sisal fiber can be initiated effectively with ceric ammonium nitrate. The grafting conditions were optimized by changing the concentration of initiator and monomer. The change in crystallinity of the grafted polymeric samples was concluded from the XRD patterns. The prepared cellulose grafted acrylonitrile copolymer was used as an adsorbent to remove Cr (VI) ions from aqueous solutions. The efficiency of the adsorbent was identified from the variation in the percentage of adsorption with contact time, adsorbent dose and pH. From the observed results it was evident that the adsorption of metal ions increases with the increase in contact time and metal ion concentration. An optimum pH was found to be 5.0 for the removal of Cr (VI) from the aqueous solution. The results of the Langmuir, Freundlich, and pseudo first- and second-order studies revealed that the adsorption was found to fit well with Freundlich isotherm and follows pseudo second-order kinetics. From the above results, it was concluded that the cellulose-g-acrylonitrile copolymer was found to be an efficient adsorbent for the removal of Cr (VI) from aqueous waste generated from industries.

  10. Multifunctional methacrylate-based coatings for glass and metal surfaces

    Science.gov (United States)

    Pospiech, Doris; Jehnichen, Dieter; Starke, Sandra; Müller, Felix; Bünker, Tobias; Wollenberg, Anne; Häußler, Liane; Simon, Frank; Grundke, Karina; Oertel, Ulrich; Opitz, Michael; Kruspe, Rainer

    2017-03-01

    In order to prevent freshwater biofouling glass and metal surfaces were coated with novel transparent methacrylate-based copolymers. The multifunctionality of the copolymers, such as adhesion to the substrate, surface polarity, mechanical long-term stability in water, and ability to form metal complexes was inserted by the choice of suitable comonomers. The monomer 2-acetoacetoxy ethyl methacrylate (AAMA) was used as complexing unit to produce copper(II) complexes in the coating's upper surface layer. The semifluorinated monomer 1H,1H,2H,2H-perfluorodecyl methacrylate was employed to adjust the surface polarity and wettability. Comprehensive surface characterization techniques, such as X-ray photoelectron spectroscopy (XPS) and contact angle measurements showed that surface compositions and properties can be easily adjusted by varying the concentrations of the comonomers. The formation of copper(II) complexes along the copolymer chains and their stability against washing out with plenty of water was proven by XPS. Copolymers containing semifluorinated comonomers significantly inhibited the growth of Achnanthidium species. Copolymers with copper-loaded AAMA-sequences were able to reduce both the growth of Achnanthidium spec. and Staphylococcus aureus.

  11. Cerium-Hydride Secondary Building Units in a Porous Metal-Organic Framework for Catalytic Hydroboration and Hydrophosphination.

    Science.gov (United States)

    Ji, Pengfei; Sawano, Takahiro; Lin, Zekai; Urban, Ania; Boures, Dean; Lin, Wenbin

    2016-11-16

    We report the stepwise, quantitative transformation of Ce(IV)6(μ3-O)4(μ3-OH)4(OH)6(OH2)6 nodes in a new Ce-BTC (BTC = trimesic acid) metal-organic framework (MOF) into the first Ce(III)6(μ3-O)4(μ3-OLi)4(H)6(THF)6Li6 metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis.

  12. Nucleoside-O-Methyl-(H)-Phosphinates: Novel Monomers for the Synthesis of Methylphosphonate Oligonucleotides Using H-Phosphonate Chemistry.

    Science.gov (United States)

    Kostov, Ondřej; Páv, Ondřej; Rosenberg, Ivan

    2017-09-18

    This unit comprises the straightforward synthesis of protected 2'-deoxyribonucleoside-O-methyl-(H)-phosphinates in both 3'- and 5'-series. These compounds represent a new class of monomers compatible with the solid-phase synthesis of oligonucleotides using H-phosphonate chemistry and are suitable for the preparation of both 3'- and 5'-O-methylphosphonate oligonucleotides. The synthesis of 4-toluenesulfonyloxymethyl-(H)-phosphinic acid as a new reagent for the preparation of O-methyl-(H)-phosphinic acid derivatives is described. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  13. Polymerization of nonfood biomass-derived monomers to sustainable polymers.

    Science.gov (United States)

    Zhang, Yuetao; Chen, Eugene Y-X

    2014-01-01

    The development of sustainable routes to fine chemicals, liquid fuels, and polymeric materials from natural resources has attracted significant attention from academia, industry, the general public, and governments owing to dwindling fossil resources, surging energy demand, global warming concerns, and other environmental problems. Cellulosic material, such as grasses, trees, corn stover, or wheat straw, is the most abundant nonfood renewable biomass resources on earth. Such annually renewable material can potentially meet our future needs with a low carbon footprint if it can be efficiently converted into fuels, value added chemicals, or polymeric materials. This chapter focuses on various renewable monomers derived directly from cellulose or cellulose platforms and corresponding sustainable polymers or copolymers produced therefrom. Recent advances related to the polymerization processes and the properties of novel biomass-derived polymers are also reviewed and discussed.

  14. Biosynthesis of monomers for plastics from renewable oils.

    Science.gov (United States)

    Lu, Wenhua; Ness, Jon E; Xie, Wenchun; Zhang, Xiaoyan; Minshull, Jeremy; Gross, Richard A

    2010-11-03

    Omega-hydroxyfatty acids are excellent monomers for synthesizing a unique family of polyethylene-like biobased plastics. However, ω-hydroxyfatty acids are difficult and expensive to prepare by traditional organic synthesis, precluding their use in commodity materials. Here we report the engineering of a strain of the diploid yeast Candida tropicalis to produce commercially viable yields of ω-hydroxyfatty acids. To develop the strain we identified and eliminated 16 genes encoding 6 cytochrome P450s, 4 fatty alcohol oxidases, and 6 alcohol dehydrogenases from the C. tropicalis genome. We also show that fatty acids with different chain lengths and degrees of unsaturation can be more efficiently oxidized by expressing different P450s within this strain background. Biocatalysis using engineered C. tropicalis is thus a potentially attractive biocatalytic platform for producing commodity chemicals from renewable resources.

  15. Production and monomer composition of exopolysaccharides by yogurt starter cultures.

    Science.gov (United States)

    Frengova, G I; Simova, E D; Beshkova, D M; Simov, Z I

    2000-12-01

    As components of starter cultures for Bulgarian yogurt, Streptococcus salivarius subsp. thermophilus and Lactobacillus delbrueckii subsp. bulgaricus revealed extensive exopolysaccharide (EPS) production activity when cultivated in whole cow's milk. The polymer-forming activity of thermophilic streptococci was lower (230-270 mg EPS/L) than that of the lactobacilli (400-540 mg EPS/L). Mixed cultures stimulated EPS production in yogurt manufacture, and a maximum concentration of 720-860 mg EPS/L was recorded after full coagulation of milk. The monomer structure of the exopolysaccharides formed by the yogurt starter cultures principally consists of galactose and glucose (1:1), with small amounts of xylose, arabinose, and/or mannose.

  16. 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.

  17. LF-NMR study of effect the octadecylamine addition in the copolymerization process between acrylic acid and styrene monomers; Estudo por RMN de baixo campo do efeito da adicao de octadecilamina na copolimerizacao dos monomeros de acido acrilico e estireno

    Energy Technology Data Exchange (ETDEWEB)

    Pedroza, Oscar J.O.; Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano]. E-mail: oscarjop@ima.ufrj.br, mibt@ima.ufrj.br

    2005-07-01

    The copolymer content at least two monomer units that are the repetitive unities in the polymeric chains. The use of Low Field Nuclear Magnetic Resonance (LF-NMR), MARAN ultra 23, was applied to measure the proton spin-lattice relaxation time values. The process of copolymerization between the acrylic acid (A) and the styrene (S) monomers was studied with the addition of the octadecylamine (D) in the acrylic acid monomer. These materials were submitted at reflux by 24 hours. After this process the polymerization was carried out at room temperature. The values of the relaxation parameter are showed in Table 1. The co polymerizations between acrylic acid and styrene monomers were influenced by the octadecylamine addition. The results showed that an increase in the amine concentration promotes flexibility in the final material. This can be explained in terms of chains size after amine addition, which promotes an increasing in the free space among the polymer chains. (author)

  18. Derivation of S and Pb in phanerozoic intrusion-related metal deposits from neoproterozoic sedimentary pyrite, Great Basin, United States

    Science.gov (United States)

    Vikre, P.G.; Poulson, S.R.; Koenig, A.E.

    2011-01-01

    The thick (???8 km), regionally extensive section of Neoproterozoic siliciclastic strata (terrigenous detrital succession, TDS) in the central and eastern Great Basin contains sedimentary pyrite characterized by mostly high d34S values (-11.6 to 40.8%, derived from reduction of seawater sulfate, and by markedly radiogenic Pb isotopes ( 207Pb/204Pb derivation of deposit S and Pb from TDS pyrite. Minor element abundances in TDS pyrite (e.g., Pb, Zn, Cu, Ag, and Au) compared to sedimentary and hydrothermal pyrite elsewhere are not noticeably elevated, implying that enrichment in source minerals is not a precondition for intrusion-related metal deposits. Three mechanisms for transferring components of TDS sedimentary pyrite to intrusion-related metal deposits are qualitatively evaluated. One mechanism involves (1) decomposition of TDS pyrite in thermal aureoles of intruding magmas, and (2) aqueous transport and precipitation in thermal or fluid mixing gradients of isotopically heavy S, radiogenic Pb, and possibly other sedimentary pyrite and detrital mineral components, as sulfide minerals in intrusion-related metal deposits. A second mechanism invokes mixing and S isotope exchange in thermal aureoles of Pb and S exsolved from magma and derived from decomposition of sedimentary pyrite. A third mechanism entails melting of TDS strata or assimilation of TDS strata by crustal or mantle magmas. TDS-derived or assimilated magmas ascend, decompress, and exsolve a mixture of TDS volatiles, including isotopically heavy S and radiogenic Pb from sedimentary pyrite, and volatiles acquired from deeper crustal or mantle sources. In the central and eastern Great Basin, the wide distribution and high density of small to mid-sized vein, replacement, and skarn intrusion-related metal deposits in lower Paleozoic rocks that contain TDS sedimentary pyrite S and Pb reflect (1) prolific Jurassic, Cretaceous, and Tertiary magmatism, (2) a regional, substrate reservoir of S and Pb in

  19. Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters.

    Science.gov (United States)

    Mizutani, Masato; Satoh, Kotaro; Kamigaito, Masami

    2010-06-02

    All polymerization reactions are categorized into two large different families, chain- and step-growth polymerizations, which are typically incompatible. Here, we report the simultaneous chain- and step-growth polymerization via the metal-catalyzed radical copolymerization of conjugated vinyl monomers and designed monomers possessing unconjugated C horizontal lineC and active C-Cl bonds. Especially, almost ideal linear random copolymers containing both vinyl polymer and polyester units in a single polymer chain were formed by the CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine- or RuCp*Cl(PPh(3))(2)-catalyzed copolymerization of methyl acrylate (MA) for the chain-growth polymerization and 3-butenyl 2-chloropropionate (1) for the step-growth polymerization. In contrast, other transition metal catalysts, such as CuCl with tris[2-(dimethylamino)ethyl]amine or N,N,N',N'',N''-pentamethyldiethylenetriamine and FeCl(2)/PnBu(3), resulted in branched structures via the concomitant chain-growth copolymerization of 1 with MA. The polymerization mechanism was studied in detail by NMR and MALDI-TOF-MS analyses of the polymerizations as well as the model reactions. Furthermore, a series of copolymers changing from random to multiblock polymer structures were obtained by varying the feed ratios of the two monomers. These copolymers can be easily degraded into lower molecular weight oligomers or polymers via methanolysis of the ester-linkages in the main chain using sodium carbonate.

  20. Exposing Differences in Monomer Exchange Rates of Multicomponent Supramolecular Polymers in Water.

    Science.gov (United States)

    Baker, Matthew B; Gosens, Ronald P J; Albertazzi, Lorenzo; Matsumoto, Nicholas M; Palmans, Anja R A; Meijer, E W

    2016-02-02

    The formation of multicomponent and bioactive supramolecular polymers is a promising strategy for the formation of biomaterials that match the dynamic and responsive nature of biological systems. In order to fully realize the potential of this strategy, knowledge of the location and behavior of bioactive components within the system is crucial. By employing synthetic strategies to create multifunctional monomers, coupled with FRET and STORM techniques, we have investigated the formation and behavior of a bioactive and multicomponent supramolecular polymer. By creating a peptide-dye-monomer conjugate, we were able to measure high degrees of monomer incorporation and to visualize the equal distribution of monomers within the supramolecular polymer. Furthermore, by tracking the movement of monomers, we uncovered small differences in the dynamics of the bioactive monomers.

  1. Enhanced stability of monomer fold correlates with extreme drug resistance of HIV-1 protease.

    Science.gov (United States)

    Louis, John M; Tözsér, József; Roche, Julien; Matúz, Krisztina; Aniana, Annie; Sayer, Jane M

    2013-10-29

    During treatment, mutations in HIV-1 protease (PR) are selected rapidly that confer resistance by decreasing affinity to clinical protease inhibitors (PIs). As these unique drug resistance mutations can compromise the fitness of the virus to replicate, mutations that restore conformational stability and activity while retaining drug resistance are selected on further evolution. Here we identify several compensating mechanisms by which an extreme drug-resistant mutant bearing 20 mutations (PR20) with >5-fold increased Kd and >4000-fold decreased affinity to the PI darunavir functions. (1) PR20 cleaves, albeit poorly, Gag polyprotein substrates essential for viral maturation. (2) PR20 dimer, which exhibits distinctly enhanced thermal stability, has highly attenuated autoproteolysis, thus likely prolonging its lifetime in vivo. (3) The enhanced stability of PR20 results from stabilization of the monomer fold. Both monomeric PR20(T26A) and dimeric PR20 exhibit Tm values 6-7.5 °C higher than those for their PR counterparts. Two specific mutations in PR20, L33F and L63P at sites of autoproteolysis, increase the Tm of monomeric PR(T26A) by ~8 °C, similar to PR20(T26A). However, without other compensatory mutations as seen in PR20, L33F and L63P substitutions, together, neither restrict autoproteolysis nor significantly reduce binding affinity to darunavir. To determine whether dimer stability contributes to binding affinity for inhibitors, we examined single-chain dimers of PR and PR(D25N) in which the corresponding identical monomer units were covalently linked by GGSSG sequence. Linking of the subunits did not appreciably change the ΔTm on inhibitor binding; thus stabilization by tethering appears to have little direct effect on enhancing inhibitor affinity.

  2. 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

    “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....

  3. Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin

    OpenAIRE

    Ohta, Yukari; Hasegawa, Ryoichi; Kurosawa, Kanako; Maeda, Allyn H.; Koizumi, Toshio; Nishimura,Hiroshi; Okada, Hitomi; Qu, Chen; Saito, Kaori; Watanabe, Takashi; Hatada, Yuji

    2016-01-01

    Abstract Enzymatic catalysis is an ecofriendly strategy for the production of high‐value low‐molecular‐weight aromatic compounds from lignin. Although well‐definable aromatic monomers have been obtained from synthetic lignin‐model dimers, enzymatic‐selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a casca...

  4. Studies on the Influence of Monomers on the Performance Properties of Epoxy Acrylate Resin

    Directory of Open Access Journals (Sweden)

    Amrita Sharma

    2008-01-01

    Full Text Available Twelve blend samples were prepared by physical mixing of epoxy acrylate resins with various monomers viz. ethoxylated phenol monoacrylate (EOPA, tripropylene glycol diacrylate (TPGDA and trimethylol propane tri acrylate(TMPTA, having weight ratio of epoxy acrylate resin and monomers are 50:50, 60:40, 70:30, 80:20. These samples were cured under UV radiation using 5% photo initiator by weight. These blends were evaluated for mechanical, chemical & thermal properties. It was found that the sample having mono & tri functional monomers shows better properties than the samples having di functional monomer.

  5. Rare π5^6Pb Interactions in a Two-dimensional Rare Metal-organic Coordination Polymer with Two Distinct Kinds of Axially Chiral Units

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    A new metal-organic coordination polymer [Pb(mfpdc)(CH3OH)]n (1, mfpdc = 2,6-dimethyl-4-(2-furanyl) pyridine-3,5-dicarboxylate) was synthesized and characterized by single-crystal X-ray analyses. The crystal is orthorhombic, space group Pbca, a = 15.6297(18), b = 9.4803(11), c = 18.598(2) A, V= 2755.8(6) A3, Z = 8, Mr= 498.44, Dc= 2.403 Mg/m3, F(000) = 1872, the final R = 0.0275 and wR = 0.0726 (1 〉 2σ(I)). There are interesting polynuclear zigzag (PbOs)n chains in the structure of 1, and there have interesting axially chiral S- and R-unit Pb4L units constructed from prochiral organic ligands through C-H...O bonding. The (R/S)-Pb4L units by sharing Pb centers generate a 2-D coordination network, in which there exist rare n65Pb (3.2610 A) interactions. The solid-state photoluminescent emission of compound 1 appears at 487 nm.

  6. Materials considerations in the design of a metal-hydride heat pump for an advanced extravehicular mobility unit

    Science.gov (United States)

    Liebert, B. E.

    1986-01-01

    A metal-hydride heat pump (HHP) has been proposed to provide an advanced regenerable nonventing thermal sink for the liquid-cooled garment worn during an extravehicular activity (EVA). The conceptual design indicates that there is a potential for significant advantages over the one presently being used by shuttle crew personnel as well as those that have been proposed for future use with the space station. Compared to other heat pump designs, a HHP offers the potential for extended use with no electrical power requirements during the EVA. In addition, a reliable, compact design is possible due to the absence of moving parts other than high-reliability check valves. Because there are many subtleties in the properties of metal hydrides for heat pump applications, it is essential that a prototype hydride heat pump be constructed with the selected materials before a committment is made for the final design. Particular care must be given to the evaporator heat exchanger worn by the astronaut since the performance of hydride heat pumps is generally heat transfer limited.

  7. 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 template...... tuning of particle size and binding properties are required to fit practical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012...

  8. Isoreticular expansion of metal-organic frameworks with triangular and square building units and the lowest calculated density for porous crystals.

    Science.gov (United States)

    Furukawa, Hiroyasu; Go, Yong Bok; Ko, Nakeun; Park, Young Kwan; Uribe-Romo, Fernando J; Kim, Jaheon; O'Keeffe, Michael; Yaghi, Omar M

    2011-09-19

    The concept and occurrence of isoreticular (same topology) series of metal-organic frameworks (MOFs) is reviewed. We describe the preparation, characterization, and crystal structures of three new MOFs that are isoreticular expansions of known materials with the tbo (Cu(3)(4,4',4''-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate)(2), MOF-399) and pto topologies (Cu(3)(4,4',4''-(benzene-1,3,5-triyl-tribenzoate)(2), MOF-143; Cu(3)(4,4',4''-(triazine-2,4,6-triyl-tris(benzene-4,1-diyl))tribenzoate)(2), MOF-388). One of these materials (MOF-399) has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and has the highest porosity (94%) and lowest density (0.126 g cm(-3)) of any MOFs reported to date.

  9. Enzymatic Polymerization of an Ibuprofen-Containing Monomer and Subsequent Drug Release.

    Science.gov (United States)

    Stebbins, Nicholas D; Yu, Weiling; Uhrich, Kathryn E

    2015-08-01

    Novel ibuprofen-containing monomers comprising naturally occurring and biocompatible compounds were synthesized and subsequently polymerized via enzymatic methods. Through the use of a malic acid sugar backbone, ibuprofen was attached as a pendant group, and then subsequently polymerized with a linear aliphatic diol (1,3-propanediol, 1,5-pentanediol, or 1,8-octanediol) as comonomer using lipase B from Candida antarctica, a greener alternative to traditional metal catalysts. Polymer structures were elucidated by nuclear magnetic resonance and infrared spectroscopies, and thermal properties and molecular weights were determined. All polymers exhibited sustained ibuprofen release, with the longer chain, more hydrophobic diols exhibiting the slowest release over the 30 d study. Polymers were deemed cytocompatible using mouse fibroblasts, when evaluated at relevant therapeutic concentrations. Additionally, ibuprofen retained its chemical integrity throughout the polymerization and in vitro hydrolytic degradation processes. This methodology of enzymatic polymerization of a drug presents a more environmentally friendly synthesis and a novel approach to bioactive polymer conjugates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.

    Science.gov (United States)

    Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J; Arion, Vladimir B

    2015-06-15

    Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry.

  11. Therapeutic Application of Natural Medicine Monomers in Cancer Treatment.

    Science.gov (United States)

    Zhong, Chen; Wall, Nathan R; Zu, Yuangang; Sui, Guangchao

    2017-07-14

    Natural medicine monomers (NMMs) isolated from plants have been recognized for their roles in treating different human diseases including cancers. Many NMMs exhibit effective anti-cancer activities and can be used as drugs or adjuvant agents to enhance the efficacy of chemotherapy and radiotherapy with low or tolerable side effects. Some NMMs, such as Paclitaxel and Camptothecin, have been extensively studied for decades and are now used as anti-cancer medicines due to their remarkable curative effects, such as inhibiting cancer cell proliferation and metastasis, and inducing cell death and differentiation. Although therapeutic effects for most NMMs have been appreciated, the underlying mechanisms of their anti-cancer activities remain largely unexplored. In this review, we have grouped NMMs into six categories based on their chemical structures, and summarized current knowledge of molecular mechanisms of anti-cancer activities to provide a theoretical basis for clinical application and new drug development of NMMs. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  12. Computational screening of oxetane monomers for novel hydroxy terminated polyethers.

    Science.gov (United States)

    Sarangapani, Radhakrishnan; Ghule, Vikas D; Sikder, Arun K

    2014-06-01

    Energetic hydroxy terminated polyether prepolymers find paramount importance in search of energetic binders for propellant applications. In the present study, density functional theory (DFT) has been employed to screen the various novel energetic oxetane derivatives, which usually construct the backbone for these energetic polymers. Molecular structures were investigated at the B3LYP/6-31G* level, and isodesmic reactions were designed for calculating the gas phase heats of formation. The condensed phase heats of formation for designed compounds were calculated by the Politzer approach using heats of sublimation. Among the designed oxetane derivatives, T4 and T5 possess condensed phase heat of formation above 210 kJ mol(-1). The crystal packing density of the designed oxetane derivatives varied from 1.2 to 1.6 g/cm(3). The detonation velocities and pressures were evaluated using the Kamlet-Jacobs equations, utilizing the predicted densities and HOFCond. It was found that most of the designed oxetane derivatives have detonation performance comparable to the monomers of benchmark energetic polymers viz., NIMMO, AMMO, and BAMO. The strain energy (SE) for the oxetane derivatives were calculated using homodesmotic reactions, while intramolecular group interactions were predicted through the disproportionation energies. The concept of chemical hardness is used to analyze the susceptibility of designed compounds to reactivity and chemical transformations. The heats of formation, density, and predicted performance imply that the designed molecules are expected to be candidates for polymer synthesis and potential molecules for energetic binders.

  13. Conformational study of neutral histamine monomer and their vibrational spectra

    Science.gov (United States)

    Mukherjee, V.; Yadav, T.

    2016-08-01

    Molecular modeling and potential energy scanning of histamine molecule, which is an important neurotransmitter, with respect to the dihedral angle of methylamine side chain have done which prefer three different conformers of histamine monomer. We have calculated molecular structures and vibrational spectra with IR and Raman intensities of these conformers using Density Functional Theory (DFT) with the exchange functional B3LYP incorporated with the basis set 6-31 ++G(d,p) and Hartree-Fock (HF) with the same basis set. We have also employed normal coordinate analysis (NCA) to scale the theoretical frequencies and to calculate potential energy distributions (PEDs) for the conspicuous assignments. Normal modes assignments of some of the vibrational frequencies of all the three conformers are in good agreement with the earlier reported experimental frequencies of histamine whereas others have modified. The standard deviations between the theoretical and experimental frequencies fall in the region 13-20 cm- 1 for the three conformers. NBO analyses of histamine conformers were also performed. The net charge transfers from ethylamine side chain to the imidazole ring. The intensive interactions between bonding and anti-bonding orbitals are found in imidazole ring. The HOMO-LUMO energy gap is nearly 5.50 eV.

  14. 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.

  15. Rheological study of polypropylene irradiated with polyfunctional monomers

    Science.gov (United States)

    Otaguro, H.; Rogero, S. O.; Yoshiga, A.; Lima, L. F. C. P.; Parra, D. F.; Artel, B. W. H.; Lugão, A. B.

    2007-12-01

    The aim of this paper is to investigate the rheological properties of polypropylene (PP) modified by ionization radiation (gamma rays) in the presence of two different monomers. The samples were mixed in a twin-screw extruder with ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TMPTMA) with concentration in the range of 0.5-5.0 mmol. After that, they were irradiated with 20 kGy dose of gamma radiation. The structural modification of polypropylene was analyzed in the melt state by measuring melt flow rate (MFR), η* (complex viscosity) and G' (storage modulus) in the angular frequency range of 10 -1 to 3 × 10 2 rad s -1. From the oscillatory rheology data, one could obtain the values of η0 (zero shear viscosity) that would be related to the molar mass. All results were discussed with respect to the crosslinking and degradation process that occur in the post-reactor treatment to produce controlled rheology polypropylene. The resulting polymeric materials were submitted the cytotoxicity in vitro test by neutral red uptake methodology with NCTC L 929 cell line from American Type Culture Collection bank. All modified PP samples presented no cytotoxicity.

  16. Blood compatibility of polyurethane surface grafted copolymerization with sulfobetaine monomer.

    Science.gov (United States)

    Jiang, Yuan; Rongbing, Bian; Ling, Tong; Jian, Shen; Sicong, Lin

    2004-07-01

    Surface modification is an effective way to improve the hemocompatibility and remain bulk properties of biomaterials. Recently, polymer tailed with zwitterions was found having good blood compatibility. In this study, the grafting copolymerization of sulfobetaine onto polyurethane surface was obtained through two steps. In the first step, polyurethane film coupled with vinyl groups was obtained through the reaction between the carboxyl group of acrylic acid (AA) and the NH-urethane group of polyurethane by dicyclohexylcarbodiimide (DCC). In the second step, sulfobetaine was grafted copolymerization on the surface using AIBN as an initiator. The reaction process was monitored with ATR-IR spectra and X-ray photoelectron spectroscopy (XPS) spectra. The wettability of films was investigated by water contact angle measurement. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet rich plasma (PRP) and protein absorption in bovine fibrinogen (BFG). Low platelet adhesion was observed on the grafted films incubated in PRP for 1 and 3 h, respectively. The protein absorption was reduced on the grafted films after incubated in bovine fibrinogen for 2 h. All of these results revealed that the improved blood compatibility was obtained by grafting copolymerization with zwitterionic monomer of sulfobetaine onto polyurethane film. In addition, introducing vinyl groups onto surface through DCC and AA is a novel method to functionalize polyurethane for further modification.

  17. The Theaflavin Monomers Inhibit the Cancer Cells Growth in Vitro

    Institute of Scientific and Technical Information of China (English)

    You-Ying TU; An-Bin TANG; Naoharu WATANABE

    2004-01-01

    The inhibition effects of tea theaflavins complex (TFs), theaflavin-3-3 '-digallate (TFDG),theaflavin-3'-gallate (TF2B), and an unidentified compound (UC) on the growth of human liver cancer BEL-7402 cells, gastric cancer MKN-28 cells and acute promyelocytic leukemia LH-60 cells were investigated.TFs was obtained through the catalysis of catechins with immobilized polyphenols oxidase. TFDG, TF2B and UC were isolated from TFs with high speed countercurrent chromatography (HSCCC). The results showed that TF2B significantly inhibited the growth of all three kinds of cancer cells, TFs, TFDG and UC had some effect on BEL-7402 and MKN-28, but little activity on LH-60. The inhibition effects of TF2B, TFDG, and UC on BEL-7402 and MKN-28 were stronger than TFs. The relationship coefficients between monomer concentration and its inhibition rate against MKN-28 and BEL-7402 were 0.87 and 0.98 for TF2B, 0.96 and 0.98 for UC, respectively. The IC50 values ofTFs, TF2B, and TFDG were 0.18, 0.11, and 0.16 mM on BEL-7402 cells, and 1.11, 0.22, and 0.25 mM on MKN-28 cells respectively.

  18. 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 monome...

  19. 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 po...

  20. Monomers, polymers and articles containing the same from sugar derived compounds

    Science.gov (United States)

    Gallagher, James; Reineke, Theresa; Hillmyer, Marc A.

    2016-11-29

    Disclosed herein are monomers formed by reacting a sugar derived compound(s) comprising a lactone and two hydroxyls with a compound(s) comprising an isocyanate and an acrylate or methacrylate. Polymers formed from such monomers, and articles formed from the polymers are also disclosed.

  1. Random sampling for the monomer-dimer model on a lattice

    NARCIS (Netherlands)

    J. van den Berg (Rob); R.M. Brouwer (Rachel)

    1999-01-01

    textabstractIn the monomer-dimer model on a graph, each matching (collection of non-overlapping edges) ${M$ has a probability proportional to $lambda^{|M|$, where $lambda > 0$ is the model parameter, and $|M|$ denotes the number of edges in $M$. An approximate random sample from the monomer-dimer

  2. 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...

  3. Monomers, polymers and articles containing the same from sugar derived compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gallagher, James; Reineke, Theresa; Hillmyer, Marc A.

    2016-11-29

    Disclosed herein are monomers formed by reacting a sugar derived compound(s) comprising a lactone and two hydroxyls with a compound(s) comprising an isocyanate and an acrylate or methacrylate. Polymers formed from such monomers, and articles formed from the polymers are also disclosed.

  4. Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF.

    Science.gov (United States)

    Alezi, Dalal; Spanopoulos, Ioannis; Tsangarakis, Constantinos; Shkurenko, Aleksander; Adil, Karim; Belmabkhout, Youssef; O Keeffe, Michael; Eddaoudi, Mohamed; Trikalitis, Pantelis N

    2016-10-05

    The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or "cubic graphite" structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal-organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm(3) g(-1), respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g(-1) and 210.4 cm(3) (STP) cm(-3) at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH4 adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm(-3) at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.

  5. A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.

    Science.gov (United States)

    Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2016-01-01

    How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times.

  6. Monomer adsorption of indocyanine green to gold nanoparticles.

    Science.gov (United States)

    Guerrini, Luca; Hartsuiker, Liesbeth; Manohar, Srirang; Otto, Cees

    2011-10-05

    NIR-dye encoded gold nanoparticles (GNP) are rapidly emerging as contrast agents in many bio-imaging/sensing applications. The coding process is usually carried out without control or a clear understanding of the metal-liquid interface properties which, in contrast, are critical in determining the type and extension of dye-metal interaction. In this paper, we investigated the effect of gold surface composition on the adsorption of indocyanine green (ICG) on GNP, simulating the surface conditions of gold nanorods on citrate-capped gold nanospheres. These substrates allowed a careful control of the metal-liquid interface composition and, thus, detailed absorption and fluorescence concentration studies of the effects of each individual chemical in the colloidal solution (i.e. bromide anions, cetyl trimethylammonium ions and Ag(+) ions) on the ICG-gold interaction. This study reveals the drastic effect that these experimental parameters can have on the ICG adsorption on GNP.

  7. Methods for the synthesis of deuterated vinyl pyridine monomers

    Science.gov (United States)

    Hong, Kunlun; Yang, Jun; Bonnesen, Peter V

    2014-02-25

    Methods for synthesizing deuterated vinylpyridine compounds of the Formula (1), wherein the method includes: (i) deuterating an acyl pyridine of the Formula (2) in the presence of a metal catalyst and D.sub.2O, wherein the metal catalyst is active for hydrogen exchange in water, to produce a deuterated acyl compound of Formula (3); (ii) reducing the compound of Formula (3) with a deuterated reducing agent to convert the acyl group to an alcohol group, and (iii) dehydrating the compound produced in step (ii) with a dehydrating agent to afford the vinylpyridine compound of Formula (1). The resulting deuterated vinylpyridine compounds are also described.

  8. Nanolayering of phosphoric acid ester monomer on enamel and dentin.

    Science.gov (United States)

    Yoshihara, Kumiko; Yoshida, Yasuhiro; Hayakawa, Satoshi; Nagaoka, Noriyuki; Irie, Masao; Ogawa, Tatsuyuki; Van Landuyt, Kirsten L; Osaka, Akiyoshi; Suzuki, Kazuomi; Minagi, Shogo; Van Meerbeek, Bart

    2011-08-01

    Following the "adhesion-decalcification" concept, specific functional monomers possess the capacity to primary chemically interact with hydroxyapatite (HAp). Such ionic bonding with synthetic HAp has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), manifest as self-assembled "nanolayering". In continuation of that basic research this study aimed to explore whether nanolayering also occurs on enamel and dentin when a 10-MDP primer is applied following a common clinical application protocol. Therefore, the interaction of an experimental 10-MDP primer and a control, commercially available, 10-MDP-based primer (Clearfil SE Bond primer (C-SE), Kuraray) with enamel and dentin was characterized by X-ray diffraction (XRD), complemented with transmission electron microscopy interfacial ultrastructural data upon their reaction with enamel and dentin. In addition, XRD was used to study the effect of the concentration of 10-MDP on nanolayering on dentin. Finally, the stability of the nanolayers was determined by measuring the bond strength to enamel and dentin when a photoinitiator was added to the experimental primer or when interfacial polymerization depended solely on the photoinitiator supplied with the subsequently applied adhesive resin. XRD confirmed nanolayering on enamel and dentin, which was significantly greater on dentin than on enamel, and also when the surface was actively rubbed with the primer. Nanolayering was also proportional to the concentration of 10-MDP in the primer. Finally, the experimental primer needed the photoinitiator to obtain a tensile bond strength to dentin comparable with that of the control C-SE primer (which also contains a photoinitiator), but not when bonded to enamel. It is concluded that self-assembled nanolayering occurs on enamel and dentin, even when following a clinically used application protocol. The lower bonding effectiveness of mild self-etch adhesives to enamel should be ascribed in part to a lower

  9. Vinyl acetate monomer (VAM) genotoxicity profile: relevance for carcinogenicity.

    Science.gov (United States)

    Albertini, Richard J

    2013-09-01

    Vinyl acetate monomer (VAM) is a site-of-contact carcinogen in rodents. It is also DNA reactive and mutagenic, but only after its carboxylesterase mediated conversion to acetaldehyde (AA), a metabolic reaction that also produces acetic acid and protons. As VAM's mutagenic metabolite, AA is normally produced endogenously; detoxification by aldehyde dehydrogenase (ALDH) is required to maintain intra-cellular AA homeostasis. This review examines VAM's overall genotoxicity, which is due to and limited by AA, and the processes leading to mutation induction. VAM and AA have both been universally negative in mutation studies in bacteria but both have tested positive in several in vitro studies in higher organisms that usually employed high concentrations of test agents. Recently however, in vitro studies evaluating submillimolar concentrations of VAM or AA have shown threshold dose-responses for mutagenicity in human cultured cells. Neither VAM nor AA induced systemic mutagenicity in in vivo studies in metabolically competent mice when tested at non-lethal doses while treatments of animals deficient in aldehyde dehydrogenase (Aldh in animals) did induce both gene and chromosome level mutations. The results of several studies have reinforced the critical role for aldehyde dehydrogenase 2 (ALDH2 in humans) in limiting AA's (and therefore VAM's) mutagenicity. The overall aim of this review of VAM's mutagenic potential through its AA metabolite is to propose a mode of action (MOA) for VAM's site-of-contact carcinogenesis that incorporates the overall process of mutation induction that includes both background mutations due to endogenous AA and those resulting from exogenous exposures.

  10. A DFT based analysis of adsorption of Hg(2+) 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

    2017-03-07

    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.

  11. Development and validation of a sensitive UPLC-MS/MS instrumentation and alkaline nitrobenzene oxidation method for the determination of lignin monomers in wheat straw.

    Science.gov (United States)

    Zheng, Mengjing; Gu, Shubo; Chen, Jin; Luo, Yongli; Li, Wenqian; Ni, Jun; Li, Yong; Wang, Zhenlin

    2017-06-15

    A method to determine the lignin monomers (p-hydroxybenzaldehyde, vanillin and syringaldehyde) in plant cell wall of wheat internode was developed and validated using a high-throughput nitrobenzene oxidation step and ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for quantification. UPLC analyses were carried out using an reversed phase C18 column (ACQUITY UPLC BEH, 1.7μm, 2.1×100mm) and gradient elution with water and acetonitrile. This method was completely validated in terms of analyzing speed, linearity, sensitivity, limits of detection (LODs) and limits of quantification (LOQs).The three lignin monomers were successfully separated within 6min and only 2min were required to regain its equilibrium. The method linearity with regression coefficients values (R2) greater than 0.997. Additionally, LODs ranged from 0.21 to 0.89μgL(-1) and LOQs ranged from 0.69 to 2.95μgL(-1). The applicability of this analytical approach for determining the three lignin monomers was confirmed by the successful analysis of real samples of wheat stem internodes. The nitrobenzene oxidation method was used for the analysis of lignin monomers. We have optimized the treatment temperature (170°C, 1h) and realized the high-throughput using the microwave digestion instrument. Recovery of this extraction method ranged from 68.4% to 77.7%. The analysis result showed that the guaiacyl unit (G) was the major component of lignin and there was a higher content of the syringyl unit (S) than that of the hydroxybenzyl unit (H). Copyright © 2017. Published by Elsevier B.V.

  12. Synthesis and optical properties of chlorin monomer, dimer and trimer on an amino nitrogen atom.

    Science.gov (United States)

    Tamiaki, Hitoshi; Nagai, Tomoaki; Tanaka, Takuya; Tatebe, Tomohiro

    2015-09-01

    Naturally occurring chlorophyll-a was chemically modified to methyl 3-aminomethyl-pyropheophorbides-a including primary, secondary, and tertiary amines. Reductive amination of methyl pyropheophorbide-d possessing the 3-formyl group with ammonia efficiently gave a chlorin dimer covalently linked with CH2NHCH2 at the 3-position, which was transformed into a trimer through the substitution at the amino group. Conformational analyses by (1)H NMR spectroscopic observation and molecular modeling estimation indicated that the dimer and trimer were apt to form closely packed structures. Chlorin chromophores in the dimer and trimer were weakly interacted in dichloromethane to shift their Qy absorption bands to longer wavelengths by 4-6nm than the maxima of the corresponding monomer. In the red-shifted Qy region, the trimer gave an S-shaped circular dichroism band by exciton coupling of composite chlorin units. All the semi-synthetic chlorophyll derivatives were highly fluorescent and no intramolecular quenching was observed even in the trimer. The behaviors would be ascribable to the formation of compact conformers and suppression of intramolecular motion, which are important to construct light-harvesting antenna complexes in phototrophs and their model systems.

  13. Influence of the chemical structure of functional monomers on their adhesive performance.

    Science.gov (United States)

    Van Landuyt, K L; Yoshida, Y; Hirata, I; Snauwaert, J; De Munck, J; Okazaki, M; Suzuki, K; Lambrechts, P; Van Meerbeek, B

    2008-08-01

    Functional monomers in adhesive systems can improve bonding by enhancing wetting and demineralization, and by chemical bonding to calcium. This study tested the hypothesis that small changes in the chemical structure of functional monomers may improve their bonding effectiveness. Three experimental phosphonate monomers (HAEPA, EAEPA, and MAEPA), with slightly different chemical structures, and 10-MDP (control) were evaluated. Adhesive performance was determined in terms of microtensile bond strength of 4 cements that differed only for the functional monomer. Based on the Adhesion-Decalcification concept, the chemical bonding potential was assessed by atomic absorption spectrophotometry of the dissolution rate of the calcium salt of the functional monomers. High bond strength of the adhesive cement corresponded to low dissolution rate of the calcium salt of the respective functional monomer. The latter is according to the Adhesion-Decalcification concept, suggestive of a high chemical bonding capacity. We conclude that the adhesive performance of an adhesive material depends on the chemical structure of the functional monomer.

  14. Monomer-dimer model on a scale-free small-world network

    Science.gov (United States)

    Zhang, Zhongzhi; Sheng, Yibin; Jiang, Qiang

    2012-02-01

    The explicit determination of the number of monomer-dimer arrangements on a network is a theoretical challenge, and exact solutions to monomer-dimer problem are available only for few limiting graphs with a single monomer on the boundary, e.g., rectangular lattice and quartic lattice; however, analytical research (even numerical result) for monomer-dimer problem on scale-free small-world networks is still missing despite the fact that a vast variety of real systems display simultaneously scale-free and small-world structures. In this paper, we address the monomer-dimer problem defined on a scale-free small-world network and obtain the exact formula for the number of all possible monomer-dimer arrangements on the network, based on which we also determine the asymptotic growth constant of the number of monomer-dimer arrangements in the network. We show that the obtained asymptotic growth constant is much less than its counterparts corresponding to two-dimensional lattice and Sierpinski fractal having the same average degree as the studied network, which indicates from another aspect that scale-free networks have a fundamentally distinct architecture as opposed to regular lattices and fractals without power-law behavior.

  15. Molecularly Imprinted Polymer (MIP) Film with Improved Surface Area Developed by Using Metal-Organic Framework (MOF) for Sensitive Lipocalin (NGAL) Determination.

    Science.gov (United States)

    Iskierko, Zofia; Sharma, Piyush Sindhu; Prochowicz, Daniel; Fronc, Krzysztof; D'Souza, Francis; Toczydłowska, Diana; Stefaniak, Filip; Noworyta, Krzysztof

    2016-08-10

    Electropolymerizable functional and cross-linking monomers were used to prepare conducting molecularly imprinted polymer film with improved surface area with the help of a sacrificial metal-organic framework (MOF). Subsequent dissolution of the MOF layer resulted in a surface developed MIP film. This surface enlargement increased the analyte accessibility to imprinted molecular cavities. Application of the porous MIP film as a recognition unit of an extended-gate field effect transistor (EG-FET) chemosensor effectively enhanced analytical current signals of determination of recombinant human neutrophil gelatinase-associated lipocalin (NGAL).

  16. NMR measurement of identical polymer samples by round robin method. 4. Analysis of composition and monomer sequence distribution in poly(methyl methacrylate-co-acrylonitrile) leading to determinations of monomer reactivity ratios

    Energy Technology Data Exchange (ETDEWEB)

    Hatada, Koichi; Kitayama, Tatsuki; Terawaki, Yoshio [Osaka Univ., Toyonaka (Japan). Faculty of Engineering Science] [and others

    1995-11-01

    In order to assess the reliability of NMR measurement of polymers, {sup 1}H and {sup 13}C NMR data for three copolymers of methyl methacrylate (MMA) and acrylonitrile (AN) prepared with AIBN were collected from 46 spectrometers whose resonance frequencies for {sup 1}H NMR measurements ranging from 90 to 500 MHz. {sup 1}H and {sup 13}C NMR spectra were measured in nitrobenzene-d{sub 5} at 110degC and acetonitrile-d{sub 3} at 70degC, respectively. Standard deviations ({sigma}`s) for chemical shift measurements of the {sup 1}H and {sup 13}C NMR signals were 0.003-0.008 ppm and 0.03-0.05 ppm, respectively. Compositions of the copolymers were determined from the relative intensities of the signals due to the OCH{sub 3} (MMA) and CH (AN) protons, and the {sigma} values for the determinations were 3.7-9.5%. The compositions determined from {sup 13}C NMR (C = O for MMA unit, CN for AN unit) agreed well with those obtained from {sup 1}H NMR. Monomer reactivity ratios r{sub ij} (i,j = 1 or 2) for a penultimate model were determined from monomer feed ratios and triad fractions obtained from the C = O (MMA) and CH (AN) carbon signals. Most of the {sigma} values for r{sub ij} determinations were 5-14%. While r{sub 22} and r{sub 12} are nearly equivalent, r{sub 11} and r{sub 21} are significantly different from each other, indicating a possible existence of the penultimate-unit effect in the copolymerization of MMA and AN. Terminal model reactivity ratios, r{sub 1} and r{sub 2}, determined formally from the compositions of three samples by Fineman-Ross method showed large {sigma} values (22-24%). (author).

  17. Valorization/Recognition of Environmental Protection Qualifications in the Chemical and Metal Industries. Synthesis of the National Reports: Federal Republic of Germany, France, Italy, Spain, United Kingdom. CEDEFOP Panorama. First Edition.

    Science.gov (United States)

    Gay, Catherine

    Reports on the development and recognition of environmental protection qualifications in the chemical and metal industries in Germany, France, Italy, Spain, and the United Kingdom were synthesized. The synthesis focused on companies' and social partners' current and planned strategies and obligations of companies regarding recognizing…

  18. Suberin-derived aliphatic monomers as biomarkers for SOM affected by root litter contribution

    Science.gov (United States)

    Kogel-Knabner, I.; Spielvogel, S.-; Prietzel, J.-

    2012-12-01

    The patchy distribution of trees and ground vegetation may have major impact on SOC variability and stability at the small scale. Knowledge about correlations between the pattern of tree and ground vegetation, SOC stocks in different soil depths and the contribution of root- vs. shoot-derived carbon to different SOC fractions is scarce. We have tested analysis of hydrolysable aliphatic monomers derived from the biopolyesters cutin- and suberin to investigate whether their composition can be traced back after decay and transformation into soil organic matter (SOM) to study SOM source, degradation, and stand history. The main objective of this study was to elucidate the relative abundance of cutin and suberin in different particle size and density fractions of a Norway spruce and a European beech site with increasing distance to stems. Soil samples, root, bark and needle/leave samples were analyzed for their cutin and/or suberin signature. Previous to isolation of bound lipids, sequential solvent extraction was used to remove free lipids and other solvent extractable compounds. Cutin- and suberin-derived monomers were extracted from the samples using base hydrolysis. Before analysis by Gas Chromatography/Mass Spectrometry (GC/MS), extracts were derivatized to convert compounds to trimethylsilyl derivatives. Statistical analysis identified four variables which as combined factors discriminated significantly between cutin and suberin based on their structural units. We found a relative enrichment of cutin and suberin contents in the occluded fraction at both sites that decreased with increasing distance to the trees. We conclude from our results that (i) patchy above- and belowground carbon input caused by heterogeneous distribution of trees and ground vegetation has major impact on SOC variability and stability at the small scale, (ii) tree species is an important factor influencing SOC heterogeneity at the stand scale due to pronounced differences in above- and

  19. Investigation of hydrogen atom addition to vinyl monomers by time resolved ESR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Beckert, D.; Mehler, K.

    1983-07-01

    By means of time resolved ESR spectroscopy in the microsecond time scale the H atom addition to different vinyl monomers was investigated. The H atoms produced by pulse radiolysis of aqueous solutions show a strong recombination CIDEP effect which also allows the recombination rate constant of H atoms to be determined. By analysis of ESR time profiles with the modified Bloch equations the relaxation times T/sub 1/, T/sub 2/, the polarization factors and the chemical rate constants with scavengers were obtained. Besides the H atom addition rate constants to different vinyl monomers the structure of the monomer radical was determined for acrylic acid.

  20. Influence of Monomer Types on the Designability of a Protein-Model Chain

    Institute of Scientific and Technical Information of China (English)

    梁好均; 王元元

    2002-01-01

    In a three-dimensional off-lattice model, the method of Shakhnovich and Gutin for minimizing the Hamiltonian is applied to the design of a protein-model chain. The effect of the number of hydrophobic and hydrophilic monomer types on the designability ora protein-model chain is investigated. The simulation results reveal that the number of hydrophobic monomer types is a much more important factor than that of the polar monomer types in the design of a protein-model chain.

  1. A review of adaptive mechanisms in cell responses towards oxidative stress caused by dental resin monomers.

    Science.gov (United States)

    Krifka, Stephanie; Spagnuolo, Gianrico; Schmalz, Gottfried; Schweikl, Helmut

    2013-06-01

    Dental composite resins are biomaterials commonly used to aesthetically restore the structure and function of teeth impaired by caries, erosion, or fracture. Residual monomers released from resin restorations as a result of incomplete polymerization processes interact with living oral tissues. Monomers like triethylene glycol dimethacrylate (TEGDMA) or 2-hydroxylethyl methacrylate (HEMA) are cytotoxic via apoptosis, induce genotoxic effects, and delay the cell cycle. Monomers also influence the response of cells of the innate immune system, inhibit specific odontoblast cell functions, or delay the odontogenic differentiation and mineralization processes in pulp-derived cells including stem cells. These observations indicate that resin monomers act as environmental stressors which inevitably disturb regulatory cellular networks through interference with signal transduction pathways. We hypothesize that an understanding of the cellular mechanisms underlying these phenomena will provide a better estimation of the consequences associated with dental therapy using composite materials, and lead to innovative therapeutic strategies and improved materials being used at tissue interfaces within the oral cavity. Current findings strongly suggest that monomers enhance the formation of reactive oxygen species (ROS), which is most likely the cause of biological reactions activated by dental composites and resin monomers. The aim of the present review manuscript is to discuss adaptive cell responses to oxidative stress caused by monomers. The particular significance of a tightly controlled network of non-enzymatic as well as enzymatic antioxidants for the regulation of cellular redox homeostasis and antioxidant defense in monomer-exposed cells will be addressed. The expression of ROS-metabolizing antioxidant enzymes like superoxide dismutase (SOD1), glutathione peroxidase (GPx1/2), and catalase in cells exposed to monomers will be discussed with particular emphasis on the role

  2. 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.

  3. Effect of monomer composition of polymer matrix on flexural properties of glass fibre-reinforced orthodontic archwire.

    Science.gov (United States)

    Ohtonen, J; Vallittu, P K; Lassila, L V J

    2013-02-01

    To compare force levels obtained from glass fibre-reinforced composite (FRC) archwires. Specifically, FRC wires were compared with polymer matrices having different dimethacrylate monomer compositions. FRC material (E-glass provided by Stick Tech Ltd, Turku, Finland) with continuous unidirectional glass fibres and four different types of dimethacrylate monomer compositions for the resin matrix were tested. Cross-sectionally round FRC archwires fitting into the 0.3 mm slot of a bracket were divided into 16 groups with six specimens in each group. Glass fibres were impregnated by the manufacturer, and they were initially light-cured by hand light-curing unit or additionally post-cured in light-curing oven. The FRC archwire specimens were tested at 37°C according to a three-point bending test in dry and wet conditions using a span length of 10 mm and a crosshead speed of 1.0 mm/minute. The wires were loaded until final failure. The data were statistically analysed using analysis of variance (ANOVA). The dry FRC archwire specimens revealed higher load values than water stored ones, regardless of the polymer matrix. A majority of the FRC archwires showed higher load values after being post-cured. ANOVA revealed that the polymer matrix, curing method, and water storage had a significant effect (P composition, curing method, and water storage affected the flexural properties and thus, force level and working range which could be obtained from the FRC archwire.

  4. Comparison of Metal-Ceramic and All-Ceramic Three-Unit Posterior Fixed Dental Prostheses: A 3-Year Randomized Clinical Trial.

    Science.gov (United States)

    Nicolaisen, Maj H; Bahrami, Golnosh; Schropp, Lars; Isidor, Flemming

    2016-01-01

    The aim of this randomized clinical study was to compare the 3-year clinical outcome of metal-ceramic fixed dental prostheses (MC-FDPs) and zirconia all-ceramic fixed dental prostheses (AC-FDPs) replacing a posterior tooth. A sample of 34 patients with a missing posterior tooth were randomly chosen to receive either a MC-FDP (n = 17) or an AC-FDP (n = 17). The FDPs were evaluated at baseline and yearly until 3 years after cementation. They were assessed using the California Dental Association assessment system. Periodontal parameters were measured at the abutment teeth, and the contralateral teeth served as control. The statistical unit was the FDP/patient. The survival rates for MC-FDPs and AC-FDPs were 100%. The success rate was 76% and 71% for MC-FDPs and AC-FDPs, respectively. Three technical complications were observed in the MC-FDP group and five in the AC-FDP group, all chipping fractures of the ceramic veneer. Furthermore, one biologic complication in the MC-FDP group (an apical lesion) was observed. No framework fractures occurred. All patients had optimal oral hygiene and showed no bleeding on periodontal probing at any of the recalls. Only minor changes in the periodontal parameters were observed during the 3 years of observation. Three-unit posterior MC-FDPs and AC-FDPs showed similar high survival rates and acceptable success rates after 3 years of function, and ceramic veneer chipping fracture was the most frequent complication for both types of restorations.

  5. Metal cofactors in the structure and activity of the fowlpox resolvase.

    Science.gov (United States)

    Culyba, Matthew J; Hwang, Young; Hu, Jimmy Yan; Minkah, Nana; Ocwieja, Karen E; Bushman, Frederic D

    2010-05-28

    Poxvirus DNA replication generates linear concatemers containing many copies of the viral genome with inverted repeat sequences at the junctions between monomers. The inverted repeats refold to generate Holliday junctions, which are cleaved by the virus-encoded resolvase enzyme to form unit-length genomes. Here we report studies of the influence of metal cofactors on the activity and structure of the resolvase of fowlpox virus, which provides a tractable model for in vitro studies. Small-molecule inhibitors of related enzymes bind simultaneously to metal cofactors and nearby surface amino acid residues, so understanding enzyme-cofactor interactions is important for the design of antiviral agents. Analysis of inferred active-site residues (D7, E60, K102, D132, and D135) by mutagenesis and metal rescue experiments specified residues that contribute to binding metal ions and that multiple binding sites are probably involved. Differential electrophoretic analysis was used to map the conformation of the DNA junction when bound by resolvase. For the wild-type complex in the presence of EDTA (ethylenediaminetetraacetic acid) or Ca(2+), migration was consistent with the DNA arms arranged in near-tetrahedral geometry. However, the D7N active-site mutant resolvase held the arms in a more planar arrangement in EDTA, Ca(2+), or Mg(2+) conditions, implicating metal-dependent contacts at the active site in the larger architecture of the complex. These data show how divalent metals dictate the conformation of FPV resolvase-DNA complexes and subsequent DNA cleavage.

  6. Preserving the Sequence of a Biopolymer's Monomers as They Enter an Electrospray Mass Spectrometer

    Science.gov (United States)

    Maulbetsch, William; Wiener, Benjamin; Poole, William; Bush, Joseph; Stein, Derek

    2016-11-01

    This paper investigates how faithfully an electrospray mass spectrometer reports the order of monomers of a single biopolymer in the context of two sequencing strategies. We develop a simplified one-dimensional theoretical model of the dynamics of Brownian particles in the Taylor cone of an electropray source, where free monomers drift towards the apex in an elongational force gradient. The likelihood that neighboring particles will invert their order decreases near the apex because the strength of the force gradient increases. Neighboring monomers on a stretched biopolymer should be cleaved by photofragmentation within about 3 nm of the apex if they are to enter the mass spectrometer in sequence with 95% probability under typical experimental conditions. Alternatively, if the monomers are cleaved processively at milliseconds-long intervals by an enzyme, their sequence will be faithfully reported with 95% confidence if the enzyme is within about 117 nm of the apex.

  7. Critical behavior in the cubic dimer model at nonzero monomer density

    Science.gov (United States)

    Sreejith, G. J.; Powell, Stephen

    2014-01-01

    We study critical behavior in the classical cubic dimer model (CDM) in the presence of a finite density of monomers. With attractive interactions between parallel dimers, the monomer-free CDM exhibits an unconventional transition from a Coulomb phase to a dimer crystal. Monomers act as charges (or monopoles) in the Coulomb phase and, at nonzero density, lead to a standard Landau-type transition. We use large-scale Monte Carlo simulations to study the system in the neighborhood of the critical point, and find results in agreement with detailed predictions of scaling theory. Going beyond previous studies of the transition in the absence of monomers, we explicitly confirm the distinction between conventional and unconventional criticality, and quantitatively demonstrate the crossover between the two. Our results also provide additional evidence for the theoretical claim that the transition in the CDM belongs in the same universality class as the deconfined quantum critical point in the SU (2) JQ model.

  8. Radiation-induced graft copolymerization of binary monomer mixture containing acrylonitrile onto polyethylene films

    Science.gov (United States)

    Choi, Seong-Ho; Nho, Young Chang

    2000-04-01

    Graft copolymerization of acrylonitrile (AN)/acrylic acid (AA), acrylonitrile (AN)/methacrylic acid (MA), and acrylonitrile (AN)/glycidyl methacrylate (GMA) onto pre-irradiated polyethylene (PE) films were studied. The effect of reaction conditions such as solvents, additives, and monomer composition on the grafting yields was investigated. The extent of grafting was found to increase with increasing sulfuric acid concentration when sulfuric acid as an additive was added to the grafting solution. In AN/AA mixture, the proportion of acrylonitrile in the copolymer increased with an increasing AN component in feed monomers. On the other hand, in AN/MA mixture, acrylonitrile component in copolymer was very slight in spite of the increase AN component in feed monomers. In the AN/GMA mixture, the proportion of acrylonitrile in the copolymer increased with increasing acrylonitrile component in AN/GMA feed monomer.

  9. Computational studies of the structural properties of the monomer and dimer of Aβ(1-28)

    Science.gov (United States)

    Dong, Xiao; Chen, Wei; Mousseau, Normand; Derreumaux, Philippe

    2007-03-01

    Neurodegenerative diseases are linked with the self-assembly of normally soluble proteins into amyloid fibrils. In this work, in silico characterization of the structures of the monomer and dimer of Aβ(1-28) are studied with the coarse-grained OPEP model using the activation-relaxation technique (ART nouveau). We find a dominant anti-parallel β-sheet structure present for both the monomer and dimer. While the monomer does not adopt a stable conformation, it fluctuates around a well-defined structure: starting from the end point, the monomer wraps a first time around, producing a β-hairpin and returns on the other side of the N-terminal, forming a three-strand β-sheet. The dimer assembles in a similar fashion, but with the two strands interlocking. The thermodynamics of the molecular assemblies and various folding path-ways are further studied using molecular dynamics.

  10. A novel quinoxaline bearing electroactive monomer: Pyrrole as the donor moiety

    Energy Technology Data Exchange (ETDEWEB)

    Taskin, Asli Tuba; Balan, Abidin; Epik, Bugra; Yildiz, Ersin [Middle East Technical University, Department of Chemistry, 06531, Ankara (Turkey); Udum, Yasemin Arslan [Gazi University, Institute of Science and Technology, Department of Advanced Technologies, 06570, Ankara (Turkey); Toppare, Levent [Middle East Technical University, Department of Chemistry, 06531, Ankara (Turkey)], E-mail: toppare@metu.edu.tr

    2009-09-30

    A novel electroactive monomer 5,8-di(1H-pyrrol-2-yl)-2,3-di(thiophen-2-yl)quinoxaline (PTQ) was successfully synthesized and its electrochromic properties were reported. Nuclear magnetic resonance ({sup 1}H NMR-{sup 13}C NMR) and mass spectroscopy were used to characterize the monomer. The monomer was electrochemically polymerized in the presence of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte in dichloromethane. Monomer reveals relatively low oxidation potential at +0.70 V. Spectroelectrochemical behaviors and switching ability of homopolymer were investigated by UV-vis spectroscopy and cyclic voltammetry. Two {pi}-{pi}* transitions were observed at 400 and 815 nm with a low band gap, 1.0 eV. Polymer possesses 66% optical contrast in the Near IR region, which may be promising in NIR electrochromic device applications.

  11. Facile synthesis of allyl resinate monomer in an aqueous solution under microwave irradiation

    Indian Academy of Sciences (India)

    Yanju Lu; Mixia Wang; Zhendong Zhao; Yuxiang Chen; Shichao Xu; Jing Wang; Liangwu Bi

    2015-07-01

    We have developed a facile method for production of allyl resinate monomer (allyl rosin ester) via a phase transfer reaction under microwave irradiation. The synthesis of allyl resinate was conducted using allyl chloride and sodium resinate as starting materials in aqueous solution at 50°C for 30 min with a yield of 94.7%, which is 20% higher than conventional heating method. The products precipitated spontaneously from the aqueous phase after reaction, which significantly facilitated the subsequent separation of monomer products. The synthesized monomer product appeared as a viscous liquid, with a viscosity of 460 mPa·s at 25°C and a density of 1.0469 g/cm3. The physical and chemical properties suggested that the synthesized monomer has great potential for free radical polymerization.

  12. Preparation of Core-Shell Coordination Molecular Assemblies via the Enrichment of Structure-Directing "Codes" of Bridging Ligands and Metathesis of Metal Units

    Energy Technology Data Exchange (ETDEWEB)

    Park, J; Chen, YP; Perry, Z; Li, JR; Zhou, HC

    2014-12-03

    A series of molybdenum- and copper-based MOPs were synthesized through coordination-driven process of a bridging ligand (3,3'-PDBAD, L-1) and dimetal paddlewheel clusters. Three conformers of the ligand exist with an ideal bridging angle between the two carboxylate groups of 0 degrees (H-2 zeta-L(1)), 120 degrees (H-2 beta-L-1), and of 90 degrees (H-2 beta-L-1), respectively. At ambient or lower temperature, (HL1)-L-2 and Mo-2(OAc)(4) or Cu-2(OAc)(4) were crystallized into a molecular square with ?-L-1 and Mo-2/Cu-2 units. With proper temperature elevation, not only the molecular square with ?-L-1 but also a lantern-shaped cage with a-L-1 formed simultaneously. Similar to how Watson-Crick pairs stabilize the helical structure of duplex DNA, the core-shell molecular assembly possesses favorable H-bonding interaction sites. This is dictated by the ligand conformation in the shell, coding for the formation and providing stabilization of the central lantern shaped core, which was not observed without this complementary interaction. On the basis of the crystallographic implications, a heterobimetallic cage was obtained through a postsynthetic metal ion metathesis, showing different reactivity of coordination bonds in the core and shell. As an innovative synthetic strategy, the site-selective metathesis broadens the structural diversity and properties of coordination assemblies.

  13. Solvent-induced secondary building unit (SBU) variations in a series of Cu(II) metal-organic frameworks derived from a bifunctional ligand.

    Science.gov (United States)

    Chen, Di-Ming; Ma, Jian-Gong; Cheng, Peng

    2015-05-21

    The role of auxiliary solvents in the formation of metal-organic frameworks (MOFs) has been studied for a series of copper-based framework systems. Herein we show the formation of three different 3D ordered frameworks with the formulae {[Cu4(cpt)4Cl4]·2DMF·dioxane·3H2O}n (1), {[Cu8(cpt)4(Hcpt)2Cl7(μ3-OH)2(H2O)4]Cl3·4CH3CN}n (2), and {[Cu8(cpt)4Cl4(μ3-OH)2(μ4-O)2]Cl2·4H2O·2CH3CN·3MeOH}n (3) [Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole], respectively, from the same reaction mixture through varying auxiliary solvents of the medium. These MOFs were fully characterized by single-crystal X-ray diffraction, showing interesting secondary building unit (SBU) variations. The varied SBUs not only bring different framework architectures to these MOFs, but also affect their framework stability. Gas sorption studies of MOF 3 reveal high CO2-N2 selectivity at 298 K and 0.16 bar (a typical partial pressure of CO2 in an industrial flue gas). A high isosteric heat of adsorption (Qst) at zero loading (53 kJ mol(-1)) was also observed in MOF 3.

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

    Science.gov (United States)

    Sarkar, Bidyut; Das, Anand K; Maiti, Sudipta

    2013-01-01

    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 (AD). 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., 2011). Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of monomers and 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 min 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 h 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.

  15. 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.

  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. Qualitative and quantitative analysis of monomers in polyesters for food contact materials.

    Science.gov (United States)

    Brenz, Fabrian; Linke, Susanne; Simat, Thomas

    2017-02-01

    Polyesters (PESs) are gaining more importance on the food contact material (FCM) market and the variety of properties and applications is expected to be wide. In order to acquire the desired properties manufacturers can combine several FCM-approved polyvalent carboxylic acids (PCAs) and polyols as monomers. However, information about the qualitative and quantitative composition of FCM articles is often limited. The method presented here describes the analysis of PESs with the identification and quantification of 25 PES monomers (10 PCA, 15 polyols) by HPLC with diode array detection (HPLC-DAD) and GC-MS after alkaline hydrolysis. Accurate identification and quantification were demonstrated by the analysis of seven different FCM articles made of PESs. The results explained between 97.2% and 103.4% w/w of the polymer composition whilst showing equal molar amounts of PCA and polyols. Quantification proved to be precise and sensitive with coefficients of variation (CVs) below 6.0% for PES samples with monomer concentrations typically ranging from 0.02% to 75% w/w. The analysis of 15 PES samples for the FCM market revealed the presence of five different PCAs and 11 different polyols (main monomers, co-monomers, non-intentionally added substances (NIAS)) showing the wide variety of monomers in modern PESs. The presented method provides a useful tool for commercial, state and research laboratories as well as for producers and distributors facing the task of FCM risk assessment. It can be applied for the identification and quantification of migrating monomers and the prediction of oligomer compositions from the identified monomers, respectively.

  18. Shrinkage strain – Rates study of dental composites based on (BisGMA/TEGDMA monomers

    Directory of Open Access Journals (Sweden)

    A. Amirouche-Korichi

    2017-02-01

    The results revealed that the fraction of opaque filler had no significant effect on the shrinkage strain-rate and on the time at maximum shrinkage strain-rate but these two parameters are closely related to the monomer ratios and viscosity of the organic matrix. The results have confirmed the proportionality of the shrinkage strain and DC and showed that the filler contents and monomer ratios would not affect this proportionality.

  19. 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....

  20. Concomitant sensitization to glutaraldehyde and methacrylic monomers among dentists and their patients

    OpenAIRE

    Maya Grigorievna Lyapina; Maria Dencheva; Assya Krasteva-Panova; Mariana Tzekova-Yaneva; Mariela Deliverska; Angelina Kisselova-Yaneva

    2016-01-01

    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-xypropoxy)phenyl]-propane (Bis-GMA), 2-hydroxy-e...

  1. 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.

  2. Impregnation of mortars with monomers and their radiolytic polymerization. [Gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Gadalla, A.M.; El-Derini, M.E.

    1984-10-01

    Mortars were cured for a sufficient period to give sufficient strength and were then dried to remove the free water without dehydrating the compounds formed. Dried specimens were evacuated and impregnated with a mixture of styrene and acrylonitrile monomers which gives high mechanical properties after polymerization. Positive pressure was then applied, and polymerization was done radiolytically. The effect of degree and period of evacuation, the positive pressure and the irradiation dose on monomer loading, tensile and compressive strength were studied, and the optimum operating conditions were established. The achieved strength was correlated with the fraction of open pores impregnated. The composites investigated have the same volume fraction of mortar, and the polymer is added at the expense of the open porosity causing nearly an exponential increase in strength. Only 80% of the open pores were filled with polymers due to the difference in density between the polymer and the monomer, loss of monomer, and the presence of entrapped gas consisting of residual air and residual water vapor and monomer vapor, as well as due to the inability to fill all the micropores with monomer. A compressive strengh four times that of plain mortar and a tensile strength eight times that of plain mortar were achieved. 18 references, 12 figures.

  3. Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin.

    Science.gov (United States)

    Ohta, Yukari; Hasegawa, Ryoichi; Kurosawa, Kanako; Maeda, Allyn H; Koizumi, Toshio; Nishimura, Hiroshi; Okada, Hitomi; Qu, Chen; Saito, Kaori; Watanabe, Takashi; Hatada, Yuji

    2017-01-20

    Enzymatic catalysis is an ecofriendly strategy for the production of high-value low-molecular-weight aromatic compounds from lignin. Although well-definable aromatic monomers have been obtained from synthetic lignin-model dimers, enzymatic-selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a cascade reaction of β-O-4-cleaving bacterial enzymes in one pot. Guaiacylhydroxylpropanone (GHP) and the GHP/syringylhydroxylpropanone (SHP) mixture are exclusive monomers from lignin isolated from softwood (Cryptomeria japonica) and hardwood (Eucalyptus globulus). The intermediate products in the enzymatic reactions show the capacity to accommodate highly heterologous substrates at the substrate-binding sites of the enzymes. To demonstrate the applicability of GHP as a platform chemical for bio-based industries, we chemically generate value-added GHP derivatives for bio-based polymers. Together with these chemical conversions for the valorization of lignin-derived phenylpropanone monomers, the specific and enzymatic production of the monomers directly from natural lignin is expected to provide a new stream in "white biotechnology" for sustainable biorefineries.

  4. A highly luminescent tetramer from a weakly emitting monomer: acid- and redox-controlled multiple complexation by cucurbit[7]uril.

    Science.gov (United States)

    Bergamini, Giacomo; Fermi, Andrea; Marchini, Marianna; Locritani, Mirko; Credi, Alberto; Venturi, Margherita; Negri, Fabrizia; Ceroni, Paola; Baroncini, Massimo

    2014-06-01

    The tetrahedral, shape-persistent molecule 1(4+), containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm(-1)) and a very strong fluorescence (Φem = 40 %), compared with the monomer 2(+) (Φem = 0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1(4+) and 2(+) show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.

  5. 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.

  6. Kinetic measurement of esterase-mediated hydrolysis for methacrylate monomers used in dental composite biomaterials

    Science.gov (United States)

    Russo, Karen Ann

    Methacrylate-based monomers are routinely used in medical biomaterials. Monomers undergo polymerization reactions to form the solid resin. These polymerization reactions can be incomplete thus making unpolymerized monomer available for possible biodistribution. Understanding the fate of these monomers is essential not only for their toxicological profile but also for development of future biomaterials. Aromatic methacrylate-based monomers included in this study were bisphenol A dimethacrylate and bisphenol A diglycidyl dimethathacrylate; aliphatic methacrylate monomers were 2-hydroxyethyl methacrylate and triethyleneglycol dimethacrylate. These compounds contain ester moieties thought to be susceptible to esterase-mediated hydrolysis. The hypothesis was that the ester bond of the methacrylate monomers can be hydrolyzed by esterases and these reactions would occur in a measurable, time-dependent manner confirmed by specific Michaelis-Menten kinetic relationships. Including aliphatic and aromatic methacrylate monomers in this work allowed for structure-based comparisons. In vitro enzymolysis of the test compounds by acetylcholinesterase and cholesterol esterase was performed in buffered solutions. The hydrolysis reactions were monitored by high performance liquid chromatography with ultraviolet detection. The disappearance of parent compound and appearance of hydrolysis products were quantitated. The aromatic methacrylate monomers, bisphenol A dimethacrylate and bisphenol A diglycidyl dimethacrylate, were resistant to acetylcholine esterase hydrolysis but were converted by cholesterol esterase. The putative xenoestrogen, bisphenol A, was identified as a hydrolysis product from bisphenol A dimethacrylate conversion. Cholesterol esterase induced hydrolysis of bisphenol A diglycidyl dimethacrylate yielded a Km value of 1584 muM and Vmax of 14 muM min-1. Triethyleneglycol was converted by both esterases with calculated Km values of 394 and 1311 muM for acetylcholine

  7. p-Coumaric acid - a monomer in the sporopollenin skeleton.

    Science.gov (United States)

    Wehling, K; Niester, C; Boon, J J; Willemse, M T; Wiermann, R

    1989-10-01

    Sporopollenin obtained from wings of Pinus mugo (Turra) pollen was analysed by pyrolysis mass spectrometry. In the spectrum, mass peaks which are characteristic for p-coumaric acid were dominant. p-Coumaric acid was the main degradation compound when the wing material was treated by a gentle method using AII3, and also when the remaining residue of the treated sporopollenin material was saponified. It is therefore assumed that p-coumaric acid is a genuine structural unit in the sporopollenin skeleton. In addition, the effects of AII3 treatment indicate that the p-coumaric acid might be bound by ether linkages.

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

    Science.gov (United States)

    Bernini, S.; Leporini, D.

    2016-05-01

    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.

  9. 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

    2014-01-01

    Objectives 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. Materials and method 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). Results 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. Significance 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. PMID:24993811

  10. 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.

  11. Testing their metal.

    OpenAIRE

    Fisher, B. E.

    1999-01-01

    Metals continually rank at the top of the U.S. Environmental Protection Agency's annual list of agents that pose the greatest hazard to the people of the United States. Metals aren't going away, either. They do not biodegrade, and they often concentrate in human and animal cells and tissue. Many metals are known human and animal carcinogens, while many others are suspected to play a role in cancer. Little is known, however, about the mechanisms by which metals cause cancer.

  12. Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects.

    Science.gov (United States)

    McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J

    2014-08-19

    Polyolefins are produced today catalytically on a vast scale, and the manufactured polymers find use in everything from artificial limbs and food/medical packaging to automotive and electrical components and lubricants. Although polyolefin monomers are typically cheap (e.g., ethylene, propylene, α-olefins), the resulting polymer properties can be dramatically tuned by the particular polymerization catalyst employed, and reflect a rich interplay of macromolecular chemistry, materials science, and physics. For example, linear low-density polyethylene (LLDPE), produced by copolymerization of ethylene with linear α-olefin comonomers such as 1-butene, 1-hexene, or 1-octene, has small but significant levels of short alkyl branches (C2, C4, C6) along the polyethylene backbone, and is an important technology material due to outstanding rheological and mechanical properties. In 2013, the total world polyolefin production was approximately 211 million metric tons, of which about 11% was LLDPE. Historically, polyolefins were produced using ill-defined but highly active heterogeneous catalysts composed of supported groups 4 or 6 species (usually halides) activated by aluminum alkyls. In 1963, Karl Ziegler and Giulio Natta received the Nobel Prize for these discoveries. Beginning in the late 1980s, a new generation of group 4 molecule-based homogeneous olefin polymerization catalysts emerged from discoveries by Walter Kaminsky, a team led by James Stevens at The Dow Chemical Company, this Laboratory at Northwestern University, and a host of talented groups in Germany, Italy, Japan, the United Kingdom, and the United States. These new "single-site" catalysts and their activating cocatalysts were far better defined and more rationally tunable in terms of structure, mechanism, thermodynamics, and catalyst activity and selectivity than ever before possible. An explosion of research advances led to new catalysts, cocatalysts, deeper mechanistic understanding of both the

  13. Metal-ligand bifunctional reactivity and catalysis of protic N-heterocyclic carbene and pyrazole complexes featuring β-NH units.

    Science.gov (United States)

    Kuwata, Shigeki; Ikariya, Takao

    2014-11-28

    Metal-ligand bifunctional cooperation has attracted much attention because it offers a powerful methodology to realize a number of highly efficient and selective catalysts. In this article, recent developments in the metal-ligand cooperative reactions of protic N-heterocyclic carbene (NHC) and pyrazole complexes bearing an acidic NH group at the position β to the metal are surveyed. Protic 2-pyridylidenes as related cooperating non-innocent ligands are also described.

  14. Thermostability of photosystem I trimers and monomers from the cyanobacterium Thermosynechococcus elongatus

    Science.gov (United States)

    Shubin, Vladimir V.; Terekhova, Irina V.; Bolychevtseva, Yulia V.; El-Mohsnawy, Eithar; Rögner, Matthias; Mäntele, Werner; Kopczak, Marta J.; Džafić, Enela

    2017-05-01

    The performance of solar energy conversion into alternative energy sources in artificial systems highly depends on the thermostability of photosystem I (PSI) complexes Terasaki et al. (2007), Iwuchukwu et al. (2010), Kothe et al. (2013) . To assess the thermostability of PSI complexes from the thermophilic cyanobacterium Thermosynechococcus elongatus heating induced perturbations on the level of secondary structure of the proteins were studied. Changes were monitored by Fourier transform infrared (FT-IR) spectra in the mid-IR region upon slow heating (1 °C per minute) of samples in D2O phosphate buffer (pD 7.4) from 20 °C to 100 °C. These spectra showed distinct changes in the Amide I region of PSI complexes as a function of the rising temperature. Absorbance at the Amide I maximum of PSI monomers (centered around 1653 cm- 1), gradually dropped in two temperature intervals, i.e. 60-75 and 80-90 °C. In contrast, absorbance at the Amide I maximum of PSI trimers (around 1656 cm- 1) dropped only in one temperature interval 80-95 °C. The thermal profile of the spectral shift of α-helices bands in the region 1656-1642 cm- 1 confirms the same two temperature intervals for PSI monomers and only one interval for trimers. Apparently, the observed absorbance changes at the Amide I maximum during heating of PSI monomers and trimers are caused by deformation and unfolding of α-helices. The absence of absorbance changes in the interval of 20-65 °C in PSI trimers is probably caused by a greater stability of protein secondary structure as compared to that in monomers. Upon heating above 80 °C a large part of α-helices both in trimers and monomers converts to unordered and aggregated structures. Spectral changes of PSI trimers and monomers heated up to 100 °C are irreversible due to protein denaturation and non-specific aggregation of complexes leading to new absorption bands at 1618-1620 cm- 1. We propose that monomers shield the denaturation sensitive sides at the

  15. Limit theorems in the imitative monomer-dimer mean-field model via Stein's method

    Science.gov (United States)

    Chen, Wei-Kuo

    2016-08-01

    We consider the imitative monomer-dimer model on the complete graph introduced in the work of Alberici et al. [J. Math. Phys. 55, 063301-1-063301-27 (2014)]. It was shown that this model is described by the monomer density and has a phase transition along certain coexistence curve, where the monomer and dimer phases coexist. More recently, it was understood [D. Alberici et al., Commun. Math. Phys. (published online, 2016)] that the monomer density exhibits the central limit theorem away from the coexistence curve and enjoys a non-normal limit theorem at criticality with normalized exponent 3/4. By reverting the model to a weighted Curie-Weiss model with hard core interaction, we establish the complete description of the fluctuation properties of the monomer density on the full parameter space via Stein's method of exchangeable pairs. Our approach recovers what were established in the work of Alberici et al. [Commun. Math. Phys. (published online, 2016)] and furthermore allows to obtain the conditional central limit theorems along the coexistence curve. In all these results, the Berry-Esseen inequalities for the Kolmogorov-Smirnov distance are given.

  16. 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.

  17. Simulations of polymer brushes with charged end monomers under external electric fields

    Science.gov (United States)

    Ding, Huanda; Duan, Chao; Tong, Chaohui

    2017-01-01

    Using Langevin dynamics simulations, the response of neutral polymer brushes with charged terminal monomers to external electric fields has been investigated. The external electric field is equivalent to the field generated by the opposite surface charges on two parallel electrodes. The effects of charge valence of terminal monomers on the structure of double layers and overall charge balance near the two electrodes were examined. Using the charge density distributions obtained from simulations, the total electric field normal to the electrodes was calculated by numerically solving the Poisson equation. Under external electric fields, the total electric field across the two electrodes is highly non-uniform and in certain regions within the brush, the total electric field nearly vanishes. The probability distribution of electric force acting on one charged terminal monomer was obtained from simulations and how it affects the probability density distribution of terminal monomers was analyzed. The response of polymer brushes with charged terminal monomers to a strongly stretching external electric field was compared with that of uniformly charged polymer brushes.

  18. Epigallocatechin-3-Gallate Reduces Cytotoxic Effects Caused by Dental Monomers: A Hypothesis

    Science.gov (United States)

    Jiao, Yang; Ma, Sai; Wang, Yirong; Li, Jing; Shan, Lequn; Chen, Jihua

    2015-01-01

    Resin monomers from dental composite materials leached due to incomplete polymerization or biodegradation may cause contact allergies and damage dental pulp. The cytotoxicity of dental resin monomers is due to a disturbance of intracellular redox equilibrium, characterized by an overproduction of reactive oxygen species (ROS) and depletion of reduced glutathione (GSH). Oxidative stress caused by dental resin monomers leads to the disturbance of vital cell functions and induction of cell apoptosis in affected cells. The nuclear factor-erythroid 2-related factor 2 (Nrf2) pathway plays a key role in the cellular defense system against oxidative and electrophilic stress. Epigallocatechin-3-gallate (EGCG) can activate the Nrf2 pathway and induce expression of a multitude of antioxidants and phase II enzymes that can restore redox homeostasis. Therefore, here, we tested the hypothesis that EGCG-mediated protection against resin monomer cytotoxicity is mediated by activation of the Nrf2 pathway. This study will help to elucidate the mechanism of resin monomer cytotoxicity and provide information that will be helpful in improving the biocompatibility of dental resin materials. PMID:26489899

  19. Water sorption and solubility of dental composites and identification of monomers released in an aqueous environment.

    Science.gov (United States)

    Ortengren, U; Wellendorf, H; Karlsson, S; Ruyter, I E

    2001-12-01

    Water sorption and solubility of six proprietary composite resin materials were assessed, and monomers eluted from the organic matrix during water storage identified. Water sorption and solubility tests were carried out with the following storage times: 4 h, 24 h and 7, 60 and 180 days. After storage, water sorption and solubility were determined. Eluted monomers were analysed by high performance liquid chromatography (HPLC). Correlation between the retention time of the registered peak and the reference peak was observed, and UV-spectra confirmed the identity. The results showed an increase in water sorption until equilibrium for all materials with one exception. The solubility behaviour of the composite resin materials tested revealed variations, with both mass decrease and increase. The resin composition influences the water sorption and solubility behaviour of composite resin materials. The HPLC analysis of eluted components revealed that triethyleneglycol dimethacrylate (TEGDMA) was the main monomer released. Maximal monomer concentration in the eluate was observed after 7 days. During the test period, quantifiable quantities of urethanedimethacrylate (UEDMA) monomer were observed, whereas 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]propane (Bis-GMA) was only found in detectable quantities. No detectable quantities of bisphenol-A were observed during the test period.

  20. Aβ1-42 monomers or oligomers have different effects on autophagy and apoptosis.

    Science.gov (United States)

    Guglielmotto, Michela; Monteleone, Debora; Piras, Antonio; Valsecchi, Valeria; Tropiano, Marta; Ariano, Stefania; Fornaro, Michele; Vercelli, Alessandro; Puyal, Julien; Arancio, Ottavio; Tabaton, Massimo; Tamagno, Elena

    2014-10-01

    The role of autophagy and its relationship with apoptosis in Alzheimer disease (AD) pathogenesis is poorly understood. Disruption of autophagy leads to buildup of incompletely digested substrates, amyloid-β (Aβ) peptide accumulation in vacuoles and cell death. Aβ, in turn, has been found to affect autophagy. Thus, Aβ might be part of a loop in which it is both the substrate of altered autophagy and its cause. Given the relevance of different soluble forms of Aβ1-42 in AD, we have investigated whether monomers and oligomers of the peptide have a differential role in causing altered autophagy and cell death. Using differentiated SK-N-BE neuroblastoma cells, we found that monomers hamper the formation of the autophagic BCL2-BECN1/Beclin 1 complex and activate the MAPK8/JNK1-MAPK9/JNK2 pathway phosphorylating BCL2. Monomers also inhibit apoptosis and allow autophagy with intracellular accumulation of autophagosomes and elevation of levels of BECN1 and LC3-II, resulting in an inhibition of substrate degradation due to an inhibitory action on lysosomal activity. Oligomers, in turn, favor the formation of the BCL2-BECN1 complex favoring apoptosis. In addition, they cause a less profound increase in BECN1 and LC3-II levels than monomers without affecting the autophagic flux. Thus, data presented in this work show a link for autophagy and apoptosis with monomers and oligomers, respectively. These studies are likely to help the design of novel disease modifying therapies.

  1. Synthesis of a resin monomer-soluble polyrotaxane crosslinker containing cleavable end groups.

    Science.gov (United States)

    Seo, Ji-Hun; Nakagawa, Shino; Hirata, Koichiro; Yui, Nobuhiko

    2014-01-01

    A resin monomer-soluble polyrotaxane (PRX) crosslinker with cleavable end groups was synthesized to develop degradable photosetting composite resins. The PRX containing 50 α-cyclodextrins (α-CDs) with disulfide end groups was initially modified with n-butylamine to obtain a resin monomer-soluble PRX. The PRX containing 13 n-butyl groups per α-CD molecule was completely soluble in conventional resin monomers such as 2-hydroxyethyl methacrylate (HEMA) and urethane dimethacrylate (UDMA). The synthesized n-butyl-containing PRX was further modified with 2-aminoethyl methacrylate to provide crosslinkable acrylic groups onto PRX. The prepared resin monomer-soluble PRX crosslinker was successfully polymerized with a mixture of HEMA and UDMA to provide photosetting plastic. It was confirmed that the Vickers hardness of the prepared plastic was greatly decreased after treatment with dithiothreitol. This indicates that the resin monomer-soluble PRX crosslinker can be applied to design degradable photosetting plastics potentially used in the industrial or biomedical field.

  2. Synthesis of a resin monomer-soluble polyrotaxane crosslinker containing cleavable end groups

    Directory of Open Access Journals (Sweden)

    Ji-Hun Seo

    2014-11-01

    Full Text Available A resin monomer-soluble polyrotaxane (PRX crosslinker with cleavable end groups was synthesized to develop degradable photosetting composite resins. The PRX containing 50 α-cyclodextrins (α-CDs with disulfide end groups was initially modified with n-butylamine to obtain a resin monomer-soluble PRX. The PRX containing 13 n-butyl groups per α-CD molecule was completely soluble in conventional resin monomers such as 2-hydroxyethyl methacrylate (HEMA and urethane dimethacrylate (UDMA. The synthesized n-butyl-containing PRX was further modified with 2-aminoethyl methacrylate to provide crosslinkable acrylic groups onto PRX. The prepared resin monomer-soluble PRX crosslinker was successfully polymerized with a mixture of HEMA and UDMA to provide photosetting plastic. It was confirmed that the Vickers hardness of the prepared plastic was greatly decreased after treatment with dithiothreitol. This indicates that the resin monomer-soluble PRX crosslinker can be applied to design degradable photosetting plastics potentially used in the industrial or biomedical field.

  3. 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.

  4. Comparison of marginal and internal fit of press-on-metal and conventional ceramic systems for three- and four-unit implant-supported partial fixed dental prostheses: An in vitro study.

    Science.gov (United States)

    Bayramoğlu, Emre; Özkan, Yasemin Kulak; Yildiz, Coşkun

    2015-07-01

    Adaptation is an important factor in the long-term clinical success of implant supported ceramic restorations. Ceramic firings may affect the adaptation of the restoration. The purpose of this study was to compare the marginal and internal adaptation of 3 different restorative materials and the effect of veneering/pressing on the material used for 3- and 4-unit implant supported fixed dental prostheses. One mandibular epoxy cast was prepared for 3-unit restorations and one for 4-unit restorations. Impressions of the casts were made and 60 stone die casts (30 3-unit, 30 4-unit) produced. The casts were divided into 3 subgroups: group MCR, conventional metal ceramic restorations; group POM, press-on-metal restorations; group ZIR, computer-aided design/computer-aided manufacturing CAD/CAM) zirconia restorations. A replica technique was used to examine the marginal and internal gap values. A total of 2400 measurements were made by making 40 measurements of each restoration. The data were evaluated statistically using analysis of variance and the least significant difference post hoc test (α=.05). The lowest marginal gaps were found in group POM (81.58 μm) and the highest in group MCR (103.82 μm). The differences in marginal adaptation measurements were found to be statistically significant. The highest values for internal adaptation were found at the occlusal surface in all groups. Although veneering metal ceramic restorations increased the misfit of the restoration, the marginal discrepancy of the materials (81 to 120 μm) can be considered clinically acceptable. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  5. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    Energy Technology Data Exchange (ETDEWEB)

    Bréchignac, Philippe, E-mail: philippe.brechignac@u-psud.fr; Falvo, Cyril; Parneix, Pascal; Pino, Thomas; Pirali, Olivier [Institut des Sciences Moléculaires d’Orsay, CNRS UMR8214, Univ Paris-Sud, F-91405 Orsay (France); Garcia, Gustavo A.; Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, B.P. 48, F-91192 Gif-sur-Yvette (France); Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony [IRAP, Université de Toulouse 3 - CNRS, 9 Av. Colonel Roche, B.P. 44346, F-31028 Toulouse Cedex 4 (France); Mulas, Giacomo [INAF - Osservatorio Astronomico di Cagliari, via della scienza 5, I-09047 Selargius (Italy)

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

  6. Child and adult exposure and health risk evaluation following the use of metal- and metalloid-containing costume cosmetics sold in the United States.

    Science.gov (United States)

    Perez, Angela L; Nembhard, Melanie; Monnot, Andrew; Bator, Daniel; Madonick, Elizabeth; Gaffney, Shannon H

    2017-03-01

    Costume cosmetics (lipstick, body paints, eyeshadow) were analyzed for metals using inductively coupled plasma mass spectrometry (ICP-MS). Sb was detected in all samples (range: 0.12-6.3 mg/kg; d.f. 100%), followed by Pb (cosmetics should be evaluated further to prevent unnecessary metal exposure. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Anchoring Strength of Thin Aligned-Polymer Films Formed by Liquid Crystalline Monomer

    Science.gov (United States)

    Murashige, Takeshi; Fujikake, Hideo; Ikehata, Seiichiro; Sato, Fumio

    2003-04-01

    We have evaluated the polar anchoring strength of a thin molecule-aligned polymer film formed by a liquid crystalline monomer. The polymer film was obtained by photopolymerization of the monomer oriented by a rubbed polyimide alignment layer in a chamber filled with N2 gas. We fabricated a nematic liquid crystal cell using the thin aligned-polymer films as alignment layers, and then evaluated the anchoring strength of the polymer by measuring the optical retardation curve of the cell driven by voltages. The experimental result showed that the anchoring strength was one order of magnitude lower than that of a conventional rubbed polyimide alignment layer, and decreased with increasing the cure temperature of the monomer film.

  8. Theoretical Researches on the Recognizing Characteristics of Atrazine Imprinted Polymers with Different Functional Monomers

    Institute of Scientific and Technical Information of China (English)

    LIU Jun-Bo; SUN Jia-Ni; TANG Shan-Shan; CHEN Kai-Yin; JIN Rui-Fa

    2012-01-01

    As a widely used herbicide, the threat of atrazine to both environment and health of people has become the focus. Therefore, the research and analysis of atrazine are getting more important. In this work, the MIT was used to detect atrazine theoretically. Atrazine was taken as a template molecule. MAA, MMA and TFMAA were taken as the functional monomers, respectively. The geometry optimization, the nature of hydrogen bonds, the NBO charge, and the binding energies of the imprinted molecule with the functional monomers were investigated at the B3LYP/6-31g(d,p) level. Results indicated that atrazine had the strongest interaction with TFMAA. When the ratio of atrazine and TFMAA was 1:6, the amount of H-bond formed from atrazine and TFMAA was the largest. Moreover, TFMAA owned the largest binding energy with atrazine while MMA owned the smallest. The study is helpful to interpret experiment phenomena of molecular imprinting and select better functional monomers.

  9. Protein imprinted polymer using acryloyl-β-cyclodextrin and acrylamide as monomers

    Science.gov (United States)

    Zhang, Wei; Qin, Lei; Chen, Run-Run; He, Xi-Wen; Li, Wen-You; Zhang, Yu-Kui

    2010-02-01

    A novel protein imprinted polymer was prepared using acryloyl-β-cyclodextrin (β-CD) and acrylamide as monomers on the surface of silica gel. The bovine hemoglobin was used as template and β-CD was allowed to self-assemble with the template protein through hydrogen bonding and hydrophobic interaction. Polymerization was carried out in the presence of acrylamide as an assistant monomer, which resulted in a novel protein imprinted polymer. After removing the template, imprinted cavities with the shape and spatial distribution of functional groups were formed. Bovine serum albumin (BSA) cytochrome c (Cyt) and lysozyme (Lyz) were employed as non-template proteins to test the imprinting effect and the specific binding of bovine hemoglobin to the polymer. The results of the adsorption experiments indicated that such protein imprinted polymer, which was synthesized with β-CD and acrylamide as monomers, could selectively recognize the template protein.

  10. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

    Science.gov (United States)

    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 (2 σ).

  11. Effect of trifunctional monomers and antioxidants on crosslinking reaction of polyethylene. [Electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Pyun, H.C.; Lee, Y.C.; Kim, K.J.; Yoon, B.M. (Korea Advanced Energy Research Inst., Seoul (Republic of Korea))

    1982-06-01

    The crosslinking reaction and oxidative stability of low-density polyethylene were studied in the presence of trifunctional monomers and antioxidants with electron beams. The trifunctional monomers used in this study are Trimethylolpropane triacrylate (TMPTA), Trimethylolpropane trimethacrylate (TMPTM) and Triallyl cyanurate (TAC). And the antioxidants are Irganox 1010 (Pentaerythritoltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenly)-propionate)), Santonox R(4,4'-Thio-bis(3-methyl-6-t-butylphenol)), Nocrac D(N-phenyl-..beta..-naphthylamine) and Bisphenol A(4,4'-Isopropylidene bisphenol). Among the monomers, TMPTA is the best crosslinking agent and provides polyethylene with oxidative stability. Among the antioxidants, Nocrac D is the best antioxidant for polyethylene.

  12. 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.

  13. Evaluation of the level of residual monomer in acrylic denture base materials having different polymerization properties.

    Science.gov (United States)

    Kalipçilar, B; Karaağaçlioğlu, L; Hasanreisoğlu, U

    1991-09-01

    The aim of this study was to evaluate the level of residual monomer in acrylic denture base materials having different polymerization properties. The investigation included a conventional-type acrylic cured under heat and pressure, as well as a pour-type resin polymerized by an injection-moulding technique at room temperature and under pressure. It was found that the residual monomer content ranged from 0.22-0.54% in pour-type resin, and from 0.23-0.52% in routinely used resins when the specimens were analysed by high performance liquid chromatography. These findings revealed that there were no significant differences between the two types of acrylic in terms of their residual monomer content.

  14. Preparation of molecularly imprinted polymers using anacardic acid monomers derived from cashew nut shell liquid.

    Science.gov (United States)

    Philip, Joseph Y N; Buchweishaija, Joseph; Mkayula, Lupituko L; Ye, Lei

    2007-10-31

    The objective of this work was to use monomers from cashew ( Anacardium occidentale L.) nut shells to develop molecularly imprinted polymers. Cashew nut shell liquid (CNSL) is a cheap and renewable agro byproduct consisting of versatile monomers. Solvent-extracted CNSL contains over 80% anacardic acid (AnAc) with more than 90% degree of unsaturation in its C 15 side chain. From AnAc monomer, anacardanyl acrylate (AnAcr) and anacardanyl methacrylate (AnMcr) monomers were synthesized and their chemical structures were characterized by Fourier transform IR and NMR. Different imprinted bulk polymers based on AnAc, AnAcr, and AnMcr functional monomers have been prepared. In the present study, each functional monomer was separately copolymerized in toluene with ethylene glycol dimethacrylate and divinylbenzene as cross-linkers, using racemic propranolol as a model template. While the AnAc based polymer revealed a meager rebinding ability, the imprinted polymers made from AnAcr and AnMcr displayed highly specific propranolol binding. At a polymer concentration of 2 mg/mL, AnAcr and AnMcr based imprinted polymers were able to bind over 50% of trace propranolol (initial concentration 1.2 nM). Under the same condition propranolol uptake by the two nonimprinted control polymers was less than 20%. Chiral recognition properties of these polymers were further confirmed using tritium-labeled (S)-propranolol as a tracer in displacement experiments, suggesting that the apparent affinity of the imprinted chiral sites for the correct enantiomer is at least 10 times that of the mismatched (R)-propranolol. Moreover, cross reactivity studies of these polymers showed that the (S)-imprinted sites have higher cross-reactivity toward (R, S)-metoprolol than (R)-propranolol and (R)-timolol.

  15. 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.

  16. Intra- And Inter-Monomer Interactions are Required to Synergistically Facilitate ATP Hydrolysis in HSP90

    Energy Technology Data Exchange (ETDEWEB)

    Cunningham, C.N.; Krukenberg, K.A.; Agard, D.A.

    2009-05-12

    Nucleotide-dependent conformational changes of the constitutively dimeric molecular chaperone Hsp90 are integral to its molecular mechanism. Recent full-length crystal structures (Protein Data Bank codes 2IOQ, 2CG9, AND 2IOP) of Hsp90 homologs reveal large scale quaternary domain rearrangements upon the addition of nucleotides. Although previous work has shown the importance of C-terminal domain dimerization for efficient ATP hydrolysis, which should imply cooperativity, other studies suggest that the two ATPases function independently. Using the crystal structures as a guide, we examined the role of intra- and intermonomer interactions in stabilizing the ATPase activity of a single active site within an intact dimer. This was accomplished by creating heterodimers that allow us to differentially mutate each monomer, probing the context in which particular residues are important for ATP hydrolysis. Although the ATPase activity of each monomer can function independently, we found that the activity of one monomer could be inhibited by the mutation of hydrophobic residues on the trans N-terminal domain (opposite monomer). Furthermore, these trans interactions are synergistically mediated by a loop on the cis middle domain. This loop contains hydrophobic residues as well as a critical arginine that provides a direct linkage to the {gamma}-phosphate of bound ATP. Small angle x-ray scattering demonstrates that deleterious mutations block domain closure in the presence of AMPPNP (5{prime}-adenylyl-{beta},{gamma}-imidodiphosphate), providing a direct linkage between structural changes and functional consequences. Together, these data indicate that both the cis monomer and the trans monomer and the intradomain and interdomain interactions cooperatively stabilize the active conformation of each active site and help explain the importance of dimer formation.

  17. Visible Light Curable Restorative Composites for Dental Applications Based on Epoxy Monomer

    Directory of Open Access Journals (Sweden)

    Alessandra Vitale

    2014-01-01

    Full Text Available A cationic photo-curable cycloaliphatic epoxy resin has been investigated as reactive monomer in blue light crosslinking process. We have demonstrated that camphorquinone is able to abstract labile hydrogen from the epoxy monomer, giving rise to the formation of carbon-centered radicals that are oxidized by the onium salt; a complete epoxy group conversion was reached after 50 s of irradiation. The presence of water up to 1 wt% was tolerated without any important detrimental effect on the kinetics of light-curing. The presence of the inorganic filler up to 65 wt% did not significantly influence the curing process.

  18. Theoretical investigation on functional monomer and solvent selection for molecular imprinting of tramadol

    Science.gov (United States)

    Fonseca, Matheus C.; Nascimento, Clebio S.; Borges, Keyller B.

    2016-02-01

    The purpose of this Letter was to study for the first time the interaction process of tramadol (TRM) with distinct functional monomers (FM) in the formation of molecular imprinted polymer (MIP), using density functional theory (DFT) calculations at B3LYP/6-31G(d,p). As result we were able to establish that the best MIP synthesis conditions are obtained with acrylic acid as FM in 1:3 molar ratio and with chloroform as solvent. This condition presented the lowest stabilization energy for the pre-polymerization complexes. Besides, the intermolecular hydrogen bonds found between the template molecule and functional monomers play a primary role to the complex stability.

  19. INFLUENCES OF WATER-SOLUBLE CATIONIC MONOMERS ON THE POLYMERIZATION RATE IN THE INVERSE EMULSION

    Institute of Scientific and Technical Information of China (English)

    HOU Sijian; HA Runhua

    1996-01-01

    This investigation deals with the free radical polymerization both of (2-methacryloyloxyethyl) trimethyl ammonium chloride (QACEMA) and of diallyldimethyl ammonium chloride (DADMAC) in inverse emulsion. The influences of some factors, such as the concentration of monomers, initiator and emulsifier are discussed. The polymerization rate equations of above two monomers can be written as follows:Rp = k[M]1.21[I]0.82[E]0.57 (for QACEMA)Rp = k′[M]1.34[I]0.90[E]0.62 (for DADMAC)

  20. 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...... pendant groups significantly improves the hydrolytic stability as well as the radical oxidative stability of the membranes. In addition, the SPI membranes exhibit high proton conductivities of 0.1 S cm(-1) in the fully hydrated state at 60 degrees C and high elastic modulus and tensile strength...

  1. One-pot synthesis of cyclic triamides with a triangular cavity from trans-stilbene and diphenylacetylene monomers.

    Science.gov (United States)

    Yokoyama, Akihiro; Maruyama, Takurou; Tagami, Kei; Masu, Hyuma; Katagiri, Kosuke; Azumaya, Isao; Yokozawa, Tsutomu

    2008-08-01

    Base-promoted self-condensation reactions of trans-stilbene and diphenylacetylene monomers bearing 4-alkylamino and 4'-methoxycarbonyl groups were investigated. Reactions of N-propyl monomers under pseudohigh-dilution conditions (a THF solution of monomer was added dropwise to a THF solution of LiHMDS) afforded the corresponding cyclic triamides in good yields. X-ray crystallographic analysis showed that these cyclic triamides possessed an almost equilateral triangle structure with a cavity surrounded by tilted benzene rings.

  2. [Aging effect on mechanical properties in fluid resin. (Part 3) Affection of residual monomer on the surface morphology after tensile test by microscopic observation (author's transl)].

    Science.gov (United States)

    Horiuchi, A

    1981-04-01

    Affection of residual monomer on the surface morphology after tensile test was observed by an scanning microscope. Evaporation or leaching of the monomer gave big influence on the morphology of pearls and matrix. The observation suggested that the residual monomer existed mainly in the matrix. When the residual monomer disappeared, the surface morphology did not change by tensile load. It is the most important point to get good denture with fluid resin that we could decrease the residual monomer as possible.

  3. Occurrence of naturally acetylated lignin units.

    Science.gov (United States)

    Del Río, José C; Marques, Gisela; Rencoret, Jorge; Martínez, Angel T; Gutiérrez, Ana

    2007-07-11

    This work examines the occurrence of native acetylated lignin in a large set of vascular plants, including both angiosperms and gymnosperms, by a modification of the so-called Derivatization Followed by Reductive Cleavage (DFRC) method. Acetylated lignin units were found in the milled wood lignins of all angiosperms selected for this study, including mono- and eudicotyledons, but were absent in the gymnosperms analyzed. In some plants (e.g., abaca, sisal, kenaf, or hornbeam), lignin acetylation occurred at a very high extent, exceeding 45% of the uncondensed (alkyl-aryl ether linked) syringyl lignin units. Acetylation was observed exclusively at the gamma-carbon of the lignin side chain and predominantly on syringyl units, although a predominance of acetylated guaiacyl over syringyl units was observed in some plants. In all cases, acetylation appears to occur at the monomer stage, and sinapyl and coniferyl acetates seem to behave as real lignin monomers participating in lignification.

  4. Basic building units, self-assembly and crystallization in the formation of complex inorganic open architectures

    Indian Academy of Sciences (India)

    C N R Rao

    2001-10-01

    Careful investigations of open-framework metal phosphates reveal that the formation of these complex architectures is likely to involve a process wherein one-dimensional ladders or chains, and possibly zero-dimens ional monomers, transform to higher dimensional structures. The one-dimensional ladder appears to be the primary building unit of these structures. At one stage of the building-up process, spontaneous self-assembly of a low-dimensional structure such as the ladder seems to occur, followed by crys tallization of a two- or three-dimensional structure. Accordingly, many of the higher dimensional structures retain the structural features of the 1D structure, indicating the occurrence of self-assembly. These findings mark the beginnings of our understan ding of complex supramolecular inorganic materials.

  5. Technical report: Water quality and metal and metalloid contaminants in sediments, and fish of Koyukuk, Nowitna, and the Northern Unit of Innoko National Wildlife Refuges, Alaska, 1991

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This study was conducted by U.S. Fish and Wildlife Service biologists during 1991. The study goals were to monitor water quality and concentrations of metals and...

  6. The role of polycarbonate monomer bisphenol-A in insulin resistance

    Directory of Open Access Journals (Sweden)

    Milos Pjanic

    2017-09-01

    Full Text Available 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

  7. Heterogeneous glycoform separation by process chromatography: I: Monomer purification and characterization.

    Science.gov (United States)

    Li, Yi; Xu, Xuankuo; Shupe, Alan; Yang, Rong; Bai, Kevin; Das, Tapan; Borys, Michael C; Li, Zheng Jian

    2015-07-24

    Fc fusion proteins with high and low sialylation were purified and separated by preparative ion-exchange and hydrophobic interaction chromatography. Heterogeneity in sialylation and glycosylation led to variation in surface charge and hydrophobicity, and resulted in multiple distinct glycoform populations in response to various purification conditions. Monomer with high sialic acid content has higher surface charge and adsorbs stronger to ion-exchange resin, while the less sialylated monomer interacts more favorably with hydrophobic resin. Extensive biophysical characterization was carried out for purified monomers at different level of sialylation. In general, different monomeric glycoforms have different surface charge and hydrophobicity, different thermal stability, and different aggregation propensity. The surface charge corresponds well with sialic acid content, as evidenced by electrophoresis, N-link domain analysis, and zeta potential results. The sialylation also contributes to minor modification of protein size, molecular mass and tertiary structure. Notably, fluorescence emission spectra and thermal transition became less distinguishable when the monomers containing low and high sialic acid were prepared in high ionic strength solution. Such finding reiterates the fact that the electrostatic forces, which are largely dependent on sialic acid content of protein, plays a dominant role in many intra- and inter-molecular interactions. Overall, the characterization data agreed well with separation behaviors and provided valuable insight to control of glycoform profile in purification process. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. PLASMA POLYMERIZATION OF HYDROPHILIC AND HYDROPHOBIC MONOMERS FOR SURFACE MODIFICATION OF NUCLE-MICROPOROUS MEMBRANE

    Institute of Scientific and Technical Information of China (English)

    LI Xuefen; LI Zhifen; CHEN Chuanfu; WU Wenhui

    1990-01-01

    Surface modification of nucle-microporous membrane by plasma polymerization of HEMA, NVP and D4 has been studied. The hydrophilicity of membranes was increased with increasing of plasma polymerization time of hydrophilic monomers HEMA and NVP. The flow rate of water through the membrane was increased remarkably after plasma polymerization of HEMA on it.

  9. Glycerol derivatives of cutin and suberin monomers: synthesis and self-assembly.

    Science.gov (United States)

    Douliez, Jean-Paul; Barrault, Joël; Jerome, François; Heredia, Antonio; Navailles, Laurence; Nallet, Frédéric

    2005-01-01

    Glycerol derivatives of cutin and suberin monomers were synthesized by acid catalysis. Their dispersion in an aqueous solution was examined by phase contrast microscopy, neutron scattering, and solid state NMR. It is shown that the phase behavior strongly depends on the nature of the derivatives forming either lumps of aggregated membranes or well dispersed membranes.

  10. [Discussing of influence mechanism of Chinese herbal monomer on physical stability of cream].

    Science.gov (United States)

    Yin, Hui-Fu; Nie, He-Yun; Wang, Sen; Zhu, Wei-Feng; Li, Rong-Miao

    2014-10-01

    This study left flavonoids and alkaloids Chinese herbal monomer with common parent nucleus as cream base carriages drug respectively, cream base were prepared with stable span 60-tween 80 emulsification system. The near-infrared stability analysis technology was performed to quantitatively characterize the physical stability of cream. Base on the theory of gel network structure, theory of emulsification, theory of solubility parameter and theory of double layer, the influence mechanism of Chinese herbal monomer on physical stability of cream was discussed. The results showed that tetrahydropalmatine, matrine and naringenin had similar solubility parameter value with cream base material, creams prepared with those Chinese herbal monomer have higher Zeta potential value and stronger physical stability, and that those creams had similar microstructure information with cream base. However, a larger solubility parameter difference exists between baicalin, baicalein, berberine, palmatine and cream base material. Creams prepared with those Chinese herbal monomers had lower Zeta potential value and poorer physical stability, and that those creams had great different microstructure information with cream base.

  11. Regulation of the PI3K pathway through a p85a monomer-homodimer equilibrium

    KAUST Repository

    Aljedani, Safia

    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.

  12. Determination of Residual Monomers in Polycarboxylate Superplasticizer Using High Performance Liquid Chromatography

    Institute of Scientific and Technical Information of China (English)

    GUO Liping; WANG Shaofeng; ZHANG Anfu; LEI Jiaheng; DU Xiaodi

    2011-01-01

    A procedure was developed for the determination of residual monomers in polycarboxylate superplasticizer (PCs) by reversed-phase high performance liquid chromatography (RP-HPLC). Four kinds of residual monomers were well separated and determined on a SinoChrom ODS-BP (C18) column with mobile phases composed of acetonitrile and phosphate buffer solution. The monomers were detected by UV detector at 205 nm and quantitatively analyzed with an external standard method. For those residual monomers, the linear response ranged from 4.0× 10-6 mol·L-1 to 2.0× 10-3 mol·L-1. The determination limit of acrylic acid, sodium methylallyl sulfonate and 2-Acrylamido-2-methylpropane sulfonic acid was 0.02× 10-5 mol·L-1, while that of methoxy-polyethylene glycol monoacrylate was 0.1 × 10-5 mol· L-1. The relative standard deviation (RSD) of high concentration samples was less than 1%, while that of the low concentration samples was between 1%-4%. The standard (additional) recovery ratio was 97.4% -104.2%.

  13. 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...

  14. Development of ionic gels using thiol-based monomers in ionic liquid

    Science.gov (United States)

    Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu

    2016-04-01

    Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.

  15. The monomer-dimer problem and moment Lyapunov exponents of homogeneous Gaussian random fields

    CERN Document Server

    Vladimirov, Igor G

    2012-01-01

    We consider an "elastic" version of the statistical mechanical monomer-dimer problem on the n-dimensional integer lattice. Our setting includes the classical "rigid" formulation as a special case and extends it by allowing each dimer to consist of particles at arbitrarily distant sites of the lattice, with the energy of interaction between the particles in a dimer depending on their relative position. We reduce the free energy of the elastic dimer-monomer (EDM) system per lattice site in the thermodynamic limit to the moment Lyapunov exponent (MLE) of a homogeneous Gaussian random field (GRF) whose mean value and covariance function are the Boltzmann factors associated with the monomer energy and dimer potential. In particular, the classical monomer-dimer problem becomes related to the MLE of a moving average GRF. We outline an approach to recursive computation of the partition function for "Manhattan" EDM systems where the dimer potential is a weighted l1-distance and the auxiliary GRF is a Markov random fie...

  16. Thermosets of epoxy monomer from Tung oil fatty acids cured in two synergistic ways

    Science.gov (United States)

    A new epoxy monomer from tung oil fatty acids, glycidyl ester of eleostearic acid (GEEA), was synthesized and characterized by 1H-NMR and 13C-NMR spectroscopy. Differential scanning calorimetry analysis (DSC) and FT-IR were utilized to investigate the curing process of GEEA cured by both dienophiles...

  17. ENZYMATIC COUPLING OF THE HERBICIDE BENTAZON WITH HUMUS MONOMERS AND CHARACTERIZATION OF REACTION PRODUCTS (R823847)

    Science.gov (United States)

    To elucidate the binding mechanism of the herbicide bentazon (3-isopropyl-1H-2,1,3-benzothiadiazine-4(3H)-one 2,2-dioxide) with humic monomers in the presence of an oxidative enzyme, the reaction of bentazon with catechol, caffeic acid, protocatechuic...

  18. Monomer-dimer equilibrium in glutathione transferases: a critical re-examination.

    Science.gov (United States)

    Fabrini, Raffaele; De Luca, Anastasia; Stella, Lorenzo; Mei, Giampiero; Orioni, Barbara; Ciccone, Sarah; Federici, Giorgio; Lo Bello, Mario; Ricci, Giorgio

    2009-11-03

    Glutathione transferases (GSTs) are dimeric enzymes involved in cell detoxification versus many endogenous toxic compounds and xenobiotics. In addition, single monomers of GSTs appear to be involved in particular protein-protein interactions as in the case of the pi class GST that regulates the apoptotic process by means of a GST-c-Jun N-terminal kinase complex. Thus, the dimer-monomer transition of GSTs may have important physiological relevance, but many studies reached contrasting conclusions both about the modality and extension of this event and about the catalytic competence of a single subunit. This paper re-examines the monomer-dimer question in light of novel experiments and old observations. Recent papers claimed the existence of a predominant monomeric and active species among pi, alpha, and mu class GSTs at 20-40 nM dilution levels, reporting dissociation constants (K(d)) for dimeric GST of 5.1, 0.34, and 0.16 microM, respectively. However, we demonstrate here that only traces of monomers could be found at these concentrations since all these enzymes display K(d) values of <1 nM, values thousands of times lower than those reported previously. Time-resolved and steady-state fluorescence anisotropy experiments, two-photon fluorescence correlation spectroscopy, kinetic studies, and docking simulations have been used to reach such conclusions. Our results also indicate that there is no clear evidence of the existence of a fully active monomer. Conversely, many data strongly support the idea that the monomeric form is scarcely active or fully inactive.

  19. Monomers of the Neurospora plasma membrane H+-ATPase catalyze efficient proton translocation.

    Science.gov (United States)

    Goormaghtigh, E; Chadwick, C; Scarborough, G A

    1986-06-05

    Liposomes prepared by sonication of asolectin were fractionated by glycerol density gradient centrifugation, and the small liposomes contained in the upper region of the gradients were used for reconstitution of purified, radiolabeled Neurospora plasma membrane H+-ATPase molecules by our previously published procedures. The reconstituted liposomes were then subjected to two additional rounds of glycerol density gradient centrifugation, which separate the H+-ATPase-bearing proteoliposomes from ATPase-free liposomes by virtue of their greater density. The isolated H+-ATPase-bearing proteoliposomes in two such preparations exhibited a specific H+-ATPase activity of about 11 mumol of Pi liberated/mg of protein/min, which was approximately doubled in the presence of nigericin plus K+, indicating that a large percentage of the H+-ATPase molecules in both preparations were capable of generating a transmembrane protonic potential difference sufficient to impede further proton translocation. Importantly, quantitation of the number of 105,000-dalton ATPase monomers and liposomes in the same preparations by radioactivity determination and counting of negatively stained images in the electron microscope indicated ATPase monomer to liposome ratios of 0.97 and 1.06. Because every liposome in the preparations must have had at least one ATPase monomer, these ratios indicate that very few of the liposomes had more than one, and simple calculations show that the great majority of active ATPase molecules in the preparations must have been present as proton-translocating monomers. The results thus clearly demonstrate that 105,000-dalton monomers of the Neurospora plasma membrane H+-ATPase can catalyze efficient ATP hydrolysis-driven proton translocation.

  20. Nonferrous Metal Processing Plants

    Data.gov (United States)

    Department of Homeland Security — This map layer includes nonferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  1. Ferrous Metal Processing Plants

    Data.gov (United States)

    Department of Homeland Security — This map layer includes ferrous metal processing plants in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the...

  2. Antibacterial Activity and Bonding Ability of an Orthodontic Adhesive Containing the Antibacterial Monomer 2-Methacryloxylethyl Hexadecyl Methyl Ammonium Bromide

    Science.gov (United States)

    Yu, Fan; Dong, Yan; Yu, Hao-han; Lin, Ping-ting; Zhang, Ling; Sun, Xiang; Liu, Yan; Xia, Yu-ning; Huang, Li; Chen, Ji-hua

    2017-01-01

    Irreversible white spot lesion (WSL) occurs in up to 50% of patients during orthodontic treatment. Therefore, orthodontic adhesives need to be able to inhibit or reduce bacterial growth in order to prevent or minimize WSL. This study evaluated the antibacterial effect and shear bond strength (SBS) of a resin-based orthodontic adhesive containing the antibacterial monomer 2-methacryloxylethyl hexadecyl methyl ammonium bromide (MAE-HB). MAE-HB was added at three concentrations (1, 3, and 5 wt%) to a commercial orthodontic adhesive Transbond XT, while the blank control comprised unmodified Transbond XT. Their antibacterial effects on Streptococcus mutans were investigated after 0 and 180 days of aging. The SBS of metal brackets bonded to the buccal enamel surface of human premolars was assessed. Compared with the blank control, the MAE-HB-incorporated adhesive exhibited a significant contact inhibitory effect on the growth of S. mutans (P < 0.05), even after 180 days of aging. SBS and adhesive remnant index values revealed that the bonding ability of the experimental adhesive was not significantly adversely affected by the incorporation of MAE-HB at any of the three concentrations. Therefore, orthodontic adhesives with strong and long-lasting bacteriostatic properties can be created through the incorporation of MAE-HB without negatively influencing bonding ability. PMID:28169312

  3. 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.

  4. 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.

  5. Shear Bond Strength of MDP-Containing Self-Adhesive Resin Cement and Y-TZP Ceramics: Effect of Phosphate Monomer-Containing Primers

    Directory of Open Access Journals (Sweden)

    Jin-Soo Ahn

    2015-01-01

    Full Text Available Purpose. This study was conducted to evaluate the effects of different phosphate monomer-containing primers on the shear bond strength between yttria-tetragonal zirconia polycrystal (Y-TZP ceramics and MDP-containing self-adhesive resin cement. Materials and Methods. Y-TZP ceramic surfaces were ground flat with #600-grit SiC paper and divided into six groups (n=10. They were treated as follows: untreated (control, Metal/Zirconia Primer, Z-PRIME Plus, air abrasion, Metal/Zirconia Primer with air abrasion, and Z-PRIME Plus with air abrasion. MDP-containing self-adhesive resin cement was applied to the surface-treated Y-TZP specimens. After thermocycling, a shear bond strength test was performed. The surfaces of the Y-TZP specimens were analyzed under a scanning electron microscope. The bond strength values were statistically analyzed using one-way analysis of variance and the Student–Newman–Keuls multiple comparison test (P<0.05. Results. The Z-PRIME Plus treatment combined with air abrasion produced the highest bond strength, followed by Z-PRIME Plus application, Metal/Zirconia Primer combined with air abrasion, air abrasion alone, and, lastly, Metal/Zirconia Primer application. The control group yielded the lowest results (P<0.05. Conclusion. The application of MDP-containing primer resulted in increased bond strength between Y-TZP ceramics and MDP-containing self-adhesive resin cements.

  6. Focused ion beam and field-emission microscopy of metallic filaments in memory devices based on thin films of an ambipolar organic compound consisting of oxadiazole, carbazole, and fluorene units

    Science.gov (United States)

    Pearson, Christopher; Bowen, Leon; Lee, Myung Won; Fisher, Alison L.; Linton, Katherine E.; Bryce, Martin R.; Petty, Michael C.

    2013-01-01

    We report on the mechanism of operation of organic thin film resistive memory architectures based on an ambipolar compound consisting of oxadiazole, carbazole, and fluorene units. Cross-sections of the devices have been imaged by electron microscopy both before and after applying a voltage. The micrographs reveal the growth of filaments, with diameters of 50 nm–100 nm, on the metal cathode. We suggest that these are formed by the drift of aluminium ions from the anode and are responsible for the observed switching and negative differential resistance phenomena in the memory devices.

  7. Study of the structure and properties of metal of the major steam lines of a CCGT-420 unit made from high-chromium X10CrMoVNb9-1 (P91) steel

    Science.gov (United States)

    Grin', E. A.; Anokhov, A. E.; Pchelintsev, A. V.; Krüger, E.-T.

    2016-07-01

    The technology of manufacture of live steam lines and hot reheat lines at FINOW Rohrsysteme GmbH are discussed. These pipelines are designed for high-performance CCGT units and are made from high-chromium martensitic steel X10CrMoVNb9-1 (P91). The principles of certification and evaluation of conformance of thermal and mechanical equipment made from new construction materials with the TRCU 032-2013 technical regulation of the Customs Union are detailed. The requirements outlined in Russian and international regulatory documents regarding the manufacture of pipes and semifinished products for pipeline systems are compared. The characteristic features of high-chromium martensitic steel, which define the requirements for its heat treatment and welding, are outlined. The methodology and the results of a comprehensive analysis of metal of pipes, fittings, and weld joints of steam lines are presented. It is demonstrated that the short-term mechanical properties of metal (P91 steel) of pipes, bends, and weld joints meet the requirements of European standards and Russian technical specifications. The experimental data on long-term strength of metal of pipes from a live steam line virtually match the corresponding reference curve from the European standard, while certain experimental points for metal of bends of this steam line and metal of pipes and bends from a hot reheat line lie below the reference curve, but they definitely stay within the qualifying (20%) interval of the scatter band. The presence of a weakened layer in the heat-affected zone of weld joints of steel P91 is established. It is shown that the properties of this zone govern the short-term and long-term strength of weld joints in general. The results of synthesis and analysis of research data support the notion that the certification testing of steam lines and other equipment made from chromium steels should necessarily involve the determination of long-term strength parameters.

  8. Cyclosophorohexadecaose and succinoglycan monomers as catalytic carbohydrates for the Strecker reaction.

    Science.gov (United States)

    Lee, Sanghoo; Cho, Eunae; Kwon, Chanho; Jung, Seunho

    2007-12-10

    Some microbial carbohydrates have been used as catalysts for the multicomponent Strecker reaction using trimethylsilyl cyanide (TMSCN). Alpha-Cyclosophorohexadecaose (alpha-C16) derived from Xanthomonas species and succinoglycan monomers derived from Rhizobium species acted as catalytic carbohydrates in the mixture solutions of methanol and water. Malonaldehyde bis(phenylimine) as a substrate was completely converted (yield: 100%) into its product to 100% by both alpha-C16 and the succinoglycan monomer (M2), having acetyl, pyruvyl, and succinyl groups as substituents after 1h. The catalytic abilities of the carbohydrates were dependent on the inherent structures of the substrates used in this study, where substrate 1 having a symmetrical structure rather than the others was favorably reacted with the alpha-C16 and M2. Through this study, we suggest that the microbial carbohydrates used in this study could be expected to be environmentally-benign catalysts for the synthesis of alpha-aminonitriles.

  9. Facile synthesis of polyester dendrimers from sequential click coupling of asymmetrical monomers.

    Science.gov (United States)

    Ma, Xinpeng; Tang, Jianbin; Shen, Youqing; Fan, Maohong; Tang, Huadong; Radosz, Maciej

    2009-10-21

    Polyester dendrimers are attractive for in vivo delivery of bioactive molecules due to their biodegradability, but their synthesis generally requires multistep reactions with intensive purifications. A highly efficient approach to the synthesis of dendrimers by simply "sticking" generation by generation together is achieved by combining kinetic or mechanistic chemoselectivity with click reactions between the monomers. In each generation, the targeted molecules are the major reaction product as detected by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The only separation needed is to remove the little unreacted monomer by simple precipitation or washing. This simple clicklike process without complicated purification is particularly suitable for the synthesis of custom-made polyester dendrimers.

  10. 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.

  11. Investigation on Vibrational Spectra and Structures of 4-Mercaptopyridine Monomer and Its Dihydrate

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The optimized molecular structures and vibrational frequencies of 4-mercaptopyridine(4MPY) monomer and its dihydrate were studied by means of the density functional theory(DFT), viz. B3LYP method with the 6-311++G(d,p) basis set. On the basis of the calculations, the assignments of the vibrational spectra of the monomer and the dihydrate were performed, and so were investigated the changes in the structure and the vibrational spectrum of the dihydrate as well as the intermolecular force resulting in the formation of the dihydrate. The calculated results show that each of the water molecule planes is vertical to the pyridine ring plane in the dihydrate that is formed via the H-bonds between 4MPY and water molecules. Furthermore, the structure and the vibrational spectrum of 4MPY can be consi-derably affected by the water molecules.

  12. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells

    Directory of Open Access Journals (Sweden)

    Andrea Nitti

    2016-12-01

    Full Text Available π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance, bearing clear advantages over traditional carbon-carbon forming methodologies. Although their use in the final polymerization step is already established, there is a need for improving synthetic accessibility to implement them also in the monomer synthesis. In this review, we discuss recent examples highlighting this useful strategy.

  13. Composition and Process for Retarding the Premature Aging of PMR Monomer Solutions and PMR Prepegs

    Science.gov (United States)

    Alston, William B. (Inventor); Gahn, Gloria S. (Inventor)

    2000-01-01

    Polyimides are derived from solutions of at least one low-boiling organic solvent, e.g. isopropanol containing a mixture of polyimide-forming monomers. The monomeric solutions have an extended shelf life at ambient (room) temperatures as high as 80 C, and consist essentially of a mixture of monoalkyl ester-acids, alkyl diester-diacids and aromatic polyamines wherein the alkyl radicals of the esteracids are derived from lower molecular weight aliphatic secondary alcohols having 3 to 5 carbon atoms per molecule such as isopropanol, secondary butanol, 2-methyl-3-butanol, 2 pentanol or 3-pentanol. The solutions of the polyimide-forming monomers have a substantially improved shelf-life and are particularly useful in the aerospace and aeronautical industry for the preparation of polyimide reinforced fiber composites such as the polyimide cured carbon composites used in jet engines, missiles, and for other high temperature applications.

  14. A cleaner two-step synthesis of high purity diallyldimethylammonium chloride monomers for flocculant preparation

    Institute of Scientific and Technical Information of China (English)

    TIAN Bing-hui; FAN Bin; PENG Xian-jia; LUAN Zhao-kun

    2005-01-01

    In order to improve the flocculation efficiency of polydiallyldimethylammonium chloride (PDADMAC), high molecular weight PDADMAC should be prepared from high purity diallyldimethylammonium chloride(DADMAC) monomers. In this paper, a cleaner method with microwave irradiation and alkali solidification was proposed for preparing high pure DADMAC by selective heating under low temperature, and the prepared high purity DADMAC is characterized using FTIR and atomic absorption spectrometry. The new method provides a solution to the key technical problem of PDADMAC synthesis. Comparing with the conventional methods, the results showed that the advantages of the novel synthesis include: (a) high purity DADMAC is improved from 57% to 71%; (b) reaction time of tertiary amine preparation is shortened from 6 h to 7 min; (c) water instead of acetone was used as reaction medium; (d) toxic by-products,wastewater and waste gas are eliminated. Flocculant made from the synthesized high purity DADMAC monomers was proved more efficient in flocculation tests.

  15. Structure and Properties of Silk Fibers Grafted with Vinyl Siloxane Monomer

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Silk fibers were grafted with a novel vinyl siloxane monomer. The properties of silk with different grafting yield were discussed. The results showed that the crease recovery of grafted silk fabric is improved significantly, handle of grafted silk is softer, and grafting has no influence on strength of silk. Graft with low grafting yield has no effect on dyeing properties of silk. The results of IR, SEM photographs and amino acid analysis indicate that the monomer combines with silk fiber by physical sediment and chemical bond, the grafting reactions mainly oecurred on Ser., His. and Arg. of silk fibers, and ester crosslinking forms between silanol and Asp., Glu. of silk molecular side chains. X-ray diffraction patterns of silk fibers suggest that the grafting has no effect on the crystalline regions.

  16. 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, Phistology that typifies progressive, severe CKD.

  17. 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.

  18. A Mechanistic Investigation of Gelation. The Sol-Gel Polymerization of Bridged Silsesquioxane Monomers

    Energy Technology Data Exchange (ETDEWEB)

    SHEA,KENNETH J.; LOY,DOUGLAS A.

    2000-07-14

    The study of a homologous series of silsesquioxane monomers has uncovered striking discontinuities in gelation behavior. An investigation of the chemistry during the early stages of the polymerization has provided a molecular basis for these observations. Monomers containing from one to four carbon atoms exhibit a pronounced tendency to undergo inter or intramolecular cyclization. The cyclic intermediates have been characterized by {sup 29}Si NMR, chemical ionization mass spectrometry and isolation from the reaction solution. These carbosiloxanes are local thermodynamic sinks that produce kinetic bottlenecks in the production of high molecular weight silsesquioxanes. The formation of cyclics results in slowing down or in some cases completely shutting down gelation. An additional finding is that the cyclic structures are incorporated intact into the final xerogel. Since cyclization alters the structure of the building block that eventually makes up the xerogel network, it is expected that this will contribute importantly to the bulk properties of the xerogel as well.

  19. Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

    Science.gov (United States)

    Mauldin, Timothy C.

    Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution

  20. Cobalt-mediated radical polymerization of vinyl monomers: investigation of cobalt-coordination

    OpenAIRE

    2009-01-01

    Controlled Radical Polymerization techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the growing radical chains with a cobalt complex, the cobalt (II) bis(acetylacetonate). The interest of this system is not only due to its ability to control the polymerization of very reactive monomers such as vinyl acetate (VAc) and N-viny...

  1. The Acyl Desaturase CER17 Is Involved in Producing Wax Unsaturated Primary Alcohols and Cutin Monomers.

    Science.gov (United States)

    Yang, Xianpeng; Zhao, Huayan; Kosma, Dylan K; Tomasi, Pernell; Dyer, John M; Li, Rongjun; Liu, Xiulin; Wang, Zhouya; Parsons, Eugene P; Jenks, Matthew A; Lü, Shiyou

    2017-02-01

    We report n-6 monounsaturated primary alcohols (C26:1, C28:1, and C30:1 homologs) in the cuticular waxes of Arabidopsis (Arabidopsis thaliana) inflorescence stem, a class of wax not previously reported in Arabidopsis. The Arabidopsis cer17 mutant was completely deficient in these monounsaturated alcohols, and CER17 was found to encode a predicted ACYL-COENZYME A DESATURASE LIKE4 (ADS4). Studies of the Arabidopsis cer4 mutant and yeast variously expressing CER4 (a predicted fatty acyl-CoA reductase) with CER17/ADS4, demonstrated CER4's principal role in synthesis of these monounsaturated alcohols. Besides unsaturated alcohol deficiency, cer17 mutants exhibited a thickened and irregular cuticle ultrastructure and increased amounts of cutin monomers. Although unsaturated alcohols were absent throughout the cer17 stem, the mutation's effects on cutin monomers and cuticle ultrastructure were much more severe in distal than basal stems, consistent with observations that the CER17/ADS4 transcript was much more abundant in distal than basal stems. Furthermore, distal but not basal stems of a double mutant deficient for both CER17/ADS4 and LONG-CHAIN ACYL-COA SYNTHETASE1 produced even more cutin monomers and a thicker and more disorganized cuticle ultrastructure and higher cuticle permeability than observed for wild type or either mutant parent, indicating a dramatic genetic interaction on conversion of very long chain acyl-CoA precursors. These results provide evidence that CER17/ADS4 performs n-6 desaturation of very long chain acyl-CoAs in both distal and basal stems and has a major function associated with governing cutin monomer amounts primarily in the distal segments of the inflorescence stem.

  2. Chiral separation by (S)-naproxen imprinted monolithic column with mixed functional monomers

    Institute of Scientific and Technical Information of China (English)

    Zhen Ying Li; Zhao Sheng Liu; Qing Wei Zhang; Hong Quan Duan

    2007-01-01

    Molecularly imprinted polymers (MIPs), using (S)-naproxen as template and the combination of butyl methacrylate (BMA) and column was evaluated in HPLC mode. The result showed that the monolithic MIPs with the combination of two monomers produced better chiral resolution of rac-naproxen (Rs = 1.55) and column efficiencies of imprinted molecules (N = 2860 plates/m)than that with pure MAA.

  3. Chemical analysis of monomers in epoxy resins based on bisphenols F and A.

    Science.gov (United States)

    Pontén, A; Zimerson, E; Sörensen, O; Bruze, M

    2004-05-01

    Diglycidyl ether of bisphenol A (DGEBA) is the monomer and most important contact allergen in epoxy resin(s) based on bisphenol A (DGEBA-R). Both thin-layer chromatography (TLC) and high-pressure liquid chromatography (HPLC) methods are available for the analysis of products containing DGEBA-R. With respect to detection and quantification, epoxy resins of the bisphenol F-type, i.e. epoxy resins containing the isomers of diglycidyl ethers of bisphenol F (DGEBF), are not as well investigated as DGEBA-R. The isomers of DGEBF are p,p'-DGEBF, o,p'-DGEBF and o,o'-DGEBF. Both p,p'-DGEBF and o,p'-DGEBF have been shown to be contact allergens in humans, and all 3 isomers are sensitizers in the guinea pig maximization test. We aimed (i). to develop HPLC methods for separation and purification of the individual DGEBF isomers, (ii). to detect and quantify the DGEBF isomers in epoxy resins of the bisphenol F-type and (iii). to evaluate and develop the TLC as a method for the detection of the DGEBF monomers. We found the total content of the DGEBF isomers in the investigated epoxy resins of the bisphenol F-type to vary from 17.0 to 81.7% w/w. Some of them also contained 0.1-2.4% w/w DGEBA. The HPLC method showed a sensitivity that was 2000-20 000x higher than that obtained with the TLC method for the DGEBF monomers. We concluded that the range of the DGEBF isomer content in epoxy resins of the bisphenol F-type is approximately the same as the monomer content in liquid compared to solid DGEBA-R. The relevance of contact allergy to DGEBA-R can remain unrecognized if the suspected product is an epoxy resin of the bisphenol F-type, which is analysed with the TLC method.

  4. Direct Arylation Strategies in the Synthesis of π-Extended Monomers for Organic Polymeric Solar Cells

    OpenAIRE

    Andrea Nitti; Riccardo Po; Gabriele Bianchi; Dario Pasini

    2016-01-01

    π-conjugated macromolecules for organic polymeric solar cells can be rationally engineered at the molecular level in order to tune the optical, electrochemical and solid-state morphology characteristics, and thus to address requirements for the efficient solid state device implementation. The synthetic accessibility of monomers and polymers required for the device is getting increasing attention. Direct arylation reactions for the production of the π-extended scaffolds are gaining importance,...

  5. Controlled Release of Benzocaine from Monomer and Copolymer Carriers in Synthetic Gastro-intestinal Media

    Directory of Open Access Journals (Sweden)

    Houaria Merine

    2014-05-01

    Full Text Available New dosage forms able to control drug release in the gastro-intestinal media have been prepared and investigated in this paper. Two different type of medicinal agent bonding (MA, in our case Benzocaine (Bz, were chosen in order to examine drug release. i MA attached to ethylenic monomer (m,p-vinylbenzaldehyde, condensation reaction. ii The copolymer carrier (Cp is obtained by copolymerizing this monomer. These two carriers were well characterized by microanalysis, FTIR, DSC (Tg and GPC (Ip and the two fraction α and β were calculated from elemental analyses of Cp. The results showed good polydispersity and low average molecular weight. MA linked to an organic product by the azomethine function (C=N, hydrolytically sensitive, allowed controlled release of Bz, from the monomer carrier and from the bending Schiff bases groups. Theoretical and experimental analyses of controlled release of Bz kinetics from monomer and copolymer carriers were conducted for the case of contact with synthetic gastro-intestinal fluids at various pH (1,2; 6,0 and 8,0 at 37°C. The process was found to be controlled by the nature of media (heterogeneous, which involved the preliminary hydrolysis, and the drug (Bz diffusing out of structure of copolymer (Cp to the external aqueous media. The results obtained on the rate of delivery showed a clear difference between pH = 1,2 and pH = 6,0 and 8,0 based on: i The cation of p-aminoniumbenzoic acid (PABAH+ release at pH = 1,2 ii Bz release at pH = 6,0 and 8,0

  6. Ferrocene-Based Monomers, Oligomers and Polymers as Electro-Active Materials

    OpenAIRE

    Al Khalyfeh, Khaled

    2016-01-01

    The present PhD thesis deals with the synthesis and characterization of functionalized ferrocenes with up to four aldehyde and vinyl groups and their usage as monomers to produce novel ferrocene-based oligomers with conjugated backbones via ADMET (acyclic diene metathesis) and HWE (Horner-Wadsworth-Emmons) reaction protocols. In addition, ferrocene-containing polymers (linear, cross-linked and co-polymers) with aliphatic backbones generated by anionic bulk and solution polymerization routes, ...

  7. Effect of trifluoroethylene monomers on molecular conformation of poly (vinylidene fluoride-trifluoroethylene) copolymer

    Institute of Scientific and Technical Information of China (English)

    Li Ji-Chao; Wang Chun-Lei; Zhong Wei-Lie

    2004-01-01

    Hartree-Fock and density functional theory (DFT) methods were employed to study poly (vinylidene fluoridetrifluoroethylene) [P(VDF-TrFE)] molecular chains with different VDF contents. The dependence of dipole moment of P(VDF-TrFE) chains on VDF content obtained from our calculation is in good agreement with the experiment. The TrFE monomer plays an important role in introducing the gauche bond into copolymer chains. A possible mechanism was interpreted.

  8. Hemoglobin-imprinted polymer gel prepared using modified glucosamine as functional monomer

    Institute of Scientific and Technical Information of China (English)

    Hai Li Zhao; Tian Ying Guo; Yong Qing Xia; Mou Dao Song

    2008-01-01

    A new functional glycomonomer was obtained from modified glucosamine.Hemoglobin-imprinted polymer gel was prepared with allyl-bromide modified glucosamine as functional monomer,poly(ethylene-glycol)diaorylate(PEGDA)as cross-linker and ammonium persulfate[(NH4)2S2O8]/sodium hydrogen sulfite(NaHSO3)as initiators in a phosphate buffer.The adsorption capacity and selective adsorption of the molecular imprinting polymer(MIP)were also discussed.

  9. D-polyglutamine amyloid recruits L-polyglutamine monomers and kills cells

    Science.gov (United States)

    Kar, Karunakar; Arduini, Irene; Drombosky, Kenneth W.; van der Wel, Patrick C. A.; Wetzel, Ronald

    2014-01-01

    Polyglutamine (polyQ) amyloid fibrils are observed in disease tissue and have been implicated as toxic agents responsible for neurodegeneration in expanded CAG repeat diseases like Huntington’s disease (HD). Despite intensive efforts, the mechanism of amyloid toxicity remains unknown. As a novel approach to probing polyQ toxicity, we investigate here how some cellular and physical properties of polyQ amyloid vary with the chirality of the glutamine residues in the polyQ. We challenged PC12 cells with small amyloid fibrils composed of either L- or D-polyQ peptides and found that D-fibrils are as cytotoxic as L-fibrils. We also found using fluorescence microscopy that both aggregates effectively seed the aggregation of cell-produced L-polyQ proteins, suggesting a surprising lack of stereochemical restriction in seeded elongation of polyQ amyloid. To investigate this effect further, we studied chemically synthesized D- and L-polyQ in vitro. We found that, as expected, D-polyQ monomers are not recognized by proteins that recognize L-polyQ monomers. However, amyloid fibrils prepared from D-polyQ peptides can efficiently seed the aggregation of L-polyQ monomers in vitro, and vice versa. This result is consistent with our cell results on polyQ recruitment, but is inconsistent with previous literature reports on the chiral specificity of amyloid seeding. This chiral cross-seeding can be rationalized by a model for seeded elongation featuring a “rippled β-sheet” interface between seed fibril and docked monomers of opposite chirality. The lack of chiral discrimination in polyQ amyloid cytotoxicity is consistent with several toxicity mechanisms, including recruitment of cellular polyQ proteins. PMID:24291210

  10. Vegetable oil-derived epoxy monomers and polymer blends: A comparative study with review

    OpenAIRE

    T. P. Schuman; Wang, R.

    2013-01-01

    Glycidyl esters of epoxidized fatty acids derived from soybean oil (EGS) and linseed oil (EGL) have been synthesized to have higher oxirane content, more reactivity and lower viscosity than epoxidized soybean oil (ESO) or epoxidized linseed oil (ELO). The EGS and ESO, for comparison, were used neat and in blends with diglycidyl ether of bisphenol A (DGEBA). Thermosetting resins were fabricated with the epoxy monomers and either BF3 catalyst or anhydride. The curing behaviors, glass transition...

  11. 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.

  12. HEMA inhibits interfacial nano-layering of the functional monomer MDP.

    Science.gov (United States)

    Yoshida, Y; Yoshihara, K; Hayakawa, S; Nagaoka, N; Okihara, T; Matsumoto, T; Minagi, S; Osaka, A; Van Landuyt, K; Van Meerbeek, B

    2012-11-01

    Previous research showed that the functional monomer 10-methacryloxydecyl dihydrogen phosphate (MDP) ionically bonds to hydroxyapatite (HAp) and forms a nano-layered structure at the interface with HAp-based substrates. Such hydrophobic nano-layering is considered to contribute to the long-term durability of the bond to tooth tissue. However, dental adhesives are complex mixtures usually containing different monomers. This study investigated the effect of the monomer 2-hydroxyethylmethacrylate (HEMA) on the chemical interaction of MDP with HAp by x-ray diffraction (XRD), nuclear magnetic resonance (NMR), and quartz crystal microbalance (QCM). We examined the chemical interaction of 5 experimental MDP solutions with increasing concentrations of HEMA. XRD revealed that addition of HEMA inhibits nano-layering at the interface, while NMR confirmed that MDP remained adsorbed onto the HAp surface. QCM confirmed this adsorption of MDP to HAp, as well as revealed that the demineralization rate of HAp by MDP was reduced by HEMA. It was concluded that even though the adsorption of MDP to HAp was not hindered, addition of HEMA inhibited interfacial nano-layering. Potential consequences with regard to bond durability necessitate further research.

  13. Chemical graft polymerization of sulfobetaine monomer on polyurethane surface for reduction in platelet adhesion.

    Science.gov (United States)

    Yuan, Jiang; Chen, Li; Jiang, Xuefeng; Shen, Jian; Lin, Sicong

    2004-11-25

    Surface modification is an effective way to improve the hemocompatibility and remain bulk properties of biomaterials. Recently, polymer tailored with zwitterions was found having good blood compatibility. In this study, the zwitterionic monomer of sulfobetaine was graft polymerized onto polyurethane (PU) surface in a three-step heterogenous system through the vinyl bonds of acrylic acid (AA) or hydroxyethyl methacrylate (HEMA), which was immobilized with hexamethylene diisocyanate (HDI) beforehand. First, PU was activated with isocyanate groups using HDI as coupling agent. Second, AA or HEMA was introduced through reaction of AA or HEMA with NCO groups bonded on PU surface. Last, zwitterionic monomer of sulfobetain was graft polymerized with vinyl group of AA or HEMA using AIBN as polymerization initiator. The reaction process was monitored with ATR-IR spectra and XPS spectra. Variation of graft yield with temperature and monomer feed concentration was investigated and feasible conditions were optimized. The wettability of films was investigated by water contact angle measurement and water absorbance. Platelet adhesion experiment was conducted as a preliminary test to confirm the improved blood compatibility of PU. The number of platelets adhering to PU decreased greatly comparing with the originals after 1 and 3 h of contact with human plate-rich plasma (PRP).

  14. Poly-amido-saccharides: synthesis via anionic polymerization of a β-lactam sugar monomer.

    Science.gov (United States)

    Dane, Eric L; Grinstaff, Mark W

    2012-10-01

    Enantiopure poly-amido-saccharides (PASs) with a defined molecular weight and narrow dispersity are synthesized using an anionic ring-opening polymerization of a β-lactam sugar monomer. The PASs have a previously unreported main chain structure that is composed of pyranose rings linked through the 1- and 2-positions by an amide with α-stereochemistry. The monomer is synthesized in one-step from benzyl-protected D-glucal and polymerized using mild reaction conditions to give degrees of polymerization ranging from 25 to >120 in high yield. Computational modeling reveals how the monomer's structure and steric bulk affect the thermodynamics and kinetics of polymerization. Protected and deprotected polymers and model compounds are characterized using a variety of methods (NMR, GPC, IR, DLS, etc.). On the basis of circular dichroism, the deprotected polymer possesses a regular secondary structure in aqueous solution, which agrees favorably with the prediction of a helical structure using molecular modeling. Furthermore, we provide evidence suggesting that the polymers bind the lectin concanavalin A at the same site as natural carbohydrates, showing the potential of these polymers to mimic natural polysaccharides. PASs offer the advantages associated with synthetic polymers, such as greater control over structure and derivitization. At the same time, they preserve many of the structural features of natural polysaccharides, such as a stereochemically regular, rigid pyranose backbone, that make natural carbohydrate polymers important materials both for their unique properties and useful applications.

  15. Molecularly imprinted microspheres prepared by precipitation polymerization at high monomer concentrations

    Directory of Open Access Journals (Sweden)

    Renkecz Tibor

    2014-01-01

    Full Text Available Highly crosslinked polymer microparticles have been prepared by precipitation polymerization using high monomer loadings (≥25 v/v % which generally would lead to bulk monoliths. The microparticle format was achieved by the use of non-solvating diluents either alone or in combination with co-solvents. Two distinct morphologies were observed. Monodisperse smooth microspheres were obtained using a thermodynamically good co-solvent whereas segmented irregular particles were formed with poorer co-solvents. It has been found that during polymerization the forming polymer particles were enriched in the co-solvent and this effect was more pronounced when good co-solvents were used. The type of functional monomer, crosslinker and co-solvent, and the non-solvent/co-solvent ratio were identified as influential parameters on the microparticle morphology. With the proposed methodology molecularly imprinted microparticles have been prepared successfully for three different templates, naproxen, diclofenac and toltrazuril using various functional monomers, crosslinkers and polymerization solvent mixtures.

  16. Vinyl monomers-induced synthesis of polyvinyl alcohol-stabilized selenium nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Chetan P.; Singh, Krishan K. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Kumar, Manmohan, E-mail: manmoku@barc.gov.in [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Bajaj, Parma N. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2010-01-15

    A simple wet chemical method has been developed to synthesize selenium nanoparticles (size 100-200 nm), by reaction of sodium selenosulphate precursor with different vinyl monomers, such as acrylamide, N,N'-dimethylene bis acrylamide, methyl methacrylate, sodium acrylate, etc., in aqueous medium, under ambient conditions. Polyvinyl alcohol has been used to stabilize the selenium nanoparticles. Average size of the synthesized selenium nanoparticles can be controlled by adjusting concentration of both the precursors and the stabilizer. Rate of the reaction as well as size of the resultant selenium nanoparticles have been correlated with the functional groups of the different monomers. UV-vis optical absorption spectroscopy, X-ray diffraction, energy dispersive X-rays, differential scanning calorimetry, atomic force microscopy, scanning electron microscopy and transmission electron microscopy techniques have been employed to characterize the synthesized selenium nanoparticles. Gas chromatographic analysis of the reaction mixture established the non-catalytic role of the vinyl monomers, which were found to be consumed during the course of the reaction.

  17. 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}.

  18. Formation of monomer residues in PS, PC, PA-6 and PVC upon {gamma}-irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Young Park, Gun [Graduate School of Biotechnology, Korea University, 1.5-Ka, Anam-Dong, Seongbuk-Ku, Seoul 136-701 (Korea, Republic of); Yong Cho, Seung [Functional Food Research Center, College of Life Sciences, Korea University, 1.5-Ka, Anam-Dong, Seongbuk-Ku, Seoul 136-701 (Korea, Republic of); Hoon Jeon, Dae [Graduate School of Biotechnology, Korea University, 1.5-Ka, Anam-Dong, Seongbuk-Ku, Seoul 136-701 (Korea, Republic of); Food Packaging Division, Korea Food and Drug Administration (KFDA), 5 Nokbun-Dong, Eunpyung-Ku, Seoul 122-704 (Korea, Republic of); Shin Kwak, In [Food Packaging Division, Korea Food and Drug Administration (KFDA), 5 Nokbun-Dong, Eunpyung-Ku, Seoul 122-704 (Korea, Republic of); Ho Lee, Kwang [Food Packaging Division, Korea Food and Drug Administration (KFDA), 5 Nokbun-Dong, Eunpyung-Ku, Seoul 122-704 (Korea, Republic of); Park, H.J. [Graduate School of Biotechnology, Korea University, 1.5-Ka, Anam-Dong, Seongbuk-Ku, Seoul 136-701 (Korea, Republic of) and Department of Packaging Science, Clemson University, Clemson, South Carolina 29634-0370 (United States)]. E-mail: hjpark@korea.ac.kr

    2006-09-15

    Food packaging polymers, polystyrene (PS), polycarbonate (PC), polyamide-6 (PA-6), and polyvinylchloride (PVC), were irradiated with dose in the range 5-200 kGy. The quantities of corresponding monomer residues (styrene monomer, bisphenol-A, {epsilon}-caprolactam, vinyl chloride) released from target materials were analyzed using a SIM mode of GC/MSD. Styrene monomer in PS showed a slight increase from 740 to 777 ppm at 5-30 kGy and then decreased as the dose increased from 30 to 200 kGy. Bisphenol-A in PC was dose independent at the low doses, 5, 10 and 30 kGy, but its level increased from 173 to 473 ppm at 30 kGy and thereafter remained unchanged through 200 kGy. {epsilon}-Caprolactam in PA-6 was also dose independent, in the range of 5-200 kGy, but its level (122-164 ppm) was found to be higher than those (71 ppm) of non-irradiated sample. As for PVC, the quantity of vinyl chloride tended to increase from 8 to 18 ppm at 5-200 kGy.

  19. 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.

  20. Energy landscapes of the monomer and dimer of the Alzheimer's peptide A β (1 -28 )

    Science.gov (United States)

    Dong, Xiao; Chen, Wei; Mousseau, Normand; Derreumaux, Philippe

    2008-03-01

    The cytoxicity of Alzheimer's disease has been linked to the self-assembly of the 40 /42 amino acid of the amyloid-β (A β ) peptide into oligomers. To understand the assembly process, it is important to characterize the very first steps of aggregation at an atomic level of detail. Here, we focus on the N-terminal fragment 1-28, known to form fibrils in vitro. Circular dichroism and NMR experiments indicate that the monomer of A β (1 -28 ) is α -helical in a membranelike environment and random coil in aqueous solution. Using the activation-relaxation technique coupled with the OPEP coarse grained force field, we determine the structures of the monomer and of the dimer of A β (1 -28 ) . In agreement with experiments, we find that the monomer is predominantly random coil in character, but displays a non-negligible β -strand probability in the N-terminal region. Dimerization impacts the structure of each chain and leads to an ensemble of intertwined conformations with little β -strand content in the region Leu17-Ala21. All these structural characteristics are inconsistent with the amyloid fibril structure and indicate that the dimer has to undergo significant rearrangement en route to fibril formation.

  1. Energy landscapes of the monomer and dimer of the Alzheimer's peptide Abeta(1-28).

    Science.gov (United States)

    Dong, Xiao; Chen, Wei; Mousseau, Normand; Derreumaux, Philippe

    2008-03-28

    The cytotoxicity of Alzheimer's disease has been linked to the self-assembly of the 4042 amino acid of the amyloid-beta (Abeta) peptide into oligomers. To understand the assembly process, it is important to characterize the very first steps of aggregation at an atomic level of detail. Here, we focus on the N-terminal fragment 1-28, known to form fibrils in vitro. Circular dichroism and NMR experiments indicate that the monomer of Abeta(1-28) is alpha-helical in a membranelike environment and random coil in aqueous solution. Using the activation-relaxation technique coupled with the OPEP coarse grained force field, we determine the structures of the monomer and of the dimer of Abeta(1-28). In agreement with experiments, we find that the monomer is predominantly random coil in character, but displays a non-negligible beta-strand probability in the N-terminal region. Dimerization impacts the structure of each chain and leads to an ensemble of intertwined conformations with little beta-strand content in the region Leu17-Ala21. All these structural characteristics are inconsistent with the amyloid fibril structure and indicate that the dimer has to undergo significant rearrangement en route to fibril formation.

  2. 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

  3. Sequence Analysis of Trimer Isomers Formed by Montmorillonite Catalysis in the Reaction of Binary Monomer Mixtures

    Science.gov (United States)

    Ertem, Gözen; Hazen, Robert M.; Dworkin, Jason P.

    2007-10-01

    Oligonucleotides are structurally similar to short RNA strands. Therefore, their formation via non-enzymatic reactions is highly relevant to Gilbert's RNA world scenario (1986) and the origin of life. In laboratory synthesis of oligonucleotides from monomers, it is necessary to remove the water molecules from the reaction medium to shift the equilibrium in favor of oligonucleotide formation, which would have been impossible for reactions that took place in dilute solutions on the early Earth. Model studies designed to address this problem demonstrate that montmorillonite, a phyllosilicate common on Earth and identified on Mars, efficiently catalyzes phosphodiester-bond formation between activated mononucleotides in dilute solutions and produces RNA-like oligomers. The purpose of this study was to examine the sequences and regiospecificity of trimer isomers formed in the reaction of 5'-phosphorimidazolides of adenosine and uridine. Results demonstrated that regiospecificity and sequence specificity observed in the dimer fractions are conserved in their elongation products. With regard to regiospecificity, 61% of the linkages were found to be RNA-like 3',5'-phosphodiester bonds. With regard to sequence specificity, we found that 88% of the linear trimers were hetero-isomers with 61% A-monomer and 39% U-monomer incorporation. These results lend support to Bernal's hypothesis that minerals may have played a significant role in the chemical processes that led to the origin of life by catalyzing the formation of phosphodiester bonds in RNA-like oligomers.

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

    DEFF Research Database (Denmark)

    Shillcock, Julian C.

    2009-01-01

    /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 exponential......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...... states corresponding to a bound adenosine triphosphate (ATP), adenosine diphosphate with inorganic phosphate (ADP/P), and ADP molecule. The simplest situation that has been studied experimentally is provided by the polymerization of ADP-actin, for which all protomers are identical. This case is used...

  5. Non-conjugated small molecule FRET for differentiating monomers from higher molecular weight amyloid beta species.

    Directory of Open Access Journals (Sweden)

    Chongzhao Ran

    Full Text Available BACKGROUND: Systematic differentiation of amyloid (Aβ species could be important for diagnosis of Alzheimer's disease (AD. In spite of significant progress, controversies remain regarding which species are the primary contributors to the AD pathology, and which species could be used as the best biomarkers for its diagnosis. These controversies are partially caused by the lack of reliable methods to differentiate the complicated subtypes of Aβ species. Particularly, differentiation of Aβ monomers from toxic higher molecular weight species (HrMW would be beneficial for drug screening, diagnosis, and molecular mechanism studies. However, fast and cheap methods for these specific aims are still lacking. PRINCIPAL FINDINGS: We demonstrated the feasibility of a non-conjugated FRET (Förster resonance energy transfer technique that utilized amyloid beta (Aβ species as intrinsic platforms for the FRET pair assembly. Mixing two structurally similar curcumin derivatives that served as the small molecule FRET pair with Aβ40 aggregates resulted in a FRET signal, while no signal was detected when using Aβ40 monomer solution. Lastly, this FRET technique enabled us to quantify the concentrations of Aβ monomers and high molecular weight species in solution. SIGNIFICANCE: We believe that this FRET technique could potentially be used as a tool for screening for inhibitors of Aβ aggregation. We also suggest that this concept could be generalized to other misfolded proteins/peptides implicated in various pathologies including amyloid in diabetes, prion in bovine spongiform encephalopathy, tau protein in AD, and α-synuclein in Parkinson disease.

  6. Wire and extended ladder model predict THz oscillations in DNA monomers, dimers and trimers

    CERN Document Server

    Lambropoulos, K; Morphis, A; Tassi, M; Lopp, R; Georgiadis, G; Theodorakou, M; Chatzieleftheriou, M; Simserides, C

    2016-01-01

    We call \\textit{monomer} a B-DNA base pair and study, analytically and numerically, electron or hole oscillations in \\textit{monomers}, \\textit{dimers} and \\textit{trimers}. We employ two Tight Binding (TB) approaches: (I) at the base-pair level, using the on-site energies of the base pairs and the hopping parameters between successive base pairs i.e. \\textit{a wire model}, and (II) at the single-base level, using the on-site energies of the bases and the hopping parameters between neighbouring bases, specifically between (a) two successive bases in the same strand, (b) complementary bases that define a base pair, and (c) diagonally located bases of successive base pairs, i.e. \\textit{an extended ladder model} since it also includes the diagonal hoppings (c). For \\textit{monomers}, with TB II, we predict periodic carrier oscillations with frequency $f \\approx$ 50-550 THz. For \\textit{dimers}, with TB I, we predict periodic carrier oscillations with $f \\approx$ 0.25-100 THz. For \\textit{trimers made of identic...

  7. 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.

  8. A Simple and Rapid Method for Quality Control of Major Histocompatibility Complex-Peptide Monomers by Flow Cytometry.

    Science.gov (United States)

    Chandran, P Anoop; Heidu, Sonja; Zelba, Henning; Schmid-Horch, Barbara; Rammensee, Hans-Georg; Pascolo, Steve; Gouttefangeas, Cécile

    2017-01-01

    Major histocompatibility complex (MHC) multimers are essential tools in T cell immunomonitoring, which are employed both in basic and clinical research, as well as for assessing clinical samples during therapy. The generation of MHC monomers loaded with synthetic peptides is an elaborate and time-consuming process. It would be beneficial to assess the quality of these monomers prior to downstream applications. In this technical note, we describe a novel flow cytometry-based, cell-free, quick, and robust assay to check the quality of MHC monomers directly after refolding or after long-term storage.

  9. A Simple and Rapid Method for Quality Control of Major Histocompatibility Complex–Peptide Monomers by Flow Cytometry

    Science.gov (United States)

    Chandran, P. Anoop; Heidu, Sonja; Zelba, Henning; Schmid-Horch, Barbara; Rammensee, Hans-Georg; Pascolo, Steve; Gouttefangeas, Cécile

    2017-01-01

    Major histocompatibility complex (MHC) multimers are essential tools in T cell immunomonitoring, which are employed both in basic and clinical research, as well as for assessing clinical samples during therapy. The generation of MHC monomers loaded with synthetic peptides is an elaborate and time-consuming process. It would be beneficial to assess the quality of these monomers prior to downstream applications. In this technical note, we describe a novel flow cytometry-based, cell-free, quick, and robust assay to check the quality of MHC monomers directly after refolding or after long-term storage. PMID:28228758

  10. Concomitant contact allergy to formaldehyde and methacrylic monomers in students of dental medicine and dental patients

    Directory of Open Access Journals (Sweden)

    Maya Lyapina

    2014-10-01

    Full Text Available Objectives: A multitude of acrylic monomers is used in dentistry. Formaldehyde is a ubiquitous chemical agent, which is an ingredient of some dental materials and may be released from methacrylate-based composites. The purpose of the study is to evaluate the incidence and the risk of cross-sensitization to some methacrylic monomers (methylmethacrylate – 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 and formaldehyde in students of dentistry, dental professionals and dental patients. Material and Methods: A total of 139 participants were included in the study, i.e., occupationally exposed dental professionals, students of the 3rd, 4th and 6th year of dental medicine, and occupationally unexposed dental patients. They were patch-tested with methacrylic monomers and formaldehyde. The results were subjected to statistical analysis (p < 0.05. Results: From the allergic to formaldehyde students of the 3rd and 4th year of dental medicine, 46.2% were also sensitized to MMA. Among the group of patients, the incidence of cross-sensitization to formaldehyde and methacrylic monomers was as follows: to TEGDMA – 20.6%, to ethyleneglycol dimethacrylate – 20.7%, to 2-HEMA – 20.7% and to tetrahydrofurfuryl methacrylate – 24.1%. Contact allergy to MMA was diagnosed among 22.7%, and to TEGDMA – among 27.1% of the students of the 3rd and 4th year of dental medicine. In the group of occupationally unexposed dental patients the prevalence of contact allergy to ethyleneglycol dimethacrylate was 20.7%, to Bis-GMA – 27.6%, to 2-HEMA – 44.9% and to tetrahydrofurfuryl methacrylate – 38.0%. Conclusions: The students of the 3rd and 4th year of dental medicine could be outlined as a group at risk of sensitization to MMA and TEGDMA and of cross-sensitization to MMA

  11. STUDY ON THE SYNTHESIS OF POLYPERFLUOROTRIAZINE——The Synthesis and Polymerization of a Novel α,ω-Diiodoperfluorooxaalkyl s-Triazine Monomer

    Institute of Scientific and Technical Information of China (English)

    HUANG Weiyuan; HUANG Bingnan; HU Changming

    1983-01-01

    In order to investigate synthetic route of polyperfluorotriazine elastomer, 2-trifluoromethyl-4,6-bis(4'-iodo-2'-oxahexafluorobutyl)-1,3,5-triazine (1), a novel triazine monomer, was synthesized from 5-iodo-3-oxa-octafluoropentanesulfonyl fluoride (2) in eight-steps. 2 was reduced by potassium sulfite to the sulfinate (3), which was treated with hydriodic acid to yield 5-iodo-3-oxa-hexafluoropentanoic acid (4). Compound 4 was transformed to 5-iodo-3-oxa-hexafluoropentanenitrile (7) through the corresponding ester 5 and amide 6. The desired product 1 was prepared by acylation-cyclodehydration of the imidoylamidine 9, obtained by condensation of the nitrile 7with the amidine 8.The various methods for the esterification of perfluorocarboxylic acid were studied and a possible mechanism for the transformation of perfluorosulfinate to the corresponding perfluorocarboxylic acid by hydriodic acid was proposed.Crude 1 contained compounds 6, 11, 13, as impurities which were removed by low temperature crystallization followed by filtration through a short alumina column. The monomer 1 was polymerized by UV-irradiation in the presence of Hg with or without solvent. Polyperfluorooxaalkyl triazine 17 thus obtained showed good thermal stability. In the main chain of the polymer there was no weak unit of the uncyclized ring. Polymer 17 had an average molecular weight of ca.1.33-2.0×104 (D. P.=27-42) and the temperature of 10% weight loss in nitrogen was 340℃.

  12. Research on corrosion resistance influencing factors of metal parts in outdoor condensing units%室外型冷凝机组金属部件耐腐蚀性能影响因素研究

    Institute of Scientific and Technical Information of China (English)

    苏梅

    2012-01-01

    Both the corrosion mechanism and the corrosion resistance influencing factors of the metal parts in outdoor units exposed in the air are summarized. Regarding the red rust area as the criterion, the experiments are made in order to judge the influence degree of the three important factors-metal backing,spray technology,coating thickness,and the pairwise interaction with the orthogonal experimental method. The results indicate that spray technology influences the corrosion resistance most. The metal backing, and the interaction of the metal backing and spray technology can influence the corrosion resistance obviously. Therefore, correctly selecting the spray technology, metal backing and taking their interaction into consideration are important for enhancing corrosion resistance of outdoor metal parts.%概述室外机金属部件暴露于大气中的腐蚀机制及金属部件耐腐蚀性能的影响因素.采用正交试验方法,以盐雾试验后的红锈面积作为判断标准,针对影响金属耐腐蚀性能的3个重要因素(金属基材、喷涂方式和涂膜厚度)及其两两交互作用对室外机金属部件耐腐蚀性能的影响程度进行试验对比.结果表明:喷涂方式对耐腐蚀性能影响最大,金属基材、金属基材与喷涂方式的交互作用对金属耐腐蚀性能影响较大.因此正确选择喷涂方式和金属基材并考虑2种影响因素的交互关系对提高室外机金属部件耐腐蚀性能具有重要意义.

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

    Science.gov (United States)

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

    2014-10-03

    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.

  14. 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.

  15. From monomer to monolayer: a global optimisation study of (ZnO)n nanoclusters on the Ag surface.

    Science.gov (United States)

    Demiroglu, Ilker; Woodley, Scott M; Sokol, Alexey A; Bromley, Stefan T

    2014-12-21

    We employ global optimisation to investigate how oxide nanoclusters of increasing size can best adapt their structure to lower the system energy when interacting with a realistic extended metal support. Specifically, we focus on the (ZnO)@Ag(111) system where experiment has shown that the infinite Ag(111)-supported ZnO monolayer limit corresponds to an epitaxially 7 : 8 matched graphene-like (Zn(3)O(3))-based hexagonal sheet. Using a two-stage search method based on classical interatomic potentials and then on more accurate density functional theory, we report global minina candidate structures for Ag-supported (ZnO)n cluster with sizes ranging from n = 1-24. Comparison with the respective global minina structure of free space (ZnO)n clusters reveals that the surface interaction plays a decisive role in determining the lowest energy Ag-supported (ZnO)n cluster structures. Whereas free space (ZnO)n clusters tend to adopt cage-like bubble structures as they grow larger, Ag-supported (ZnO)n clusters of increasing size become progressively more like planar cuts from the infinite graphene-like ZnO single monolayer. This energetic favourability for planar hexagonal Ag-supported clusters over their 3D counterparts can be partly rationalised by the ZnO-Ag(111) epitaxial matching and the increased number of close interactions with the Ag surface. Detailed analysis shows that this tendency can also be attributed to the capacity of 2D clusters to distort to improve their interaction with the Ag surface relative to more rigid 3D bubble cluster isomers. For the larger sized clusters we find that the adsorption energies and most stable structural types appear to be rather converged confirming that our study makes a bridge between the Ag-supported ZnO monomer and the infinite Ag-supported ZnO monolayer.

  16. Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.; Dedrick, Daniel E.; Reeder, Craig L.

    2012-02-01

    In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested

  17. Temperature responsive hydrogel magnetic nanocomposites for hyperthermia and metal extraction applications

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, N. Narayana, E-mail: nagireddynarayana@gmail.com [Center for Advanced Biomaterials for Healthcare, Istituto Italiano di Tecnologia@CRIB, Largo Barsanti e Matteucci 53, 80125 Napoli (Italy); Ravindra, S. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa); Reddy, N. Madhava [Department of Environmental Science, Gates Institute of Technology, NH-7, Gooty, Anantapuram, Andhra Pradesh (India); Rajinikanth, V. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa); Raju, K. Mohana [Synthetic Polymer Laboratory, Department of Polymer Science & Technology, S.K. University, Anantapuram, Andhra Pradesh (India); Vallabhapurapu, Vijaya Srinivasu [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1709 (South Africa)

    2015-11-15

    The present work deals with the development of temperature and magnetic responsive hydrogel networks based on poly (N-isopropylacrylamide)/acrylamido propane sulfonic acid. The hydrogel matrices are synthesized by polymerizing N-isopropylacrylamide (NIPAM) monomer in the presence of acrylamido propane sulphonicacid (AMPS) using a cross-linker (N,N-methylenebisacrylamide, MBA) and redox initiating system [ammonium persulphate (APS)/tetramethylethylenediamine (TMEDA)]. The magnetic nanoparticles are generated throughout the hydrogel networks using in situ method by incorporating iron ions and subsequent treatment with ammonia. A series of hydrogel-magnetic nanocomposites (HGMNC) are developed by varying AMPS composition. The synthesized hydrogel magnetic nanocomposites (HGMNC) are characterized by using Fourier Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), Thermal Analyses and Electron Microscopy analysis (Scanning and Transmission Electron Microscope). The metal extraction capacities of the prepared hydrogel (HG) and hydrogel magnetic nanocomposites (HGMNC) were studied at different temperatures. The results suggest that HGMNCs have higher extraction capacity compared to HG and HG loaded iron ions. This data also reveals that the extraction of metals by hydrogel magnetic nanocomposites (HGMNCs) is higher at higher temperatures than room temperature. The prepared HGMNCs are also subjected to hyperthermia (cancer therapy) studies. - Highlights: • We have developed temperature responsive hydrogel magnetic nanocomposites. • Addition of AMPS monomer to this magnetic hydrogel enhances the temperature sensitivity to 40–43 °C. • Similarly the sulfonic groups present in the AMPS units enhances the swelling ratio of magnetic hydrogels. • AMPS acts as good stabilizing agent for nanoparticles in the magnetic nanogel.

  18. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  19. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  20. The role of cyclase-associated protein in regulating actin filament dynamics – more than a monomer-sequestration factor

    OpenAIRE

    Ono, Shoichiro

    2013-01-01

    Dynamic reorganization of the actin cytoskeleton is fundamental to a number of cell biological events. A variety of actin-regulatory proteins modulate polymerization and depolymerization of actin and contribute to actin cytoskeletal reorganization. Cyclase-associated protein (CAP) is a conserved actin-monomer-binding protein that has been studied for over 20 years. Early studies have shown that CAP sequesters actin monomers; recent studies, however, have revealed more active roles of CAP in a...

  1. The C-terminal dimerization motif of cyclase-associated protein is essential for actin monomer regulation.

    Science.gov (United States)

    Iwase, Shohei; Ono, Shoichiro

    2016-12-01

    Cyclase-associated protein (CAP) is a conserved actin-regulatory protein that functions together with actin depolymerizing factor (ADF)/cofilin to enhance actin filament dynamics. CAP has multiple functional domains, and the function to regulate actin monomers is carried out by its C-terminal half containing a Wiskott-Aldrich Syndrome protein homology 2 (WH2) domain, a CAP and X-linked retinitis pigmentosa 2 (CARP) domain, and a dimerization motif. WH2 and CARP are implicated in binding to actin monomers and important for enhancing filament turnover. However, the role of the dimerization motif is unknown. Here, we investigated the function of the dimerization motif of CAS-2, a CAP isoform in the nematode Caenorhabditis elegans, in actin monomer regulation. CAS-2 promotes ATP-dependent recycling of ADF/cofilin-bound actin monomers for polymerization by enhancing exchange of actin-bound nucleotides. The C-terminal half of CAS-2 (CAS-2C) has nearly as strong activity as full-length CAS-2. Maltose-binding protein (MBP)-tagged CAS-2C is a dimer. However, MBP-CAS-2C with a truncation of either one or two C-terminal β-strands is monomeric. Truncations of the dimerization motif in MBP-CAS-2C nearly completely abolish its activity to sequester actin monomers from polymerization and enhance nucleotide exchange on actin monomers. As a result, these CAS-2C variants, also in the context of full-length CAS-2, fail to compete with ADF/cofilin to release actin monomers for polymerization. CAS-2C variants lacking the dimerization motif exhibit enhanced binding to actin filaments, which is mediated by WH2. Taken together, these results suggest that the evolutionarily conserved dimerization motif of CAP is essential for its C-terminal region to exert the actin monomer-specific regulatory function.

  2. Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants.

    Science.gov (United States)

    Genualdi, Susan; Nyman, Patricia; Begley, Timothy

    2014-04-01

    Due to the 2011 labelling of styrene monomer as "reasonably anticipated to be a human carcinogen" by the National Institutes of Health's National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg(-1) for the styrene monomer, 130-2900 mg kg(-1) for the sum of three styrene dimers, and 220-16,000 mg kg(-1) for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g(-1); dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g(-1) and trimer concentrations were all below the LOQ (2 ng g(-1)). Diffusion coefficients (Dp) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10(2) to 2 × 10(6)) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.

  3. Molecular weight distribution of A2-B2 type condensation polymers in the presence of capping monomer C

    Institute of Scientific and Technical Information of China (English)

    张连来; 廖琦; 顾宜; 江璐霞; 蔡兴贤

    1996-01-01

    The molecular weight distribution of A2-B2 type condensation polymers in the presence of capping monomer C has been derived with statistical calculation and Monte Carlo simulation methods. The Monte Carlo simulation result agrees with that of statistical calculation. The number distribution function and weight distribution function of seven types of molecules existing in A2-B2-C system have been obtained. The effect of reactivity of capping monomer C on these distributions are discussed.

  4. The Use of Commercial Non-Hazardous Air Pollutant Monomers to Optimize the Properties of Fatty Acid-Based Resins

    Science.gov (United States)

    2009-05-01

    Reviewing all of the data, it was found that the di-functional monomers produced resins with lower viscosities, higher modulus, and higher Tg than the...to storage modulus Tg Glass transition temperature of polymer TGA Thermogravimetric analysis UPE Unsaturated polyester VE Vinyl ester...The Use of Commercial Non-Hazardous Air Pollutant Monomers to Optimize the Properties of Fatty Acid-Based Resins by John J. La Scala, Priya

  5. 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.

  6. High-resolution structure of a retroviral protease folded as a monomer

    Energy Technology Data Exchange (ETDEWEB)

    Gilski, Miroslaw [A. Mickiewicz University, 60-780 Poznan (Poland); Polish Academy of Sciences, 61-704 Poznan (Poland); Kazmierczyk, Maciej; Krzywda, Szymon [A. Mickiewicz University, 60-780 Poznan (Poland); Zábranská, Helena [Academy of Sciences of the Czech Republic, 166 10 Prague (Czech Republic); Cooper, Seth; Popović, Zoran [University of Washington, Box 352350, Seattle, WA 98195 (United States); Khatib, Firas; DiMaio, Frank; Thompson, James; Baker, David [University of Washington, Box 357350, Seattle, WA 98195 (United States); Pichová, Iva [Academy of Sciences of the Czech Republic, 166 10 Prague (Czech Republic); Jaskolski, Mariusz, E-mail: mariuszj@amu.edu.pl [A. Mickiewicz University, 60-780 Poznan (Poland); Polish Academy of Sciences, 61-704 Poznan (Poland)

    2011-11-01

    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{sup 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

  7. 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.

  8. A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance.

    Science.gov (United States)

    Xu, Jiangtao; Jung, Kenward; Atme, Amir; Shanmugam, Sivaprakash; Boyer, Cyrille

    2014-04-09

    Controlled/living radical polymerization techniques have transformed polymer chemistry in the last few decades, affording the production of polymers with precise control over both molecular weights and architectures. It is now possible to synthesize almost an infinite variety of macromolecules using nonspecialized equipment, finding applications in high-tech industry. However, they have several shortcomings. Until recently, living radical polymerizations could not be controlled by an external stimulus, such as visible light, pH, mechanical, chemical, etc. Moreover, they are usually sensitive to trace amounts of oxygen in the system. In this Article, we report a photoinduced living polymerization technique, which is able to polymerize a large range of monomers, including conjugated and unconjugated monomers, using ultralow concentrations of an iridium-based photoredox catalyst (typically 1 ppm to monomers) and a low energy visible LED as the light source (1-4.8 W, λ(max) = 435 nm). The synthesis of homopolymers with molecular weights ranging from 1000 to 2,000,000 g/mol was successfully achieved with narrow molecular weight distributions (M(w)/M(n) < 1.3). In addition, chain extensions of poly(methacrylate)s, poly(styrene), poly(N-vinyl pyrrolidinone), poly(vinyl ester)s, and poly(acrylate)s were performed to prepare diblock copolymers. The reusability of the catalyst was demonstrated by the synthesis of a decablock polymer by multiple chain extensions. Most importantly, this process was employed to prepare well-defined polymers and multiblock copolymers in the presence of air.

  9. 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...

  10. 1,3-Diphenylethenylcarbazolyl-Based Monomer for Cross-Linked Hole Transporting Layers

    Directory of Open Access Journals (Sweden)

    Maryte Daskeviciene

    2015-05-01

    Full Text Available A new cross-linkable monomer containing 1,3-diphenylethenylcarbazolyl-based hole-transporting moieties and four reactive epoxy groups, was prepared by a multistep synthesis route from 1,3-bis(2,2-diphenylethenyl-9H-carbazol-2-ol and its application for the in situ formation of cross-linked hole transporting layers was investigated. A high concentration of flexible aliphatic epoxy chains ensures good solubility and makes this compound an attractive cross-linking agent. The synthesized compounds were characterized by various techniques, including differential scanning calorimetry, xerographic time of flight, and electron photoemission in air methods.

  11. Preparation, isolation, and characterization of cutin monomers and oligomers from tomato peels.

    Science.gov (United States)

    Osman, S F; Irwin, P; Fett, W F; O'Connor, J V; Parris, N

    1999-02-01

    Cutin in tomato peels was depolymerized in methanolic base to yield cutin monomers or a mixture of cutin oligomers. These products were isolated by typical solvent extraction methods or by precipitation, and the isolates were characterized by chromatographic and spectroscopic analyses. It was determined that the compositions of the isolates from both isolation procedures were similar, although solvent extraction gave higher yields. However, the precipitation method, which is easy to carry out and avoids the use of undesirable organic solvents, may be preferable in commercial processes for recovering these compounds.

  12. Modification of biodegradable polymers by radiation crosslinking technique with polyfunctional monomers

    Energy Technology Data Exchange (ETDEWEB)

    Yoshii, Fumio E-mail: yoshii@taka.jaeri.go.jp; Suhartini, Meri; Nagasawa, Naotsugu; Mitomo, Hiroshi; Kume, Tamikazu

    2003-08-01

    Poly({epsilon}-caprolactone) (PCL) and poly(butylene succinate-co-adipate) (PBSA) were electron beam-irradiated in the presence of five different polyfunctional monomers at ambient temperature. Trimethallyl isocyanurate (TMAIC) has been found to greatly enhance the radiation crosslinking of PCL and PBSA. It was pointed out that the optimum yield of gel fraction can be achieved when the polymers were irradiated at a dose of 50 kGy in the presence of 1% TMAIC. High gel fraction largely improves heat stability of PBSA, while biodegradability evaluated by soil burial test of the crosslinked polymers is slightly retarded, however they are effectively destroyed with a slightly smaller rate.

  13. Modification of biodegradable polymers by radiation crosslinking technique with polyfunctional monomers

    Science.gov (United States)

    Yoshii, Fumio; Suhartini, Meri; Nagasawa, Naotsugu; Mitomo, Hiroshi; Kume, Tamikazu

    2003-08-01

    Poly(ɛ-caprolactone) (PCL) and poly(butylene succinate-co-adipate) (PBSA) were electron beam-irradiated in the presence of five different polyfunctional monomers at ambient temperature. Trimethallyl isocyanurate (TMAIC) has been found to greatly enhance the radiation crosslinking of PCL and PBSA. It was pointed out that the optimum yield of gel fraction can be achieved when the polymers were irradiated at a dose of 50 kGy in the presence of 1% TMAIC. High gel fraction largely improves heat stability of PBSA, while biodegradability evaluated by soil burial test of the crosslinked polymers is slightly retarded, however they are effectively destroyed with a slightly smaller rate.

  14. Organic Crystal Engineering of Thermosetting Cyanate Ester Monomers: Influence of Structure on Melting Point

    Science.gov (United States)

    2016-05-27

    heating baseline does show a modest non - linearity due to its nearness to the onset of the wide melting peak. Because we elected not to use heating...Guenthner, Sean M. Ramirez , Michael D. Ford, Denisse Soto, Jerry A. Boatz, Kamran B. Ghiassi and Joseph M. Mabry 5d. PROJECT NUMBER 5e. TASK...longer Si-C bonds for C-C bonds in the monomer chemical structure results in the “unlocking” of new degrees of freedom in non -interlocking molecules

  15. Construction of Multi-Chromophoric Spectra from Monomer Data: Applications to Resonant Energy Transfer

    CERN Document Server

    Chenu, Aurélia

    2016-01-01

    We develop a model that establishes a quantitative link between the physical properties of molecular aggregates and their constituent building blocks. The relation is built on the coherent potential approximation, calibrated against exact results, and proven reliable for a wide range of parameters. It provides a practical method to compute spectra and transfer rates in multi-chromophoric systems from experimentally accessible monomer data. Applications to F\\"orster energy transfer reveal optimal transfer rates as functions of both the system-bath coupling and intra-aggregate coherence.

  16. 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.)

  17. Construction of Multichromophoric Spectra from Monomer Data: Applications to Resonant Energy Transfer

    Science.gov (United States)

    Chenu, Aurélia; Cao, Jianshu

    2017-01-01

    We develop a model that establishes a quantitative link between the physical properties of molecular aggregates and their constituent building blocks. The relation is built on the coherent potential approximation, calibrated against exact results, and proven reliable for a wide range of parameters. It provides a practical method to compute spectra and transfer rates in multichromophoric systems from experimentally accessible monomer data. Applications to Förster energy transfer reveal optimal transfer rates as functions of both the system-bath coupling and intra-aggregate coherence.

  18. Glucagon stop-go kinetics supports a monomer-trimer fibrillation model

    CERN Document Server

    Kosmrlj, Andrej; Kyrsting, Anders; Otzen, Daniel E; Oddershede, Lene B; Jensen, Mogens H

    2014-01-01

    We investigate in vitro fibrillation kinetics of the hormone peptide glucagon at various concentrations using confocal microscopy and determine the glucagon fibril persistence length $60 \\mu\\textrm{m}$. At all concentrations we observe that periods of individual fibril growth are interrupted by periods of stasis. The growth probability is large at high and low concentrations and is reduced for intermediate glucagon concentrations. To explain this behavior we propose a simple model, where fibrils come in two forms, one built entirely from glucagon monomers and one entirely from glucagon trimers. The opposite building blocks act as fibril growth blockers, and this generic model reproduces experimental behavior well.

  19. 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.

  20. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units

    KAUST Repository

    Yao, Zizhu

    2016-03-02

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs\\' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1 % acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.

    Science.gov (United States)

    Yao, Zizhu; Zhang, Zhangjing; Liu, Lizhen; Li, Ziyin; Zhou, Wei; Zhao, Yunfeng; Han, Yu; Chen, Banglin; Krishna, Rajamani; Xiang, Shengchang

    2016-04-11

    Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1% acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups.

  2. Distribution of dissolved organic carbon and metal-binding capacity among ultrafilterable fractions isolated from selected surface waters of the southeastern United States

    Science.gov (United States)

    Alberts, James J.; Giesy, John P.; Evans, David W.

    1984-06-01

    The binding capacities of surface waters for Cd, Cu, and Pb were determined for eight water samples representing four rivers and two swamps from Florida and Georgia in the southeastern United States The binding capacity ranges were CdBC=0 04 to 0 79 μg atm/L, CuBC=1 0 to 5 4 μg atm/L, and PbBC=5 0 to 17 8 μg atm/L Binding capacity values from the southeastern United States are shown to be in good agreement with values reported from the northeastern part of the country and northern Europe The CdBC was due primarily to inorganic ligand binding, while PbBC was predominantly a result of organic matter The CuBC was due to a complex function of both organic and inorganic binding Significant portions of the CuBC and PbBC could be removed from the waters by ultrafiltration of particles between 0·45 μm and 52 Å in diameter Ultrafiltration, even to removing particles > 13 Å diameter, did not affect the CdBC Distributional studies of the dissolved organic carbon in these systems reveal that significant fractions of the DOC are present in the ultrafilterable fraction which contains significant portions of the CuBC and PbBC

  3. Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF

    KAUST Repository

    Alezi, Dalal

    2016-10-05

    The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or “cubic graphite” structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal–organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm3 g–1, respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g–1 and 210.4 cm3 (STP) cm–3 at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH4 adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm–3 at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.

  4. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides

    Science.gov (United States)

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-01

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co3O4, ZnO, Mn2O3, MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N2, whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N2. Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N2 and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H2 and CO2 adsorption properties depending on the environment used for the thermolysis of MOFs.Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co3O4, ZnO, Mn2O3, MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N2, whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N2. Another point of interest is the fact that we have

  5. A conserved cysteine residue is involved in disulfide bond formation between plant plasma membrane aquaporin monomers.

    Science.gov (United States)

    Bienert, Gerd P; Cavez, Damien; Besserer, Arnaud; Berny, Marie C; Gilis, Dimitri; Rooman, Marianne; Chaumont, François

    2012-07-01

    AQPs (aquaporins) are conserved in all kingdoms of life and facilitate the rapid diffusion of water and/or other small solutes across cell membranes. Among the different plant AQPs, PIPs (plasma membrane intrinsic proteins), which fall into two phylogenetic groups, PIP1 and PIP2, play key roles in plant water transport processes. PIPs form tetramers in which each monomer acts as a functional channel. The intermolecular interactions that stabilize PIP oligomer complexes and are responsible for the resistance of PIP dimers to denaturating conditions are not well characterized. In the present study, we identified a highly conserved cysteine residue in loop A of PIP1 and PIP2 proteins and demonstrated by mutagenesis that it is involved in the formation of a disulfide bond between two monomers. Although this cysteine seems not to be involved in regulation of trafficking to the plasma membrane, activity, substrate selectivity or oxidative gating of ZmPIP1s (Zm is Zea mays), ZmPIP2s and hetero-oligomers, it increases oligomer stability under denaturating conditions. In addition, when PIP1 and PIP2 are co-expressed, the loop A cysteine of ZmPIP1;2, but not that of ZmPIP2;5, is involved in the mercury sensitivity of the channels.

  6. Monomer composition of polysaccharides of seed cell walls and the taxonomy of the Vochysiaceae.

    Science.gov (United States)

    Mayworm, M A; Buckeridge, M S; Salatino, A

    2000-11-01

    The distribution of polysaccharides from the seed cell walls of 57 samples of Vochysiaceae native to Brazil were studied, comprising 16 species distributed among the genera Callisthene, Qualea, Salvertia and Vochysia. The polysaccharides were extracted with hot water, then hydrolyzed with the resulting monomers analyzed by HPLC. All samples yielded arabinose, galactose, glucose. mannose and rhamnose, the relative amounts of each monomer, however, varying from one sample to another. Arabinose was always the predominant component, which implies that it might possibly be used as a marker of the Vochysiaceae. The quantitative distribution of monosaccharides was similar between the species of Qualea and Callisthene, characterized by the predominance of arabinose and mannose, and between the species of Salvertia and Vochysia, which contained higher amounts of arabinose and galactose. Such results are consistent with affinities inferred from floral morphology, wood anatomy and molecular data. Substantial intraspecific variation was observed for some species. UPGMA analysis based on the distribution of the monosaccharides reveals two main clusters, according to the links commented above. The resultant phenogram is not coherent with the current sectional classification of the Vochysiaceae, but the differences in the monosaccharides distribution between the two clusters are strongly supported by ANOVA.

  7. EFFECT OF GAMMA RAYS IN THE PREPARATION OF POLYMER AND HYDROGEL FROM ACRYLAMIDE MONOMER

    Institute of Scientific and Technical Information of China (English)

    M. M. Alam; M. F. Mina; F. Akhtar

    2003-01-01

    The formation of polymer and hydrogel from aqueous solutions having 20, 30 and 40% concentrations of acrylamide monomer by γ-ray irradiation processing in the dose range 0.06-30 kGy using a Co-60 source and their characterization have been observed. Polymer conversion and gel fraction are found to depend on radiation doses. Polymer conversion increases with the increase of dose, depending on the solution concentration, where maximum conversion is achieved at 0.18, 0.16 and 0.10 kGy for 20%, 30% and 40% concentrations, respectively. On the other hand, gel fraction increases with dose from the gel point (0.12 kGy) for all concentrations, where 100% conversion of gel occurs at doses ≥ 5 kGy. Tensile strength, viscosity and molecular weight (Mw) of polymer samples increase with both the dose and the concentration, showing a high value of Mw up to ≈108. Swelling of hydrogels under water with respect to time varies due to the variation of cross-linking density formed in the gels and the maximum swelling mainly occurs within 24 h. A remarkable change of surface morphology reveals characteristic features of monomer, polymer and hydrogel films.

  8. 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.

  9. Preparation and characterization of monomers to tetramers of a collagen-like domain from Streptococcus pyogenes.

    Science.gov (United States)

    Peng, Yong Y; Stoichevska, Violet; Howell, Linda; Madsen, Soren; Werkmeister, Jerome A; Dumsday, Geoff J; Ramshaw, John A M

    2014-01-01

    The collagen like domain Scl2 from Streptococcus pyogenes has been proposed as a potential biomedical material. It is non-cytotoxic and non-immunogenic and can be prepared in good yield in fermentation. The Scl2 collagen domain is about a quarter of the length, 234 residues, of the main collagen type, mammalian type I collagen (1014 residues) that is currently used in biomedical devices. In the present study we have made constructs comprising 1 to 4 copies of the Scl2 collagen domain, plus these same constructs with a CysCys sequence at the C-terminal, analogous to that found in mammalian type III collagens. The yields of these constructs were examined from 2 L fermentation studies. The yields of both series declined with increasing size. Circular dichroism showed that the addition of further collagen domains did not lead to a change in the melting temperature compared to the monomer domain. Addition of the CysCys sequence led to a small additional stabilization of about 2-3°C for the monomer construct when the folding (V) domain was present.

  10. Therapeutic TNF Inhibitors can Differentially Stabilize Trimeric TNF by Inhibiting Monomer Exchange

    Science.gov (United States)

    van Schie, Karin A.; Ooijevaar-de Heer, Pleuni; Dijk, Lisanne; Kruithof, Simone; Wolbink, Gertjan; Rispens, Theo

    2016-01-01

    Tumor necrosis factor (TNF) is a homotrimeric cytokine that is a key mediator of inflammation. It is unstable at physiological concentrations and slowly converts into an inactive form. Here, we investigated the mechanism of this process by using a Förster resonance energy transfer (FRET) assay that allowed monitoring of monomeric subunit exchange in time. We observed continuous exchange of monomeric subunits even at concentrations of TNF high enough to maintain its bioactivity. The kinetics of this process closely corresponds with the appearance of monomeric subunits and disappearance of trimeric TNF in time at ng/ml concentrations as monitored by high-performance size-exclusion chromatography (HP-SEC). Furthermore, of the five therapeutic TNF inhibitors that are currently used in the clinic, three (adalimumab, infliximab, etanercept) were found to completely inhibit the monomer exchange reaction and stabilize TNF trimers, whereas golimumab and certolizumab could not prevent monomer exchange, but did slow down the exchange process. These differences were not correlated with the affinities of the TNF inhibitors, measured with both surface plasmon resonance (SPR) and in fluid phase using fluorescence-assisted HP-SEC. The stabilizing effect of these TNF inhibitors might result in prolonged residual TNF bioactivity under conditions of incomplete blocking, as observed in vitro for adalimumab. PMID:27605058

  11. A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers.

    Science.gov (United States)

    Harman-Ware, Anne E; Foster, Cliff; Happs, Renee M; Doeppke, Crissa; Meunier, Kristoffer; Gehan, Jackson; Yue, Fengxia; Lu, Fachuang; Davis, Mark F

    2016-10-01

    Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, including standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. The method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses. © 2016 The Authors. Biotechnology Journal published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis of star-shaped pyrrole and thiophene functionalized monomers and optoelectrochemical properties of corresponding copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Ak, Metin [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey); Pamukkale University, Department of Chemistry, 20020 Denizli (Turkey); Toppare, Levent [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey)], E-mail: toppare@metu.edu.tr

    2009-04-15

    Star-shaped thiophene and pyrrole functionalized monomers namely 2,4,6-tris(4-(1H-pyrrol-1-yl)phenoxy)-1,3,5-triazine (TriaPy) and 2,4,6-tris(4-(1H-pyrrol-1-yl)phenoxy)-1,3,5-triazine (TriaTh) were synthesized from 2,4,6-trichloro-1,3,5-triazine, thiophen-3-ylmethanol and 4-(1H-pyrrol-1-yl)phenol. Electrochemical copolymerization of monomers with thiophene and pyrrole was achieved in tetrabutylammonium tetrafluoroborate/acetonitrile (TBAFB/AN). Resulting copolymers were characterized by Fourier transform infrared (FTIR) spectrometer, cyclic voltammetry (CV) and conductivity measurements. Spectroelectrochemical analysis reflected that copolymer films have low {lambda}{sub max} for {pi}-{pi}* electronic transitions accompanied with a rather high band gap compared to polythiophene and polypyrrole. Switching abilities of copolymer films were evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast.

  13. Recovery and Utilization of Lignin Monomers as Part of the Biorefinery Approach

    Directory of Open Access Journals (Sweden)

    Kirsten M. Davis

    2016-10-01

    Full Text Available Lignin is a substantial component of lignocellulosic biomass but is under-utilized relative to the cellulose and hemicellulose components. Historically, lignin has been burned as a source of process heat, but this heat is usually in excess of the process energy demands. Current models indicate that development of an economically competitive biorefinery system requires adding value to lignin beyond process heat. This addition of value, also known as lignin valorization, requires economically viable processes for separating the lignin from the other biomass components, depolymerizing the lignin into monomeric subunits, and then upgrading these monomers to a value-added product. The fact that lignin’s biological role is to provide biomass with structural integrity means that this heteropolymer can be difficult to depolymerize. However, there are chemical and biological routes to upgrade lignin from its native form to compounds of industrial value. Here we review the historical background and current technology of (thermo chemical depolymerization of lignin; the natural ability of microbial enzymes and pathways to utilize lignin, the current prospecting work to find novel microbial routes to lignin degradation, and some applications of these microbial enzymes and pathways; and the current chemical and biological technologies to upgrade lignin-derived monomers.

  14. The Optimization of Synthesizing Graft Copolymer of Starch with Vinyl Monomers

    Institute of Scientific and Technical Information of China (English)

    WANG Zhiyu; LIU Zuoxin

    2006-01-01

    The graft copolymerization of acrylamide (AM)/acrylic acid (AA) onto starch (St-g-pAA and St-g-p(AA-co-AM)) was carried out using an orthogonal test method. The combined effects of different reaction conditions on the water absorbency of the graft copolymers were optimized through mathematical statistical methods of range and square variance analysis. The maximum water absorbency was obtained when the ratio of dried starch to distilled water was 1∶8 (w/w), the ratio of starch to monomer 1∶6 (w/w), the initiator concentration 4.40×10-3 mol/L, the crosslinker concentration 10.86×10-2 mol/L, and the basicity to AA 0.70(mol/mol). Both the graft copolymers have an excellent water absorption capacity in distilled water and in 0.9wt% NaCl solution. It was also found that in distilled water the water absorbency of St-g-pAA was higher than that of St-g-p(AA-co-AM), while in 0.9wt% NaCl solution, the situation was just the reverse. The correlation between the water absorbency and the nature of the solution and the properties of the copolymers, which is related to the properties of the monomers, was discussed. The grafting of AA and AM onto starch was confirmed by the IR spectra of St-g-pAA and St-g-p(AA-co-AM).

  15. 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.

  16. 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.

  17. A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers

    Energy Technology Data Exchange (ETDEWEB)

    Harman-Ware, Anne E. [Bioenergy Science Center, Golden CO USA; National Bioenergy Center, National Renewable Energy Laboratory, Golden CO USA; Foster, Cliff [Great Lakes BioEnergy Research Center, Michigan State University, East Lansing MI USA; Happs, Renee M. [Bioenergy Science Center, Golden CO USA; National Bioenergy Center, National Renewable Energy Laboratory, Golden CO USA; Doeppke, Crissa [Bioenergy Science Center, Golden CO USA; National Bioenergy Center, National Renewable Energy Laboratory, Golden CO USA; Meunier, Kristoffer [Great Lakes BioEnergy Research Center, Michigan State University, East Lansing MI USA; Gehan, Jackson [Great Lakes BioEnergy Research Center, Michigan State University, East Lansing MI USA; Yue, Fengxia [Wisconsin Bioenergy Initiative, University of Wisconsin, Madison WI USA; Lu, Fachuang [Wisconsin Bioenergy Initiative, University of Wisconsin, Madison WI USA; Davis, Mark F. [Bioenergy Science Center, Golden CO USA; National Bioenergy Center, National Renewable Energy Laboratory, Golden CO USA

    2016-09-14

    Thioacidolysis is a method used to measure the relative content of lignin monomers bound by SS-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, including standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. The method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses.

  18. Characterization of cluster/monomer ratio in pulsed supersonic gas jets

    Science.gov (United States)

    Gao, Xiaohui; Shim, Bonggu; Wang, Xiaoming; Downer, Mike

    2008-11-01

    While Rayleigh scatter and interferometry are standard methods for determining average cluster size and total atomic density, respectively, in cluster gas jets, determination of cluster mass fraction has required additional input from gasdynamic simulations. Here we determine cluster mass fraction experimentally with fs-time-resolved measurement of refractive index using frequency domain interferometery (FDI) after ionization and heating by a pump pulse. The essence of this method is that the negative index contribution of monomer plasma appears immediately after ionization by the pump, whereas the positive contribution of clustered plasma becomes significant only after clusters expand to a Mie resonance condition, enabling separation of monomer and cluster densities in the time domain. This method allows us to investigate various influences (nozzle geometry, temperature, etc.) on cluster fraction, which varies widely in nominally identical gas jets, and is a critical parameter in realizing phase-matched harmonic generation at high laser intensity, which would lead to an efficient table-top soft X-ray source.

  19. Short-time dynamics of monomers and dimers in quasi-two-dimensional colloidal mixtures

    Science.gov (United States)

    Sarmiento-Gómez, Erick; Villanueva-Valencia, José Ramón; Herrera-Velarde, Salvador; Ruiz-Santoyo, José Arturo; Santana-Solano, Jesús; Arauz-Lara, José Luis; Castañeda-Priego, Ramón

    2016-07-01

    We report on the short-time dynamics in colloidal mixtures made up of monomers and dimers highly confined between two glass plates. At low concentrations, the experimental measurements of colloidal motion agree well with the solution of the Navier-Stokes equation at low Reynolds numbers; the latter takes into account the increase in the drag force on a colloidal particle due to wall-particle hydrodynamic forces. More importantly, we find that the ratio of the short-time diffusion coefficient of the monomer and that of the center of mass of the dimmer is almost independent of both the dimer molar fraction, xd, and the total packing fraction, ϕ , up to ϕ ≈0.5 . At higher concentrations, this ratio displays a small but systematic increase. A similar physical scenario is observed for the ratio between the parallel and the perpendicular components of the short-time diffusion coefficients of the dimer. This dynamical behavior is corroborated by means of molecular dynamics computer simulations that include explicitly the particle-particle hydrodynamic forces induced by the solvent. Our results suggest that the effects of colloid-colloid hydrodynamic interactions on the short-time diffusion coefficients are almost identical and factorable in both species.

  20. Analytic solution of two-density integral equations for sticky Janus dumbbells with arbitrary monomer diameters

    Science.gov (United States)

    Gazzillo, Domenico; Munaò, Gianmarco; Prestipino, Santi

    2016-06-01

    We study a pure fluid of heteronuclear sticky Janus dumbbells, considered to be the result of complete chemical association between unlike species in an initially equimolar mixture of hard spheres (species A) and sticky hard spheres (species B) with different diameters. The B spheres are particles whose attractive surface layer is infinitely thin. Wertheim's two-density integral equations are employed to describe the mixture of AB dumbbells together with unbound A and B monomers. After Baxter factorization, these equations are solved analytically within the associative Percus-Yevick approximation. The limit of complete association is taken at the end. The present paper extends to the more general, heteronuclear case of A and B species with size asymmetry a previous study by Wu and Chiew [J. Chem. Phys. 115, 6641 (2001)], which was restricted to dumbbells with equal monomer diameters. Furthermore, the solution for the Baxter factor correlation functions qi j α β ( r ) is determined here in a fully analytic way, since we have been able to find explicit analytic expressions for all the intervening parameters.

  1. Structural and Vibrational Study on Monomer and Dimer Forms and Water Clusters of Acetazolamide

    Directory of Open Access Journals (Sweden)

    Aysen E. Ozel

    2013-01-01

    Full Text Available Experimental IR and Raman spectra of solid acetazolamide have been analysed by computing the molecular structures and vibrational spectra of monomer and dimer forms and water clusters of acetazolamide. The possible stable conformers of free acetazolamide molecule in the ground state were obtained by scanning the potential energy surface through the dihedral angles, D1 (1S-2C-6S-9N, D2 (4N-5C-12N-14C, and D3 (5C-12N-14C-16C. The final geometry parameters for the obtained stable conformers were determined by means of geometry optimization, carried out at DFT/B3LYP/6-31G++(d,p theory level. Afterwards the possible dimer forms of the molecule and acetazolamide-H2O clusters were formed and their energetically preferred conformations were investigated using the same method and the same level of theory. The effect of BSSE on the structure and energy of acetazolamide dimer has been investigated. The assignment of the vibrational modes was performed based on the potential energy distribution of the vibrational modes, calculated by using GAR2PED program. The experimental vibrational wavenumbers of solid acetazolamide are found to be in better agreement with the calculated wavenumbers of dimer form of acetazolamide than those of its monomeric form. NBO analysis has been performed on both monomer and dimer geometries.

  2. O-Toluic Acid Monomer and Monohydrate: Rotational Spectra, Structures, and Atmospheric Implications

    Science.gov (United States)

    Schnitzler, Elijah G.; Zenchyzen, Brandi L. M.; Jäger, Wolfgang

    2015-06-01

    Clusters of carboxylic acids with water, sulfuric acid, and other atmospheric species potentially increase the rate of new particle formation in the troposphere. Here, we present high-resolution pure rotational spectra of o-toluic acid and its complex with water in the range of 5-14 GHz, measured with a cavity-based molecular beam Fourier-transform microwave spectrometer. In both the monomer and the complex, the carboxylic acid functional group adopts a syn- conformation, with the acidic proton oriented away from the aromatic ring. In the complex, water participates in two hydrogen bonds, forming a six-membered intermolecular ring. Despite its large calculated c-dipole moment, no c-type transitions were observed for the complex, because of a large amplitude "wagging" motion of the unbound hydrogen of water, similar to the case of the benzoic acid-water complex. No methyl internal rotation splittings were observed, consistent with a high barrier (7 kJ mol-1) calculated for the monomer at the B3LYP/6-311++G(d,p) level of theory. Using statistical thermodynamics, experimental rotational constants were combined with a theoretical frequency analysis and binding energy to give an estimate of the percentage of hydrated acid in the atmosphere under various conditions. F. Riccobono, et al., Science, 344, 717 (2014). R. Zhang, et al., Science, 304, 1487 (2004). E. G. Schnitzler and W. Jäger, Phys. Chem. Chem. Phys., 16, 2305 (2014).

  3. Self-association of oxime: electronic and vibrational structures of formaldoxime monomer, dimer, and trimer

    Science.gov (United States)

    Akagi, Kazuo; Tanabe, Yukitoshi; Yamabe, Tokio

    1983-10-01

    The self-association of oxime is investigated from the aspect of intermolecular hydrogen bonding through ab initio SCF MO calculations on formaldoxime monomer, dimer, and trimer. It is understood from population analysis that formaldoxime monomer has inherently a suitable electronic distribution for constructing OH⋯3N hydrogen-bonded cyclic dimer and trimer. The formaldoxime trimer is characterized as the depressed nine membered ring. It is also confirmed to be more stable and preferable as a predominantly existing species than the dimer, which accounts for the experimental value of average association number for oximes. Vibrational analysis reveals that upon the self-association the OH stretching vibration is red-shifted, while both the OH in-plane and out-of-plane bending ones are blue-shifted, the results of which lead to a global feature of motion that ring wagging and ring puckering are activated. Largely enhanced intensities of IR-active OH stretching vibrations are well rationalized with more prominent charge polarization centered around =NOH sites in the formaldoxime dimer and trimer.

  4. Genomic redistribution of GR monomers and dimers mediates transcriptional response to exogenous glucocorticoid in vivo.

    Science.gov (United States)

    Lim, Hee-Woong; Uhlenhaut, N Henriette; Rauch, Alexander; Weiner, Juliane; Hübner, Sabine; Hübner, Norbert; Won, Kyoung-Jae; Lazar, Mitchell A; Tuckermann, Jan; Steger, David J

    2015-06-01

    Glucocorticoids (GCs) are commonly prescribed drugs, but their anti-inflammatory benefits are mitigated by metabolic side effects. Their transcriptional effects, including tissue-specific gene activation and repression, are mediated by the glucocorticoid receptor (GR), which is known to bind as a homodimer to a palindromic DNA sequence. Using ChIP-exo in mouse liver under endogenous corticosterone exposure, we report here that monomeric GR interaction with a half-site motif is more prevalent than homodimer binding. Monomers colocalize with lineage-determining transcription factors in both liver and primary macrophages, and the GR half-site motif drives transcription, suggesting that monomeric binding is fundamental to GR's tissue-specific functions. In response to exogenous GC in vivo, GR dimers assemble on chromatin near ligand-activated genes, concomitant with monomer evacuation of sites near repressed genes. Thus, pharmacological GCs mediate gene expression by favoring GR homodimer occupancy at classic palindromic sites at the expense of monomeric binding. The findings have important implications for improving therapies that target GR.

  5. Mesostructured Metal Germanium Sulfide and Selenide Materials Based on the Tetrahedral [Ge 4S 10] 4- and [Ge 4Se 10] 4- Units: Surfactant Templated Three-Dimensional Disordered Frameworks Perforated with Worm Holes

    Science.gov (United States)

    Wachhold, Michael; Kasthuri Rangan, K.; Lei, Ming; Thorpe, M. F.; Billinge, Simon J. L.; Petkov, Valeri; Heising, Joy; Kanatzidis, Mercouri G.

    2000-06-01

    The polymerization of [Ge4S10]4- and [Ge4Se10]4- unit clusters with the divalent metal ions Zn2+, Cd2+, Hg2+, Ni2+, and Co2+ in the presence of various surfactant cations leads to novel mesostructured phases. The surfactants are the quaternary ammonium salts C12H25NMe3Br, C14H29NMe3Br, C16H33NMe3Br, and C18H37NMe3Br, which play the role of templates, helping to assemble a three-dimensional mesostructured metal-germanium chalcogenide framework. These materials are stoichiometric in nature and have the formula of (R-NMe3)2[MGe4Q10] (Q=S, Se). The local atomic structure was probed by X-ray diffuse scattering and pair distribution function analysis methods and indicates that the adamantane clusters stay intact while the linking metal atoms possess a tetrahedral coordination environment. A model can be derived, from the comparison of measured and simulated X-ray powder diffraction patterns, describing the structure as an amorphous three-dimensional framework consisting of adamantane [Ge4Q10]4- units that are bridged by tetrahedral coordinated M2+ cations. The network structures used in the simulations were derived from corresponding disordered structures developed for amorphous silicon. The frameworks in (R-NMe3)2[MGe4Q10] are perforated with worm hole-like tunnels, occupied by the surfactant cations, which show no long-range order. This motif is supported by transmission electron microscopy images of these materials. The pore sizes of these channels were estimated to lie in the range of 20-30 Å, depending on the appointed surfactant cation length. The framework wall thickness of ca. 10 Å is thereby independent from the surfactant molecules used. Up to 80% of the surfactant molecules can be removed by thermal degradation under vacuum without loss of mesostructural integrity. Physical, chemical, and spectroscopic properties of these materials are discussed.

  6. 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

  7. Detection and quantification of monomers in unstimulated whole saliva after treatment with resin-based composite fillings in vivo.

    Science.gov (United States)

    Michelsen, Vibeke B; Kopperud, Hilde B M; Lygre, Gunvor B; Björkman, Lars; Jensen, Einar; Kleven, Inger S; Svahn, Johanna; Lygre, Henning

    2012-02-01

    Resin-based dental restorative materials contain allergenic methacrylate monomers, which may be released into saliva after restorative treatment. Monomers from resin-based composite materials have been demonstrated in saliva in vitro; however, studies analyzing saliva after restorative therapy are scarce. The aim of this study was to quantify methacrylate monomers in saliva after treatment with a resin-based composite filling material. Saliva was collected from 10 patients at four start points--before treatment, and 10 min, 24 h, and 7 d after treatment--and analysed by combined chromatography/mass spectrometry. The monomers bisphenol-A diglycidyl methacrylate (Bis-GMA), 2-hydroxyethyl methacrylate (HEMA), and urethane dimethacrylate (UDMA) were detected and quantified in the samples collected shortly (10 min) after treatment. The amounts detected ranged from 0.028 to 9.65 μg ml(-1) for Bis-GMA, from 0.015 to 0.19 μg ml(-1) for HEMA, and from 0.004 to 1.2 μg ml(-1) for UDMA. Triethyleneglycol dimethacrylate (TEGDMA) was detected in four of the samples. Ethoxylated bisphenol-A dimethacrylate (Bis-EMA) was not detected. Monomers were not detected in saliva samples collected before treatment, or 24 h or 7 d after treatment, with the exception of one sample, 24 h after treatment, in which HEMA was detected. In conclusion, monomers from the investigated resin-based composite and adhesive system were present in saliva shortly after treatment. One week after treatment, no monomers could be detected in patients' saliva samples.

  8. Molecular Design, Graft Polymerization and Performance Evaluation of Radiation Curable Flame Retardant Monomers Derived from Phosphorus-Nitrogen Systems

    Science.gov (United States)

    Edwards, Brian Tyndall

    The textile industry is constantly seeking new technologies to make its production more efficient, economical and environmentally friendly. An exciting new strategy to impart value-added functional finishes to textiles is the use of radiation, such as ultraviolet (UV) light, to drive the polymerization of monomers onto the surface of the substrates. These grafted polymeric layers provide the fiber or fabric with interesting new properties, such as antimicrobial behavior, water and oil repellency or flame retardancy. With the aid of a photoinitiator, UV curing can take place very rapidly and the process is waterless and uses less energy than traditional textile wet processing. With these thoughts in mind, this research explores the molecular design, synthesis, UV induced graft polymerization and performance evaluation of nine phosphorus-based flame retardant monomers for cellulosic cotton substrates. All monomers in this work were easily prepared using one-pot reactions procedures. With the assistance of Irgacure 819 photoinitiator, seven of the nine monomers were shown to simultaneously graft and polymerize onto the surface of cotton fabrics under UV radiation. JMPRTM Pro 10 software was used to explore the effect of variables, such as monomer concentration, photoinitiator concentration and UV exposure time, on the yield of the grafted polymeric layer. Burn testing of the treated fabrics in the vertical, 45° and horizontal orientations showed that all nine monomers were effective flame retardants that function via the condensed phase mechanism by encouraging the formation of nonflammable char. These burn test results were validated by thermogravimetric analysis, which demonstrated quantitatively that all nine monomers strongly promote the generation of a protective char. Finally, scanning electron microscopy was used to examine the surface morphology of the treated fabrics and visualize the grafted polymeric layer.

  9. Determination of the Preassembled Nucleating Units That Are Critical for the Crystal Growth of the Metal-Organic Framework CdIF-4.

    Science.gov (United States)

    Wagia, Raghidah; Strashnov, Ilya; Anderson, Michael W; Attfield, Martin P

    2016-07-25

    Identifying the form and role of the chemical species that traverse the stages of crystallization is critical to understanding the formation process of coordination polymers. Herein, we report the combined use of in situ atomic force microscopy and mass spectrometry to identify preformed, complex, cadmium 2-ethylimidazole containing solution species in the growth solution of the cadmium 2-ethylimidazolate metal-organic framework CdIF-4, and show that they are critical in the surface nucleation for the crystal growth of this material. Surface nucleation appears to be instigated by these [Cdx (CH3 CO2 )y (C5 H7 N2 /C5 H8 N2 )z ]-containing solution species and not by sole addition of the ligand molecules. The CH3 CO2 (-) or Cd(CH3 CO2 )2 groups of the former are substituted subsequently as the framework growth proceeds. Our greater understanding of such solution species and their role in crystallization will guide future syntheses of designed functional coordination polymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Evaluation of fit of cement-retained implant-supported 3-unit structures fabricated with direct metal laser sintering and vacuum casting techniques.

    Science.gov (United States)

    Oyagüe, Raquel Castillo; Sánchez-Turrión, Andrés; López-Lozano, José Francisco; Montero, Javier; Albaladejo, Alberto; Suárez-García, María Jesús

    2012-07-01

    This study evaluated the vertical discrepancy of implant-fixed 3-unit structures. Frameworks were constructed with laser-sintered Co-Cr, and vacuum-cast Co-Cr, Ni-Cr-Ti, and Pd-Au. Samples of each alloy group were randomly luted in standard fashion using resin-modified glass-ionomer, self-adhesive, and acrylic/urethane-based cements (n = 12 each). Discrepancies were SEM analyzed. Three-way ANOVA and Student-Newman-Keuls tests were run (P Laser-sintered structures achieved the best fit per cement tested. Within each alloy group, resin-modified glass-ionomer and acrylic/urethane-based cements produced comparably lower discrepancies than the self-adhesive agent. The abutment position did not yield significant differences. All misfit values could be considered clinically acceptable.

  11. Novel Pb2+ ion imprinted polymers based on ionic interaction via synergy of dual functional monomers for selective solid-phase extraction of Pb2+ in water samples.

    Science.gov (United States)

    Cai, Xiaoqiang; Li, Jinhua; Zhang, Zhong; Yang, Fangfang; Dong, Ruichen; Chen, Lingxin

    2014-01-08

    A novel kind of Pb(2+) ion imprinted polymers (IIPs) was prepared based on ionic interactions via the synergy of dual functional monomers of methacrylic acid and vinyl pyridine for selective solid-phase extraction (SPE) of Pb(2+) in water samples. Suspension polymerization was employed for the formation of template Pb(2+)/monomer complex by self-assembly in the presence of ethylene glycol dimethacrylate cross-linker. The resulted Pb(2+) IIPs showed fast kinetics, high binding capacity, and the adsorption processes obeyed intraparticle diffusion kinetics and Langmuir isotherm models. The IIPs displayed excellent selectivity toward Pb(2+) over other metal ions such as Cu(2+), Cd(2+), Zn(2+), and Mn(2+) with selective coefficients above 30, as well as high anti-interference ability for Pb(2+) confronting with common coexisting various ions. Through 10 adsorption-desorption cycles, the reusable IIPs exhibited a good recoverability with the standard error within 5%. These features suggested the IIPs were ideal candidates for extraction and removal of Pb(2+) ions. Consequently, the IIPs were utilized as SPE sorbents and related parameters were optimized. An excellent linearity was presented in the range of 0.2-50 μg L(-1) (R(2) = 0.9998), as well as the limits of detection and quantification were achieved of 0.06 and 0.19 μg L(-1), respectively. A good repeatability was obtained with the relative standard deviation of 2.8%. Furthermore, real water samples were successfully analyzed and satisfactory recoveries varying from 95.5 to 104.6% were attained. The IIPs-SPE demonstrated potential application perspectives for rapid and high-effective cleanup and enrichment of trace Pb(2+) ions in complicated matrices.

  12. Structural Characterization of Monomers and Oligomers of D-Amino Acid-Containing Peptides Using T-Wave Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Pang, Xueqin; Jia, Chenxi; Chen, Zhengwei; Li, Lingjun

    2016-11-01

    The D-residues are crucial to biological function of D-amino acid containing peptides (DAACPs). Previous ion mobility mass spectrometry (IM-MS) studies revealing oligomerization patterns of amyloid cascade demonstrated conversion from native soluble unstructured assembly to fibril ß-sheet oligomers, which has been implicated in amyloid diseases, such as Alzheimer's disease and type 2 diabetes. Although neuropeptides are typically present at very low concentrations in circulation, their local concentrations could be much higher in large dense core vesicles, forming dimers or oligomers. We studied the oligomerization of protonated and metal-adducted achatin I and dermorphin peptide isomers with IM-MS. Our results suggested that dimerization, oligomerization, and metal adduction augment the structural differences between D/L peptide isomers compared to protonated monomers. Dimers and oligomers enhanced the structural differences between D/L peptide isomers in both aqueous and organic solvent system. Furthermore, some oligomer forms were only observed for either D- or L-isomers, indicating the importance of chiral center in oligomerization process. The oligomerization patterns of D/L isomers appear to be similar. Potassium adducts were detected to enlarge the structural differences between D/L isomers.

  13. Structural Characterization of Monomers and Oligomers of D-Amino Acid-Containing Peptides Using T-Wave Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Pang, Xueqin; Jia, Chenxi; Chen, Zhengwei; Li, Lingjun

    2017-01-01

    The D-residues are crucial to biological function of D-amino acid containing peptides (DAACPs). Previous ion mobility mass spectrometry (IM-MS) studies revealing oligomerization patterns of amyloid cascade demonstrated conversion from native soluble unstructured assembly to fibril ß-sheet oligomers, which has been implicated in amyloid diseases, such as Alzheimer's disease and type 2 diabetes. Although neuropeptides are typically present at very low concentrations in circulation, their local concentrations could be much higher in large dense core vesicles, forming dimers or oligomers. We studied the oligomerization of protonated and metal-adducted achatin I and dermorphin peptide isomers with IM-MS. Our results suggested that dimerization, oligomerization, and metal adduction augment the structural differences between D/L peptide isomers compared to protonated monomers. Dimers and oligomers enhanced the structural differences between D/L peptide isomers in both aqueous and organic solvent system. Furthermore, some oligomer forms were only observed for either D- or L-isomers, indicating the importance of chiral center in oligomerization process. The oligomerization patterns of D/L isomers appear to be similar. Potassium adducts were detected to enlarge the structural differences between D/L isomers.

  14. Quantitative Analysis of Volatile Impurities in Diallyldimethylammonium Chloride Monomer Solution by Gas Chromatography Coupled with Liquid-Liquid Extraction

    Directory of Open Access Journals (Sweden)

    Cheng Liu

    2017-01-01

    Full Text Available The quantitative analysis method for volatile impurities in diallyldimethylammonium chloride (DADMAC monomer solution was established in this paper. The volatile impurities were quantitatively analyzed with trichloromethane as extraction solvent and n-hexane as internal standard by using gas chromatography (GC coupled with solvent extraction, and the chromatographic conditions, quantitative methods, and extraction conditions were systematically investigated in detail. The results showed that excellent linear relationships of 5 volatile impurities (dimethylamine, allyldimethylamine, allyl chloride, allyl alcohol, and allyl aldehyde were obtained in the range of 1–100 mg·L−1. The method also showed good specificity, recovery (95.0%–107.5%, and relative standard deviation (RSD, 1.40%–7.67%. This method could accurately detect the whole volatile impurities in DADMAC monomer solution quantitatively in one time with a low detection limit. Furthermore, this method is conducive to the preparation of highly pure DADMAC monomer and the development of national and international standards of the DADMAC monomer product quality, and the results could provide a strong foundation for the regulation and mechanism research of impurities on monomer reactivity in polymerization.

  15. Biosynthesis and characterization of polyhydroxyalkanoate containing high 3-hydroxyhexanoate monomer fraction from crude palm kernel oil by recombinant Cupriavidus necator.

    Science.gov (United States)

    Wong, Yoke-Ming; Brigham, Christopher J; Rha, ChoKyun; Sinskey, Anthony J; Sudesh, Kumar

    2012-10-01

    The potential of plant oils as sole carbon sources for production of P(3HB-co-3HHx) copolymer containing a high 3HHx monomer fraction using the recombinant Cupriavidus necator strain Re2160/pCB113 has been investigated. Various types and concentrations of plant oils were evaluated for efficient conversion of P(3HB-co-3HHx) copolymer. Crude palm kernel oil (CPKO) at a concentration of 2.5 g/L was found to be most suitable for production of copolymer with a 3HHx content of approximately 70 mol%. The time profile of these cells was also examined in order to study the trend of 3HHx monomer incorporation, PHA production and PHA synthase activity. (1)H NMR and (13)C NMR analyses confirmed the presence of P(3HB-co-3HHx) copolymer containing a high 3HHx monomer fraction, in which monomers were not randomly distributed. The results of various characterization analyses revealed that the copolymers containing a high 3HHx monomer fraction demonstrated soft and flexible mechanical properties. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Structural Basis of Native CXCL7 Monomer Binding to CXCR2 Receptor N-Domain and Glycosaminoglycan Heparin

    Directory of Open Access Journals (Sweden)

    Aaron J. Brown

    2017-02-01

    Full Text Available CXCL7, a chemokine highly expressed in platelets, orchestrates neutrophil recruitment during thrombosis and related pathophysiological processes by interacting with CXCR2 receptor and sulfated glycosaminoglycans (GAG. CXCL7 exists as monomers and dimers, and dimerization (~50 μM and CXCR2 binding (~10 nM constants indicate that CXCL7 is a potent agonist as a monomer. Currently, nothing is known regarding the structural basis by which receptor and GAG interactions mediate CXCL7 function. Using solution nuclear magnetic resonance (NMR spectroscopy, we characterized the binding of CXCL7 monomer to the CXCR2 N-terminal domain (CXCR2Nd that constitutes a critical docking site and to GAG heparin. We found that CXCR2Nd binds a hydrophobic groove and that ionic interactions also play a role in mediating binding. Heparin binds a set of contiguous basic residues indicating a prominent role for ionic interactions. Modeling studies reveal that the binding interface is dynamic and that GAG adopts different binding geometries. Most importantly, several residues involved in GAG binding are also involved in receptor interactions, suggesting that GAG-bound monomer cannot activate the receptor. Further, this is the first study that describes the structural basis of receptor and GAG interactions of a native monomer of the neutrophil-activating chemokine family.

  17. Solvent-Controlled Assembly of ionic Metal-Organic Frameworks Based on Indium and Tetracarboxylate Ligand: Topology Variety and Gas Sorption Properties

    KAUST Repository

    Zheng, Bing

    2016-07-15

    Four Metal-Organic Frameworks (MOFs) based on Indium and tetracarboxylate ligand have been synthesized through regulation of the solvent conditions, the resulted compounds not only exhibited rich structural topologies (pts, soc and unique topologies), but also interesting charge reversal framework features. By regulating the solvent, different building units (indium monomer, trimer) have been generated in situ, and they are connected with the ligand to form ionic frameworks 1-4, respectively. Among the synthesized four ionic frameworks, compounds 3 and 4 could keep their crystallinity upon heating temperature up to 300oC after fully removal of solvent guest molecules, they also exhibit the charge reversal framework features (3 adopts an overall cationic framework, while 4 has an anionic framework). Both compounds 3 and 4 exhibit significant uptake capacity for CO2 and H2, besides that, compounds 3 and 4 also present excellent selective adsorption of CO2 over N2 and CH4.

  18. Combined theoretical and time-resolved photoluminescence investigations of [Mo₆Brⁱ₈Br(a)₆]²⁻ metal cluster units: evidence of dual emission.

    Science.gov (United States)

    Costuas, K; Garreau, A; Bulou, A; Fontaine, B; Cuny, J; Gautier, R; Mortier, M; Molard, Y; Duvail, J-L; Faulques, E; Cordier, S

    2015-11-21

    The combined time-resolved photoluminescence (PL) and theoretical study performed on luminescent [Mo6Br(i)8Br(a)6](2-)-based systems unambiguously shows that their NIR-luminescence is due to at least two emissive states. By quantum chemical studies, we show for the first time that important geometrical relaxations occur at the triplet states either by the outstretching of an apex away from the square plane of the Mo6 octahedron or by the elongation of one Mo-Mo bond. Experimental PL measurements demonstrate that the external environment (counter-ions, crystal packing) of the cluster has a noticeable impact on its relaxation processes. Temperature and excitation wavelength dependence of the two components of the luminescence spectra is representative of multiple competitive de-excitation processes in contradiction with Kasha's rule. Our results also demonstrate that the relaxation processes before and after emission can be tracked via fast time-resolved spectroscopy. They also show that the surroundings of the luminescent cluster unit and the excitation wavelength could be modulated for target applications.

  19. Spectroscopical properties of organic/metal nanohybrids.

    Science.gov (United States)

    Dellepiane, Giovanna; Cuniberti, Carla; Alloisio, Marina; Demartini, Anna

    2010-03-28

    The aim of our work was to prepare stable nanohybrids of controlled size and shape consisting of a noble metal core decorated with polydiacetylenes (PDAs). Due to the combination of the outstanding linear and nonlinear optical properties of the polydiacetylenic chains with the electromagnetic field-enhancing capability of metal nanostructures, these novel composites can find potential application in different fields. In particular, the different colours exhibited by PDAs in relation to the chemical nature of the monomer and the polymerization procedure, as well as in response to environmental perturbations, make them excellent materials for the fabrication of sensing devices. On the basis of our previous work on PDA self-assembled monolayers on flat metal surfaces, the results of which are briefly reported, we prepared differently-shaped gold and silver nanocores (spheres, cages) coated with various diacetylenic monomers having end-groups able to firmly anchor to the metal surface. These nanohybrids exhibit in aqueous colloidal solution an enhanced photochemical polymerization monitored step by step with UV-Vis and SERS techniques. It is shown that in these stable assemblies an intra-particle polymerization takes place and that the dominant PDA form is conditioned by the core size and geometry. While the nanoparticles are SERS active in the visible, the nanocages should be excellent SERS substrates from the visible to the near infrared regions.

  20. 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.

  1. Nonferrous Metal Mines - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer includes nonferrous metal mines in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the U.S....

  2. Ferrous Metal Mines - Direct Download

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This map layer includes ferrous metal mines in the United States. The data represent commodities covered by the Minerals Information Team (MIT) of the U.S....

  3. The Effect of Tripterygium Wilfordii Monomer T4 on Rat Spermatid Nuclear Protein Transition

    Institute of Scientific and Technical Information of China (English)

    戴文平; 刘平; 陈啸梅; 薛社普

    1996-01-01

    Rat testis elongating spermatids and epididymal sperms were collected after 7 weeks of treatment with Tripterygium wilfordii monomer T4. Total nuclear basic protein (TNBP) was extracted from the elongating spermatid nuclei and the sperm nuclei isolated by sonication. Polyacrylamide gel electrophoresis has beep used to separate the TNBP and individual proteins were quantified by scanning microdensitometry. It was found that the content of protamine was reduced and the TH (Total Histones) /RP (Rat Protamine) ratios were increased following treatment in the testis elongating spermatids, and same result was found in the epididymal sperms. These results suggest that the interruption of nuclear protein transition of testis spermatids induced by T4 might cause aberrant epididymal sperm nuclear protein and lead to infertility. The relationship between protamine and fertility was discussed.

  4. Cutin monomer induces expression of the rice OsLTP5 lipid transfer protein gene.

    Science.gov (United States)

    Kim, Tae Hyun; Park, Jong Ho; Kim, Moon Chul; Cho, Sung Ho

    2008-01-01

    Treatment with the cutin monomer 16-hydroxypalmitic acid (HPA), a major component of cutin, elicited the synthesis of hydrogen peroxide (H2O2) in rice leaves and induced the expression of the lipid transfer protein gene OsLTP5. Treatment with HPA also induced expression of OsLTP1, OsLTP2, and the pathogen-related PR-10 genes to a lesser extent. The OsLTP5 transcript was expressed prominently in stems and flowers, but was barely detectable in leaves. Expression of OsLTP5 was induced in shoots in response to ABA and salicylic acid. It is proposed that HPA is perceived by rice as a signal, inducing defense reactions.

  5. Formation of surface relief gratings with homeotropically oriented photopolymer from a photocross-linkable organic monomer.

    Science.gov (United States)

    Zhao, Dongyu; Xu, Zeda; Wang, Guojie; Cao, Hui; Li, Wenbo; He, Wanli; Huang, Wei; Yang, Zhou; Yang, Huai

    2010-02-21

    In this communication, we describe a simple process for the generation of surface relief gratings (SRG). SRG are fabricated from a photocross-linkable organic monomer PDACE (4-propyldiphenylacetylenecarboxylic acid cinnamyl ester) with cinnamyl ester and tolane groups, by using a patterned non-polarized UV light irradiation. The patterns of the surface relief structures can be easily controlled and the modulation depth can reach 130 nm. Moreover, it is interestingly observed that the photopolymer of the SRG exhibits distinctive characteristics including homeotropic orientation and fluorescence properties as a result of the photocross-linking of the dual photoreactive groups of PDACE. Finally, the mechanism of fabrication of SRG from PDACE is discussed with mean-field theory.

  6. 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.

  7. Radiation crosslinking of styrene-butadiene rubber containing waste tire rubber and polyfunctional monomers

    Science.gov (United States)

    Yasin, Tariq; Khan, Sara; Shafiq, Muhammad; Gill, Rohama

    2015-01-01

    The objective of this study was to investigate the influence of polyfunctional monomers (PFMs) and absorbed dose on the final characteristics of styrene-butadiene rubber (SBR) mixed with waste tire rubber (WTR). A series of SBR/WTR blends were prepared by varying the ratios of WTR in the presence of PFMs, namely trimethylolpropane trimethacrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA) and crosslinked using gamma rays. The physicochemical characteristics of the prepared blends were investigated. It was observed that tensile strength, hardness and gel content of the blends increased with absorbed dose while the blends containing TMPTA showed higher tensile strength, gel content and thermal stability as compared to the blends containing TMPTMA. Higher thermal stability was observed in the blends which were crosslinked by radiation as compared to the blends crosslinked by sulfur. These blends exhibited higher rate of swelling in organic solvents, whereas negligible swelling was observed in acidic and basic environment.

  8. New polymer gel dosimeters consisting of less toxic monomers with radiation-crosslinked gel matrix

    Science.gov (United States)

    Hiroki, A.; Yamashita, S.; Sato, Y.; Nagasawa, N.; Taguchi, M.

    2013-06-01

    New polymer gel dosimeters consisting of less toxic methacrylate-type monomers such as 2-hydroxymethyl methacrylate (HEMA) and polyethylene glycol 400 dimethacrylate (9G) with hydroxypropyl cellulose (HPC) gel were prepared. The HPC gels were obtained by using a radiation-induced crosslinking technique to be applied in a matrix instead of a gelatin, which is conventionally used in earlier dosimeters, for the polymer gel dosimeters. The prepared polymer gel dosimeters showed cloudiness by exposing to 60Co γ-ray, in which the cloudiness increased with the dose up to 10 Gy. At the same dose, the increase in the cloudiness appeared with increasing concentration of 9G. As a result of the absorbance measurement, it was found that the dose response depended on the composition ratio between HEMA and 9G.

  9. Janus emulsions formed with a polymerizable monomer, silicone oil, and Tween 80 aqueous solution.

    Science.gov (United States)

    Ge, Lingling; Lu, Shuhui; Guo, Rong

    2014-06-01

    Janus emulsions of a polymerizable monomer tripropyleneglycol diacrylate (TP) combined with silicone oil (SO) as inner oil phases and Tween 80 aqueous solution as continuous phase are prepared in a one-step high energy mixing process. The dependence of droplet topology on the concentration of surfactant, TP/SO ratio, and the stirring speed during emulsification is investigated. The result shows that the volume ratio of two oils within an individual droplet changes correspondingly to the total composition of emulsion. Increasing the speed of stirring results in a significant reduction in the droplet size, i.e. a five times increase in the stirring speed produces a droplet size reduction from hundreds to a few microns. What is more important, the topology of Janus drops remains similar for the different preparations. These fundamental investigations illustrate the potential for future Janus particle synthesis in batch scale with a controllable particle topology.

  10. Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers

    Science.gov (United States)

    Dubois, F.; Derouiche, Y.; Leblond, J. M.; Maschke, U.; Douali, R.

    2015-09-01

    The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009), 10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

  11. Progress of Research in Treatment of Hyperlipidemia by Monomer or Compound Recipe of Chinese Herbal Medicine

    Institute of Scientific and Technical Information of China (English)

    DOU Xiao-bing; WO Xing-de; FAN Chun-lei

    2008-01-01

    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.

  12. Synergistic Hypergolic Ignition of Amino End Group in Monomers and Polymers

    Directory of Open Access Journals (Sweden)

    S. P. Panda

    1986-10-01

    Full Text Available A few monomers, oligomers and polymers with amino end groups have been discovered to undergo synergistic ignition with red fuming nitric acid (RFNA when mixed with large quantities of magnesium powder. Aluminium powder under similar conditions does not ignite the mixture while powders of Zn, Co and Cu cause the ignition. Amongst the polymers used in the experiment commercially available nylon 6 is the most important which may be used as a binder for rocket propellant fuel grains, hypergolic with RFNA. Degree of polymerisation or the chain length of the polymers does not drastically affect the synergistic ignition of the polymer mixture with magnesium powder but high molecular weight and fully aromatised polymers like Kevlar and Nomex fail to ignite under similar conditions. Based upon the earlier work of the authors, explanations for the phenomena oberved have been provided in terms of creation of hot spots leading to ignition at the amino end groups.

  13. Enzymatic polymerization of bio-based monomers for applications in hydrogels and coatings

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Nguyen, Hiep Dinh; Storgaard, Thomas

    Enzymatic polymerization has been gradually building up during the last 30 years as an alternative to classical polyesterificaiton processes, which permits preparation of polyesters under more benign conditions with high selectivity1. In particular, the high selectivity is an interesting property...... 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...... on PEG have been prepared and functionalized through aza-michael additions as well as through thiol-ene chemistry2. Thereby the enzymatically prepared polymer backbone can be considered a scaffold for functional water soluble materials. Finally, these polymers have been applied for preparation...

  14. Extraction, characterization of components, and potential thermoplastic applications of camelina meal grafted with vinyl monomers.

    Science.gov (United States)

    Reddy, Narendra; Jin, Enqi; Chen, Lihong; Jiang, Xue; Yang, Yiqi

    2012-05-16

    Camelina meal contains oil, proteins, and carbohydrates that can be used to develop value-added bioproducts. In addition to containing valuable polymers, coproducts generated during the production of biofuels are inexpensive and renewable. Camelina is a preferred oilseed crop for biodiesel production because camelina is easier to grow and provides better yields. In this research, the components in camelina meal were extracted and studied for their composition, structure, and properties. The potential of using the camelina meal to develop thermoplastics was also studied by grafting various vinyl monomers. Oil (19%) extracted from camelina meal could be useful for food and fuel applications, and proteins and cellulose in camelina meal could be useful in the development of films, fibers, and thermoplastics. Thermoplastic films developed from grafted camelina meal had excellent wet tensile properties, unlike thermoplastics developed from other biopolymers. Camelina meal grafted with butylmethacrylate (BMA) had high dry and wet tensile strengths of 53.7 and 17.3 MPa, respectively.

  15. Crosslinking-property relationships in PMR polyimide composites. I. [polymerization of monomer reactants

    Science.gov (United States)

    Pater, R. H.; Whitley, K.; Morgan, C.; Chang, A.

    1991-01-01

    The effect of the crosslink density of the matrix on physical and mechanical properties of a graphite-fiber-reinforced PMR (for polymerization of monomer reactants) polyimide composites during isothermal aging was investigated in experiments where unidirectional composite specimens of Celion 6000/PMR-P1 were isothermally exposed at 288 C in air for various time periods up to 5000 hrs. It was found that, as the crosslink density increased, the glass transition temperature, density, and elevated-temperature interlaminar shear strength of a composite increased, while the initial moisture absorption and the coefficient of thermal expansion decreased. However, after reaching the highest possible matrix crosslink density, several of the composite properties began to deteriorate rapidly.

  16. Water and acrylamide monomer transfer rates from a settling basin to groundwaters.

    Science.gov (United States)

    Binet, Stéphane; Bru, Kathy; Klinka, Thomas; Touzé, Solène; Motelica-Heino, Mickael

    2015-05-01

    The aim of this paper was to estimate the potential leakage of acrylamide monomer, used for flocculation in a settling basin, towards the groundwaters. Surface-groundwater interactions were conceptualized with a groundwater transport model, using a transfer rate to describe the clogged properties of the interface. The change in the transfer rate as a function of the spreading of the clogged layer in the settling basin was characterized with respect to time. It is shown that the water and the Acrylamide transfer rate are not controlled by the spreading of the clogged layer until this layer fully covers the interface. When the clogged layer spreads out, the transfer rate remains in the same order of magnitude until the area covered reaches 80 %. The main flux takes place through bank seepage. In these early stage conditions of a working settling basin, the acrylamide flux towards groundwaters remains constant, at close to 10 g/year (±5).

  17. Synthesis of fluorinated dimethacrylate monomer and its application in preparing Bis-GMA free dental resin.

    Science.gov (United States)

    Yin, Mei; Guo, Sen; Liu, Fang; He, Jingwei

    2015-11-01

    With the aim to reduce human exposure to Bis-phenol A derivatives, a novel fluorinated dimethacrylate monomer FUDMA was synthesized and mixed with triethyleneglycol dimethacrylate (TEGDMA) to prepare 2,2-bis[4-(2-hydroxy-3-methacryloy- loxypropyl)phenyl]propane (Bis-GMA) free dental resin system. Physicochemical properties, such as double bond conversion (DC), polymerization shrinkage (VS), water sorption (WS) and solubility (SL), flexural strength (FS) and modulus (FM), and fracture energy of FUDMA/TEGDMA resin system were investigated. Bis-GMA/TEGDMA resin system was used as a control. The results showed that, compared with Bis-GMA/TEGDMA resin system, FUDMA/TEGDMA had advantages like higher DC, lower VS, and higher fracture energy, but had no disadvantages. Therefore, FUDMA/TEGDMA resin system had better comprehensive physicochemical properties than Bis-GMA/TEGDMA resin system, and FUDMA had potential to be used as a substitute for Bis-GMA.

  18. Linear Copolymer of N-Isopropylacrylamide and 2-Hydroxyethylacrylate: Synthesis, Characterization and Monomer Reactivity Ratios

    Directory of Open Access Journals (Sweden)

    Nakan U

    2016-09-01

    Full Text Available Сopolymerization of N-isopropylacrylamide (NIPAAm with 2-hydroxyethyl acrylate (2-HEA carried out by solvent ethanol solution method, at 600C, using Azoisobutyronitrile (AIBN as an initiator. The hydrophilic copolymers were characterized by elemental analysis, DSC, TGA and turbidimetric method. The results showed thermal stability increase with increase of NIPAAm in the copolymers. It was found that copolymer solutions have lower critical solution temperature (by turbidimetric analysis. The reactivity ratios of monomers were determined using linear methods like Fineman-Ross and Kelen-Tudos. The reactivity ratios of r1 and r2 were found to be 0,86, 0,72 and 1,02, 1,04 respectively.

  19. Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers.

    Science.gov (United States)

    Dubois, F; Derouiche, Y; Leblond, J M; Maschke, U; Douali, R

    2015-09-01

    The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009)10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

  20. Microporous Polymers from a Carbazole-Based Triptycene Monomer: Synthesis and Their Applications for Gas Uptake.

    Science.gov (United States)

    Zhai, Tian-Long; Tan, Liangxiao; Luo, Yi; Liu, Jun-Min; Tan, Bien; Yang, Xiang-Liang; Xu, Hui-Bi; Zhang, Chun

    2016-01-01

    Two kinds of novel organic microporous polymers TCPs (TCP-A and TCP-B) were prepared by two cost-effective synthetic strategies from the monomer of tricarbazolyltriptycene (TCT). Their structure and properties were characterized by FT-IR, solid (13) C NMR, powder XRD, SEM, TEM, and gas absorption measurements. TCP-B displayed a high surface area (1469 m(2)  g(-1) ) and excellent H2 storage (1.70 wt % at 1 bar/77 K) and CO2 uptake abilities (16.1 wt % at 1 bar/273 K), which makes it a promising material for potential application in gas storage.

  1. Combinatory approach of methacrylated alginate and acid monomers for concrete applications.

    Science.gov (United States)

    Mignon, Arn; Devisscher, Dries; Graulus, Geert-Jan; Stubbe, Birgit; Martins, José; Dubruel, Peter; De Belie, Nele; Van Vlierberghe, Sandra

    2017-01-02

    Polysaccharides, and especially alginate, can be useful for self-healing of cracks in concrete. Instead of weak electrostatic bonds present within calcium alginate, covalent bonds, by methacrylation of the polysaccharides, will result in mechanically stronger superabsorbent polymers (SAPs). These methacrylated alginate chains as backbone are combined with two acrylic monomers in a varying molar fraction. These SAPs show a moisture uptake capacity up to 110% their own weight at a relative humidity of 95%, with a negligible hysteresis. The swelling capacity increased (up to 246 times its own weight) with a decreasing acrylic acid/2 acrylamido-2-methylpropane sulfonic acid ratio. The SAPs also showed a thermal stability up to 200°C. Interestingly, the SAP composed of alginate and acrylic acid exerted a very limited decrease in compressive strength (up to 7% with addition of 1wt% SAP) rendering this material interesting for the envisaged self-healing application. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. 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...... was studied by ten successive exposures of a plate to 3% acetic acid for 30 min at 95 degrees C. The results indicate that continuous migration of formaldehyde and melamine takes place during the lifetime of these articles. The molar ratio of released formaldehyde to melamine was seen to decrease from 12...

  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. 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.)

  5. Monomer Basis Representation Method For Calculating The Spectra Of Molecular Clusters I. The Method And Qualitative Models

    CERN Document Server

    Ocak, Mahir E

    2012-01-01

    Firstly, a sequential symmetry adaptation procedure is derived for semidirect product groups. Then, this sequential symmetry adaptation procedure is used in the development of new method named Monomer Basis Representation (MBR) for calculating the vibration-rotation-tunneling (VRT) spectra of molecular clusters. The method is based on generation of optimized bases for each monomer in the cluster as a linear combination of some primitive basis functions and then using the sequential symmetry adaptation procedure for generating a small symmetry adapted basis for the solution of the full problem. It is seen that given an optimized basis for each monomer the application of the sequential symmetry adaptation procedure leads to a generalized eigenvalue problem instead of a standard eigenvalue problem if the procedure is used as it is. In this paper, MBR method will be developed as a solution of that problem such that it leads to generation of an orthogonal optimized basis for the cluster being studied regardless of...

  6. Molecular alignment enhancement phenomenon of polymer formed from a liquid crystal monomer in a liquid crystal solvent

    Science.gov (United States)

    Fujikake, Hideo; Murashige, Takeshi; Sato, Hiroto; Kawakita, Masahiro; Kikuchi, Hiroshi

    2003-03-01

    We report an abnormal alignment enhancement phenomenon of polymer molecules. The alignment order of a rigid-skeleton polymer made from a liquid crystalline monomer in a low-molecular-weight liquid crystal solvent was drastically enhanced with increasing temperature, even though the alignment order of the solution of the liquid crystal and monomer decreased. From polymer molecular alignment observations using polarizing Raman scattering microscopy, it was found that the polymer alignment order was three times greater than that of the original aligned monomer and polymer. This super alignment technique of polymer using a molecular-scaled self-assembly mechanism is applicable to the formation of electrically and/or optically functional nanopolymer wires.

  7. Quantitation of oxidized triglyceride monomers and dimers as an useful measurement for early and advanced stages of oxidation

    Directory of Open Access Journals (Sweden)

    Márquez-Ruiz, G.

    1996-04-01

    Full Text Available Quantitation of oxidized triglyceride monomers and dimers is reported as a good measurement for early and advanced stages of oxidation. Applicability of this approach to follow-up oxidation was tested in samples of trilinolein and methyl linoleate stored at either room temperature or 60°C for different periods of time. Oxidized monomers, dimers and polymers were determined in 50 mg-samples by adding monostearin as internal standard and applying a combination of adsorption chromatography, using silica cartridges, followed by high-performance size-exclusion chromatography. Additionally, peroxide values and tocopherol contents were measured. Results showed that a significant rise of dimeric compounds denoted the end of the induction period while oxidized monomers were the only group of compounds showing a progressive increase during the early stages of oxidation.

  8. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides.

    Science.gov (United States)

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-21

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co(3)O(4), ZnO, Mn(2)O(3), MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N(2), whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N(2). Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N(2) and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H(2) and CO(2) adsorption properties depending on the environment used for the thermolysis of MOFs.

  9. Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides.

    Science.gov (United States)

    Debuigne, Antoine; Morin, Aurélie N; Kermagoret, Anthony; Piette, Yasmine; Detrembleur, Christophe; Jérôme, Christine; Poli, Rinaldo

    2012-10-01

    This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered with the aim of studying the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidonepolymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, through a covalent bond and a dative bond, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. Possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding the factors influencing Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide) materials, which are an important class of polymers that sustain numerous applications today.

  10. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman

    2015-07-01

    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

  11. Identification and quantification of monomers released from dental composites using HPLC

    Directory of Open Access Journals (Sweden)

    Lucí Regina Panka Archegas

    2009-08-01

    Full Text Available The aim of this study was to detect and quantify the main residual monomers released from composites, using high performance liquid chromatography (HPLC. Discs were made with dental composites (Herculite XRV, Tetric Ceram and Filtek Z250 and immersed in deionized water at 37ºC for 28 days, with water changes in 1, 7, 14 and 21 days. The mean concentration of residual monomers were subject to the Kruskal-Wallis test (pA liberação de monômeros residuais pode afetar o comportamento clínico e a biocompatibilidade dos materiais resinosos. O objetivo deste estudo foi detectar e quantificar os principais monômeros residuais liberados de resinas compostas, usando cromatografia líquida de alta performance (HPLC. Discos foram construídos de resinas compostas de uso odontológico (Herculite XRV, Tetric Ceram and Filtek Z250 e imersos em água deionizada a 37ºC durante 28 dias, com mudanças de água em 24 horas, 7, 14 e 21 dias. As concentrações médias dos monômeros residuais foram submetidas ao teste de Kruskal-Wallis (p<0,05. Tetric Ceram apresentou as maiores concentrações de monômeros lixiviados. Bis-GMA foi o monômero liberado em menores concentrações para todos os materiais. Não houve diferença estatística significante entre TEGDMA e UDMA. A maioria dos monômeros demonstrou máxima concentração no período de 7 dias. A análise por meio de HPLC identificou Bis-GMA, TEGDMA e UDMA em quantidades detectáveis para todas as resinas compostas testadas.

  12. Properties of silorane-based dental resins and composites containing a stress-reducing monomer.

    Science.gov (United States)

    Eick, J David; Kotha, Shiva P; Chappelow, Cecil C; Kilway, Kathleen V; Giese, Gregory J; Glaros, Alan G; Pinzino, Charles S

    2007-08-01

    To evaluate properties of silorane-based resins and composites containing a stress reducing monomer. Resin mixtures and composites were formulated containing (a) a developmental stress reducing monomer [TOSU; Midwest Research Institute]; (b) Sil-Mix (3M-ESPE); (c) photo cationic initiator system. Standard BISGMA/TEGDMA resin (B/T) and composite (Filtek Z250) were used as controls. Polymerization volume change was measured using a NIST mercury dilatometer and polymerization stress using an Enduratec mechanical testing machine. Three point bend tests determined flexural elastic modulus, work of fracture, and ultimate strength (ADA 27; ISO 4049). Fracture toughness was measured using ASTM E399-90. Four groups of resins and composites were tested: Sil-Mix, methacrylate standard, and Sil-Mix with two addition levels of TOSU. An ANOVA was used and significant differences ranked using Student-Newman-Keuls test (alpha=0.05). Polymerization stress values for resins containing TOSU were significantly less than the other materials. Polymerization shrinkage values for Sil-Mix formulations were significantly less than for B/T, but were not different from each other. TOSU-containing formulations generally had somewhat lower mechanical properties values than Sil-Mix or B/T. Polymerization stress values for Sil-Mix-based composites were significantly less as compared to Z250. The 1wt.% TOSU composite had the lowest stress. No difference between composite groups was noted for fracture toughness or work of fracture. For ultimate strength, the 5wt.% TOSU formulation differed significantly from Z250. All Sil-Mix formulations had elastic modulus values significantly different from Z250. The ability of TOSU to reduce polymerization stress without a proportional reduction in mechanical properties provides a basis for improvement of silorane-based composites.

  13. Time-kill behaviour against eight bacterial species and cytotoxicity of antibacterial monomers.

    Science.gov (United States)

    Li, Fang; Weir, Michael D; Fouad, Ashraf F; Xu, Hockin H K

    2013-10-01

    The objectives of this study were to investigate: (1) the antibacterial activity of two antibacterial monomers, dimethylaminododecyl methacrylate (DMADDM) and dimethylammoniumethyl dimethacrylate (DMAEDM), against eight different species of oral pathogens for the first time; (2) the cytotoxicity of DMAEDM and DMADDM. DMAEDM and DMADDM were synthesized by reacting a tertiary amine group with an organo-halide. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against eight species of bacteria were tested. Time-kill determinations were performed to examine the bactericidal kinetics. Cytotoxicity of monomers on human gingival fibroblasts (HGF) was assessed using a methyl thiazolyltetrazolium assay and live/dead viability assay. DMADDM showed strong bactericidal activity against all bacteria, with MIC of 1.2-9.8μg/mL. DMAEDM had MIC of 20-80mg/mL. Time-kill determinations indicated that DMADDM and DMAEDM had rapid killing effects against eight species of bacteria, and eliminated all bacteria in 30min at the concentration of 4-fold MBC. Median lethal concentration for DMADDM and DMAEDM was between 20 and 40μg/mL, which was 20-fold higher than 1-2μg/mL for BisGMA control. DMAEDM and DMADDM were tested in time-kill assay against eight species of oral bacteria for the first time. Both were effective in bacteria-inhibition, but DMADDM had a higher potency than DMAEDM. Different killing efficacy was found against different bacteria species. DMAEDM and DMADDM had much lower cytotoxicity than BisGMA. Therefore, DMADDM and DMAEDM are promising for use in bonding agents and other restorative/preventive materials to combat a variety of oral pathogens. Published by Elsevier Ltd.

  14. Structural effect of monomer type on properties of copolyimides and copolyimide-silica hybrid materials

    Directory of Open Access Journals (Sweden)

    Kizilkaya Canan

    2015-01-01

    Full Text Available In this work, the effect of two different diamine monomers, containing phosphine oxide, on thermal, mechanical and morphological properties of copolyimides and their hybrid materials was investigated. Gas separation properties of the synthesized copolyimides were also analysed. Two different diamine monomers with phosphine oxide were bis(3-aminophenyl phenylphosphine oxide (BAPPO and bis(3-aminophenoxy-4-phenyl phenylphosphine oxide (m-BAPPO. In the synthesis of copolyimides 3,3’-diamino-diphenyl sulfone (DDS was also used as the diamine, as well as 2,2’-bis(3,4-dicarboxyphenylhexafluoropropane dianhydride (6FDA. Copolyimide films were prepared by thermal imidization. Hybrid materials containing 5 % SiO2 were synthesised further by sol-gel technique. The Fourier-transform infrared spectroscopy (FTIR, Nuclear magnetic resonance spectroscopy (NMR confirmed the expected structure. Dynamic mechanical analysis (DMA demonstrated that m-BAPPO based copolyimides had lower glass transition temperatures (Tg than BAPPO based copolyimides. m-BAPPO containing copolyimide without silica shifted the thermal decomposition temperature to a higher value. The moduli and strength values of BAPPO diamine containing copolyimide and its hybrid were higher than those of m-BAPPO containing materials. The contact angle measurements showed the hydrophobicity. Scanning electron microscope (SEM analysis exhibited the silica particles dispersion in the copolyimides. These copolyimides may be used in the coating industry. The CO2 permeability and the permselectivity were the highest among the other values in this study, when m-BAPPO containing copolyimide in the absence of silica was used. The gas permeabilities obtained from this work were in this decreasing order: PCO2 > PO2 > PN2.

  15. Association of Fibrin Monomer Polymerization Function, Cerebrovascular Risk Factors and Ischemic Cerebrovascular Disease in Old People

    Institute of Scientific and Technical Information of China (English)

    洪梅; 魏文宁; 李红戈; 杨锐; 杨焰

    2003-01-01

    Summary: In order to investigate the association of fibrin monomer polymerization function (FMPF)with traditional cerebrovascular risk factors and ischemic cerebrovascular disease in old people, 1 : 1paired case-control comparative study was performed for FMPF and traditional cerebrovascular riskfactors on 110 cases of old ischemic cerebrovascular disease and 110 controls matched on age, sex andliving condition. The results showed that cerebrovascular risk factors were more prevalent in casegroup than in control group. In the case group, FMPF was significantly higher than in controlgroup. There was a significant positive correlation between hypertension and fibrin monomer poly-merization velocity (FMPV), hypertension and fibrinogen (Fbg), alcohol consumption and Fbg, butno significant correlation between diabetic mellitus, smoking and FMPF was found. Among the pa-rameters of blood lipids, there were significant positive correlations between total cholesterol (TC)and parameters of FMPF to varying degrees, triglycerides (TG) and FMPV, TG and Fbg. Our re-sults also showed there were significant linear trends between TC and FMPV (P<0. 001), TC andFbg (P=0. 0087), TG and FMPV/Amax (maximum absorbance)(P=0. 0143) respectively. Multi-ple logistic regression analysis revealed that FMPF in case group remained significantly higher thancontrol group after adjustment of all risk factors that were significant in univariate analysis. It wasconcluded that there is a possible pathophysiological link between FMPF and cerebrovascular risk fac-tors. An elevated FMPF is associated with ischemic cerebrovascular disease and an independent riskfactor of this disease. In old people, detection of FMPF might be a useful screening to identify indi-viduals at increased cerebrothrombotic risk.

  16. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  17. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2009-12-14

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60+-0.05 eV and 7.6+-0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra, suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the CH+ signal at 9.20+-0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH+ appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  18. 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.

  19. Formation of a cyclic dimer containing two mirror image monomers in the solid state controlled by van der Waals forces.

    Science.gov (United States)

    Zhang, Zibin; Yu, Guocan; Han, Chengyou; Liu, Jiyong; Ding, Xia; Yu, Yihua; Huang, Feihe

    2011-09-16

    Two new copillar[5]arenes were prepared. They are arranged in two completely different motifs, a cyclic dimer containing two monomers with two different conformations that are mirror images of each other and linear supramolecular polymers in the solid state. Not only has it been shown that to form this kind of dimer is a unique feature associated with pillar[5]arene macrocycles but also it was demonstrated that weak van der Waals forces can be used to control the self-organization of monomers during their supramolecular polymerization process.

  20. Analysis of Doppler Radar Data about a Super Monomer Hailstorms in the Northeastern Qinghai-Tibet Plateau

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    [Objective] The Doppler radar data about a super monomer hailstorms in the northeastern Qinghai-Tibet Plateau in the Zhongchuan Airport in the Lanzhou City on September 6,2010 was studied.[Method] By dint of routine data and radar data,the low vortex shear line type and the super monomer hailstorm around the Zhongchuan Airport in the Lanzhou City on September 6,2010 were expounded.Basic product and secondary product of Doppler radar were used in this process to reflect the characteristics of strong convecti...

  1. 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)

  2. Synthesis and Ring-Opening Metathesis Polymerization of Second-Generation Dendronized Poly(ether Monomers Initiated by Ruthenium Carbenes

    Directory of Open Access Journals (Sweden)

    Guzmán Pablo E.

    2016-03-01

    Full Text Available The Ring-Opening Metathesis Polymerization (ROMP of second-generation dendronized monomers is described. Using the highly active and fast-initiating third-generation ruthenium complex [(H2IMes(pyr2Cl2RuCHPh], moderate to high molecular weight polymers (430-2230 kDa are efficiently synthesized with low dispersities (Ð = 1.01-1.17. This study highlights the power of the metathesis approach toward polymer synthesis in a context where monomer structure can significantly impede polymerization.

  3. Pressure induced enhancement of the magnetic ordering temperature in rhenium(IV) monomers

    Science.gov (United States)

    Woodall, Christopher H.; Craig, Gavin A.; Prescimone, Alessandro; Misek, Martin; Cano, Joan; Faus, Juan; Probert, Michael R.; Parsons, Simon; Moggach, Stephen; Martínez-Lillo, José; Murrie, Mark; Kamenev, Konstantin V.; Brechin, Euan K.

    2016-12-01

    Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the `transformation' from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts. Here we report the effect of pressure on two such mononuclear rhenium(IV) compounds that exhibit long-range magnetic order under ambient conditions via a spin canting mechanism, with Tc controlled by the strength of the intermolecular interactions. As these are determined by intermolecular distance, `squeezing' the molecules closer together generates remarkable enhancements in ordering temperatures, with a linear dependence of Tc with pressure.

  4. Synthesis and properties of fluorescent hybrid nanocomposites based on copolyacrylates with dansyl semicarbazide units

    Energy Technology Data Exchange (ETDEWEB)

    Buruiana, Emil C., E-mail: emilbur@icmpp.r [' Petru Poni' Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania); Chibac, Andreea L.; Buruiana, Tinca; Musteata, Valentina [' Petru Poni' Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania)

    2011-07-15

    Our study examined a series of hybrid composites containing copolyacrylate with semicarbazide-dansyl groups prepared by conventional radical polymerization of monomers in the organic montmorillonite modified with alkyl chains of variable length or using the sol-gel technique. The structure and the chemical composition of the copolymers N-methacryloyloxyethylcarbamoyl-5- (dimethylaminonaphtalene-1-sulfonohydrazine)-co-methyl metahacrylate (DnsSA-co-MMA) and N-methacryloyloxyethylcarbamoyl -5-(dimethylaminonaphtalene-1-sulfonohydrazine)-co-dodecylacrylamide (DnsSA-co-DA) as well as their nanocomposites (HC-P1, HC-P2, HC-P3, HC-P4) were confirmed by spectral analysis ({sup 1}H NMR, FTIR, UV/vis), thermal methods and atomic force microscopy. To quantify the effect of the inorganic component compared to pure photopolymers we evaluated the properties of hybrid composites, including dielectric characterization. Additionally, these materials have been tested in experiments of fluorescence quenching by acids (HCl, p-toluenesulfonic acid, 1-S-camphorsulfonic acid), metallic cation (Cu{sup 2+}) and nitrobenzene. The results suggest that such nanocomposites could find applications as fluorescence-based chemosensors in homogeneous organic solutions or thin films. - Highlights: {yields} Dansylated hybrid composites were prepared by polymerization of monomers in organo-MMT or by sol-gel. {yields} Quenching effects by acids, Cu{sup 2+} and nitrobenzene in solution/film were evidenced. {yields} A fluorescence dequenching was observed for the composite with silsesquixane units. {yields} A reversible process occurs in the composite film exposed to nitrobenzene vapors.

  5. Capture and Reversible Storage of Volatile Iodine by Novel Conjugated Microporous Polymers Containing Thiophene Units.

    Science.gov (United States)

    Qian, Xin; Zhu, Zhao-Qi; Sun, Han-Xue; Ren, Feng; Mu, Peng; Liang, Weidong; Chen, Lihua; Li, An

    2016-08-17

    Conjugated microporous polymers having thiophene building blocks (SCMPs), which originated from ethynylbenzene monomers with 2,3,5-tribromothiophene, were designedly synthesized through Pd(0)/CuI catalyzed Sonogashira-Hagihara cross-coupling polymerization. The morphologies, structure and physicochemical properties of the as-synthesized products were characterized through scanning electron microscope (SEM), thermogravimeter analysis (TGA), (13)C CP/MAS solid state NMR and Fourier transform infrared spectroscope (FTIR) spectra. Nitrogen sorption-desorption analysis shows that the as-synthesized SCMPs possesses a high specific surface area of 855 m(2) g(-1). Because of their abundant porosity, π-conjugated network structure, as well as electron-rich thiophene building units, the SCMPs show better adsorption ability for iodine and a high uptake value of 222 wt % was obtained, which can compete with those nanoporous materials such as silver-containing zeolite, metal-organic frameworks (MOFs) and conjugated microporous polymers (CMPs), etc. Our study might provide a new possibility for the design and synthesis of functional CMPs containing electron-rich building units for effective capture and reversible storage of volatile iodine to address environmental issues.

  6. Chemical Reactivity Perspective into the Group 2B Metals Halides.

    Science.gov (United States)

    Özen, Alimet Sema; Akdeniz, Zehra

    2016-06-30

    Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

  7. Manipulation of Guaiacyl and Syringyl Monomer Biosynthesis in an Arabidopsis Cinnamyl Alcohol Dehydrogenase Mutant Results in Atypical Lignin Biosynthesis and Modified Cell Wall Structure

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Nickolas A.; Tobimatsu, Yuki; Ciesielski, Peter N.; Ximenes, Eduardo; Ralph, John; Donohoe, Bryon S.; Ladisch, Michael; Chapple, Clint

    2015-08-01

    Modifying lignin composition and structure is a key strategy to increase plant cell wall digestibility for biofuel production. Disruption of the genes encoding both cinnamyl alcohol dehydrogenases (CADs), including CADC and CADD, in Arabidopsis thaliana results in the atypical incorporation of hydroxycinnamaldehydes into lignin. Another strategy to change lignin composition is downregulation or overexpression of ferulate 5-hydroxylase (F5H), which results in lignins enriched in guaiacyl or syringyl units, respectively. Here, we combined these approaches to generate plants enriched in coniferaldehyde-derived lignin units or lignins derived primarily from sinapaldehyde. The cadc cadd and ferulic acid hydroxylase1 (fah1) cadc cadd plants are similar in growth to wild-type plants even though their lignin compositions are drastically altered. In contrast, disruption of CAD in the F5H-overexpressing background results in dwarfism. The dwarfed phenotype observed in these plants does not appear to be related to collapsed xylem, a hallmark of many other lignin-deficient dwarf mutants. cadc cadd, fah1 cadc cadd, and cadd F5H-overexpressing plants have increased enzyme-catalyzed cell wall digestibility. Given that these CAD-deficient plants have similar total lignin contents and only differ in the amounts of hydroxycinnamaldehyde monomer incorporation, these results suggest that hydroxycinnamaldehyde content is a more important determinant of digestibility than lignin content.

  8. The Crystal and Molecular Structure of an Asymmetric Diacetylene Monomer, 6-(2-methyl-4-nitroanilino)-2,4-hexadiyne-1-ol

    Science.gov (United States)

    Vlasse, Marcus; Paley, Mark S.

    1993-01-01

    The crystal and molecular structure of an asymmetric diacetylene monomer has been determined from x-ray diffraction data. The crystals, obtained from an acetone/pentane solution, are orthorhombic, Fdd2 with Z = 16 in a unit cell having dimensions of a = 42.815(6) A, b = 22.224(5) A, c = 4.996(l) A. The structure was solved by direct methods and refined by least- squares techniques to an R(sub F) of 6.4% for 988 reflections and 171 variables. The diacetylene chains are disposed in the unit cell in a complex manner in order to satisfy the hydrogen- bonding, crystal packing, and symmetry requirements of the system. The solid state polymerization mechanism is discussed with respect to the geometric disposition of the diacetylene chains. These chains are far apart and incorrectly oriented with respect to each other to permit polymerization in the crystal by means of 1,4-addition, consistent with the Baughman mechanistic model.

  9. Ligand and Metal Effects on the Stability and Adsorption Properties of an Isoreticular Series of MOFs Based on T-Shaped Ligands and Paddle-Wheel Secondary Building Units.

    Science.gov (United States)

    Xiong, Ying; Fan, Yan-Zhong; Damasceno Borges, Daiane; Chen, Cheng-Xia; Wei, Zhang-Wen; Wang, Hai-Ping; Pan, Mei; Jiang, Ji-Jun; Maurin, Guillaume; Su, Cheng-Yong

    2016-11-02

    The synthesis of stable porous materials with appropriate pore size and shape for desired applications remains challenging. In this work a combined experimental/computational approach has been undertaken to tune the stability under various conditions and the adsorption behavior of a series of MOFs by subtle control of both the nature of the metal center (Co(2+) , Cu(2+) , and Zn(2+) ) and the pore surface by the functionalization of the organic linkers with amido and N-oxide groups. In this context, six isoreticular MOFs based on T-shaped ligands and paddle-wheel units with ScD0.33 topology have been synthesized. Their stabilities have been systematically investigated along with their ability to adsorb a wide range of gases (N2 , CO2 , CH4 , CO, H2, light hydrocarbons (C1 -C4 )) and vapors (alcohols and water). This study has revealed that the MOF frameworks based on Cu(2+) are more stable than their Co(2+) and Zn(2+) analogues, and that the N-oxide ligand endows the MOFs with a higher affinity for CO2 leading to excellent selectivity for this gas over other species.

  10. Synthesis and Characterization of Metal Nanoparticle Embedded Conducting Polymer–Polyoxometalate Composites

    Directory of Open Access Journals (Sweden)

    Kishore PilliSatyananda

    2007-01-01

    Full Text Available AbstractPhosphomolybdate has been employed simultaneously as the oxidizing agent for the monomer polymerization and the reduced polyoxometalate is used as reducing agent for the reduction of metal ions. The composites thus obtained have been characterized and may have many potential applications.

  11. Low-melting elemental metal or fusible alloy encapsulated polymerization initiator for delayed initiation

    Energy Technology Data Exchange (ETDEWEB)

    Hermes, Robert E.

    2017-08-15

    An encapsulated composition for polymerization includes an initiator composition for initiating a polymerization reaction, and a capsule prepared from an elemental metal or fusible alloy having a melting temperature from about 20.degree. C. to about 200.degree. C. A fluid for polymerization includes the encapsulated composition and a monomer. When the capsule melts or breaks open, the initiator is released.

  12. Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    Energy Technology Data Exchange (ETDEWEB)

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-09-06

    A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  13. Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    Science.gov (United States)

    Janke, Christopher J; Dai, Sheng; Oyola, Yatsandra

    2014-05-13

    A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  14. Toward Spatiotemporally Controlled Synthesis of Photoresponsive Polymers: Computational Design of Azobenzene-Containing Monomers for Light-Mediated ROMP.

    Science.gov (United States)

    Zhou, Qunfei; Fursule, Ishan; Berron, Brad J; Beck, Matthew J

    2016-09-15

    Density functional theory calculations have been used to identify the optimum design for a novel, light-responsive ring monomer expected to allow spatial and temporal control of ring-opening metathesis polymerization (ROMP) via light-mediated changes in ring strain energy. The monomer design leverages ring-shaped molecules composed of 4,4'-diaminoazobenzene (ABn) closed by alkene-α,ω-dioic acid linkers. The atomic geometries, formation enthalpies and ring strain energies of azobenzene (AB)-containing rings with various length linkers have been calculated. The AB(2,2) monomer is identified as having optimal properties for light-mediated ROMP, including high thermodynamic stability, low ring strain energy (RSE) with cis-AB, and high RSE with trans-AB. Time-dependent DFT calculations have been used to explore the photoisomerization mechanism of isolated AB and AB-containing rings, and calculations show that trans-to-cis and cis-to-trans photoisomerization of the optimal AB(2,2) ring molecule can be achieved with monochromatic green and blue light, respectively. The AB(2,2) monomer identified here is expected to allow precise, reversible, spatial and temporal light-mediated control of ROMP through AB photoisomerization, and to have promising potential applications in the fabrication of patterned and/or responsive AB-containing polymer materials.

  15. Interaction potential for water dimer from symmetry-adapted perturbation theory based on density functional description of monomers

    NARCIS (Netherlands)

    Bukowski, R.; Szalewicz, K.; Groenenboom, G.C.; Avoird, A. van der

    2006-01-01

    A new six-dimensional interaction potential for the water dimer has been obtained by fitting interaction energies computed at 2510 geometries using a variant of symmetry-adapted perturbation theory (SAPT) based on density functional theory (DFT) description of monomers, referred to as SAPT(DFT). The

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

    Science.gov (United States)

    Vatanpour, Vahid; Zoqi, Naser

    2017-02-01

    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 highest fouling resistance.

  17. Novel polymer composites from waste ethylene-propylene-diene-monomer rubber by supercritical CO2 foaming technology.

    Science.gov (United States)

    Jeong, Keuk Min; Hong, Yeo Joo; Saha, Prosenjit; Park, Seong Ho; Kim, Jin Kuk

    2014-11-01

    In this study, a composite has been prepared by mixing waste rubber, such as ethylene-propylene-diene-monomer and low-density poly ethylene foaming, with supercritical carbon dioxide. In order to optimise the foaming process of the waste ethylene-propylene-diene-monomer-low-density poly ethylene composite, the variations of pressure and temperature on the foamed Microcell formation were studied. As indicated in scanning electron microscope photographs, the most uniform microcellular pattern was found at 200 bar and 100 °C using 30% by weight of waste ethylene-propylene-diene-monomer. Carbon dioxide could not be dissolved uniformly during foaming owing to extensive cross-linking of the waste ethylene-propylene-diene-monomer used for the composite. As a result the presence of un-uniform microcells after foaming were observed in the composite matrix to impart inferior mechanical properties of the composite. This problem was solved with uniform foaming by increasing the cross-link density of low-density poly ethylene using 1.5 parts per hundred dicumyl peroxide that enhances composite tensile and compressive strength up to 57% and 15%, respectively. The composite has the potential to be used as a foaming mat for artificial turf.

  18. Molecular Dynamics Simulation of a Coarse Grained Model of Tetra-PEG Gel with Monomers of 5 and 9 particles

    Science.gov (United States)

    Ogawa, Shizuka; Waide, Sayaka; Takasu, Masako; Miyakawa, Takeshi; Morikawa, Ryota; Sakai, Takamasa; Chung, Ung-il

    We study the early process of gelation using our model of 5 particles and 9 particles in a monomer. We compare our models and obtain slower reaction for model of 9 particles. We also study the effect of random force and obtain slower reaction with random force but more extended structure.

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

    Energy Technology Data Exchange (ETDEWEB)

    Du, Fengxia [Laboratory of Genome Variations and Precision Bio-Medicine, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 100101 (China); Zhang, Minjie [Laboratory of Genome Variations and Precision Bio-Medicine, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 100101 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Li, Xiaohua; Yang, Caiyun [Laboratory of Genome Variations and Precision Bio-Medicine, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 100101 (China); Meng, Hao; Wang, Dong; Chang, Shuang [Laboratory of Genome Variations and Precision Bio-Medicine, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 100101 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xu, Ye [Department of Radiation Oncology, Division of Genomic Stability, Dana Farber Cancer Institute, Harvard Medical School, MA 02134 (United States); Price, Brendan, E-mail: Brendan_Price@dfci.harvard.edu [Department of Radiation Oncology, Division of Genomic Stability, Dana Farber Cancer Institute, Harvard Medical School, MA 02134 (United States); Sun, Yingli, E-mail: sunyl@big.ac.cn [Laboratory of Genome Variations and Precision Bio-Medicine, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 100101 (China)

    2014-10-03

    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.

  20. KINETIC-STUDY OF THE PHOTOINITIATED POLYMERIZATION OF A LIQUID-CRYSTALLINE DIACRYLATE MONOMER BY DSC IN THE ISOTHERMAL MODE

    NARCIS (Netherlands)

    Doornkamp, Annette; VANEKENSTEIN, GORA; TAN, YY

    1992-01-01

    The photoinitiated polymerization of the liquid crystalline (LC) diacrylate monomer 1,4-(-2-methyl phenylene)-bis[4-(6-acryloyloxy-hexamethyleneoxy)benzoate] with T(k,n) = 85-degrees-C and T(i) = 118-degrees-C, was studied by d.s.c. at various temperatures under different conditions. In the

  1. Lipase-catalyzed Regioselective Synthesis of Vinyl Ester Derivatives of Thiamphenicol: Novel Thiamphenicol Monomers for Preparation of Macromolecular Antibiotic

    Institute of Scientific and Technical Information of China (English)

    Yu Zhen SHI; Zhi Chun CHEN; Na WANG; Qi WU; Xian Fu LIN

    2005-01-01

    Three polymerizable vinyl thiamphenicol esters with different acyl donor carbon chain length (C4, C6, C10) were regioselectivly synthesized by Lipozyme(R) (immobilized from mucor miehei) in acetone at 50 ℃ for 12 h to give 73%, 81%, 63% yield, respectively. The products were valuable monomers for preparation of macromolecular antibiotic.

  2. Epoxy monomers derived from tung oil fatty acids and its regulable thermosets cured in two synergistic ways

    Science.gov (United States)

    A new bio-based epoxy monomer with conjugated double bonds, glycidyl ester of eleostearic acid (GEEA), was synthesized from tung oil fatty acids and characterized by 1H-NMR, 13C-NMR and Mass Spectrometry Analysis (MSA). Differential Scanning Calorimetry (DSC) analysis and FT-IR were utilized to inve...

  3. An epoxy monomer derived from Tung oil fatty acids and its products cured by two synergistic reactions

    Science.gov (United States)

    A new bio-based epoxy monomer containing conjugated double bonds, the glycidyl ester of eleostearic acid (GEEA), was synthesized from tung oil fatty acids. It was characterized using 1H-NMR, 13C-NMR and mass spectrometric analysis. Differential scanning calorimetry (DSC) and FT-IR spectroscopy were ...

  4. Kosterlitz-Thouless transitions and phase diagrams of the interacting monomer-dimer model on a checkerboard lattice.

    Science.gov (United States)

    Li, Sazi; Li, Wei; Chen, Ziyu

    2014-11-01

    Using the tensor network approach, we investigate the monomer-dimer models on a checkerboard lattice, in which there are interactions (with strength v) between the parallel dimers on half of the plaquettes. For the fully packed interacting dimer model, we observe a Kosterlitz-Thouless (KT) transition between the low-temperature symmetry breaking and the high-temperature critical phases; for the doped monomer-dimer case with finite chemical potential μ, we also find an order-disorder phase transition which is of second order instead. We use the boundary matrix product state approach to detect the KT and second-order phase transitions and obtain the phase diagrams v-T and μ-T. Moreover, for the noninteracting monomer-dimer model (setting μ=ν=0), we get an extraordinarily accurate determination of the free energy per site (negative of the monomer-dimer constant h_{2}) as f=-0.662798972833746 with the dimer density n=0.638123109228547, both of 15 correct digits.

  5. Novel reactions of quadricyclane: a new route to monomers for low-absorbing polymers in 157-nm photoresists

    Science.gov (United States)

    Marsella, John A.; Abdourazak, Atteye H.; Carr, Richard V. C.; Markley, Thomas J.; Robertson, Eric A., III

    2004-05-01

    Norbornene monomers with fluorinated substituents are often used in copolymers targeted for photoresist applications at 157 nm. Homopolymers of these norbornene monomers typically exhibit an absorption coefficient greater than 1.5 μm-1. Comonomers, which are often perfluoroolefins, are needed to meet the transparency requirement for 157 nm lithography, namely an absorption coefficient less than 1.0 μm-1. Clearly, a norbornene monomer that gives a homopolymer with an optical density less than 1.0 μm-1 would require less, if any, perfluoroolefin comonomer, providing a distinct advantage in the production of the base resin. Research in Air Products and Chemicals" labs has led to the discovery that fluorinated hydroxyalkyl ether derivatives of norbornene ring systems with suitable substitution patterns can give homopolymers with absorption coefficients of less than 1 μm-1. The monomers are produced via a novel reaction pathway involving quadricyclane. This pathway provides a versatile and rich synthetic chemistry, and the potential for eliminating, or at least substantially decreasing, perfluoroolefin incorporation into 157 nm photoresists. Specific examples of these reactions are discussed here, along with VUV-VASE and etch resistance data for a series of polymers derived from quadricyclane reactions.

  6. Zwitterionic Group VIII transition metal initiators supported by olefin ligands

    Science.gov (United States)

    Bazan, Guillermo C.; Chen, Yaofeng

    2011-10-25

    A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

  7. 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

  8. Effect of Rhizopus oryzae Fermentation on Kenaf-Based Polylactic Acid’s Monomer

    Directory of Open Access Journals (Sweden)

    Nur Aimi Mohd Nasir

    2011-12-01

    Full Text Available 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 cellulose into glucose- a carbon source for Rhizopus to grow. Then, the fermentation process was carried out in shake flask for 3 days at pH 6. Several conditions for fermentation process had been chosen which were 25oC at 150 rpm, 25 oC at 200 rpm, 37 oC at 150 rpm and 37oC at 200 rpm. In this fermentation process, 0.471 g/L, 0.428 g/L, 0.444 g/L and 0.38 g/L of lactic acid was produced respectively. Sample at 25oC at 200 rpm produced maximum amount of lactic acid compared to others.ABSTRAK: Biojisim kenaf berpotensi sebagai bahan mentah dalam penghasilan monomer asid polylactic (poliester alifatik termoplastik diterbitkan daripada sumber boleh diperbaharu seperti kanji jagung yang merupakan asid laktik menerusi penapaian oleh Rhizopus oryzae (sejenis fungus yang hidup dalam jirim organik yang telah mati. Struktur biojisim kenaf adalah kompleks disebabkan kandungan lignin dan selulosanya. Hal ini menyebabkan ia perlu melalui proses pra-rawatan sebagai langkah awal sebelum proses penapaian dijalankan. Dalam kertas ini, biojirim kenaf dirawat dengan asid sulfurik (H2SO4 yang dicairkan untuk menghidrolisis kandungan selulosa di dalamnya di samping menukar selulosa menjadi glukosa - sumber karbon bagi tumbesaran Rhizopus. Kemudian, proses penapaian dijalankan di dalam kelalang goncang selama 3 hari pada pH 6. Beberapa ciri proses penapaian telah dipilih iaitu 25 oC pada 150 rpm, 25 oC pada 200 rpm, 37 oC pada 150 rpm dan 37 oC pada 200 rpm. Dalam proses penapaian

  9. 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

  10. ATP-dependent regulation of actin monomer-filament equilibrium by cyclase-associated protein and ADF/cofilin.

    Science.gov (United States)

    Nomura, Kazumi; Ono, Shoichiro

    2013-07-15

    CAP (cyclase-associated protein) is a conserved regulator of actin filament dynamics. In the nematode Caenorhabditis elegans, CAS-1 is an isoform of CAP that is expressed in striated muscle and regulates sarcomeric actin assembly. In the present study, we report that CAS-2, a second CAP isoform in C. elegans, attenuates the actin-monomer-sequestering effect of ADF (actin depolymerizing factor)/cofilin to increase the steady-state levels of actin filaments in an ATP-dependent manner. CAS-2 binds to actin monomers without a strong preference for either ATP- or ADP-actin. CAS-2 strongly enhances the exchange of actin-bound nucleotides even in the presence of UNC-60A, a C. elegans ADF/cofilin that inhibits nucleotide exchange. UNC-60A induces the depolymerization of actin filaments and sequesters actin monomers, whereas CAS-2 reverses the monomer-sequestering effect of UNC-60A in the presence of ATP, but not in the presence of only ADP or the absence of ATP or ADP. A 1:100 molar ratio of CAS-2 to UNC-60A is sufficient to increase actin filaments. CAS-2 has two independent actin-binding sites in its N- and C-terminal halves, and the C-terminal half is necessary and sufficient for the observed activities of the full-length CAS-2. These results suggest that CAS-2 (CAP) and UNC-60A (ADF/cofilin) are important in the ATP-dependent regulation of the actin monomer-filament equilibrium.

  11. Aggregation of frog rhodopsin to oligomers and their dissociation to monomer: application of BN- and SDS-PAGE.

    Science.gov (United States)

    Shukolyukov, S A

    2009-06-01

    After solubilization of frog rod outer segments (ROS) with mild detergents (digitonin, n-dodecyl-beta-D-maltoside, Chaps, Triton X-100) and subsequent one-dimensional blue native polyacrylamide gel electrophoresis (1D BN-PAGE), the position of rhodopsin (Rh) on the gradient gel does not match the monomer with molecular weight of 40 kDa but appears self-associated into aggregate of Rh (RhA) with molecular mass varying in different detergents from 85 to 125 kDa. Short-term treatment (~2 h) of the excised BN-PAGE strip containing RhA by denaturing detergent mixture (10% SDS + 1 mM dithiothreitol (DTT)) followed by 2D SDS-PAGE revealed dissociation of the RhA into opsin monomer and unidentified proteins. Long-term treatment (approximately 2 days) of RhA that included extraction, denaturation, concentration, and electrophoresis induced, along with dissociation of RhA into opsin monomer + unidentified proteins, also formation of opsin dimers, trimers, and higher oligomers owing to a secondary aggregation of opsin. Direct solubilization of the ROS by harsh SDS + DTT detergent mixture followed by 1D SDS-PAGE revealed only opsin monomer that upon heating disappeared, transforming into higher oligomers owing to secondary aggregation. The data show that degree of Rh oligomerization depends on specific conditions in which it stays. In the native state in the photoreceptor membrane as well as in mild detergents frog Rh exists mainly as dimers or higher oligomers. After solubilization with denaturing detergents, RhA can dissociate into monomers that then spontaneously self-associate into higher oligomers under the influence of various factors (for example, heating).

  12. Determination of Residual Monomers Released from Soft Lining Materials with the use of HPLC

    Directory of Open Access Journals (Sweden)

    Afrodite Sofou

    2007-12-01

    Full Text Available A study was carried out to examine the post polymerized leachability of three non phthalic and four phthalic residual monomers, from twelve commercially available soft lining materials, using HPLC. Specimens of equal dimensions were constructed from each brand of material following a standardized procedure and were stored in three different conditions of storage i.e. distilled water, artificial saliva and a binary mixture of ethanol-water, with the resulting liquids providing samples for analysis in the HPLC apparatus. Three different experiments were performed for each brand of material and each condition of storage, in order to examine the parameters time and temperature. The results obtained from this study suggest that a wide spectrum of residues is diffusing out of the twelve examined soft lining materials. The non phthalic compounds were leaching at high concentrations while all the phthalates examined exhibited different degrees of elusion commensurate with the storage condition, brand of material and type of experiment. The main non phthalic component extracted from all the materials was methyl methacrylate, while the mainly extracted phthalic compound was different from each material. The level of elusion seems to be increasing dependent on time, medium of storage, and temperature as well.

  13. Graft polymerization of styryl bisphosphonate monomer onto polypropylene films for inhibition of biofilm formation.

    Science.gov (United States)

    Steinmetz, Hanna P; Rudnick-Glick, Safra; Natan, Michal; Banin, Ehud; Margel, Shlomo

    2016-11-01

    There has been increased concern during the past few decades over the role bacterial biofilms play in causing a variety of health problems, especially since they exhibit a high degree of resistance to antibiotics and are able to survive in hostile environments. Biofilms consist of bacterial aggregates enveloped by a self-produced matrix attached to the surface. Ca(2+) ions promote the formation of biofilms, and enhance their stability, viscosity, and strength. Bisphosphonates exhibit a high affinity for Ca(2+) ions, and may inhibit the formation of biofilms by acting as sequestering agents for Ca(2+) ions. Although the antibacterial activity of bisphosphonates is well known, research into their anti-biofilm behavior is still in its early stages. In this study, we describe the synthesis of a new thin coating composed of poly(styryl bisphosphonate) grafted onto oxidized polypropylene films for anti-biofilm applications. This grafting process was performed by graft polymerization of styryl bisphosphonate vinylic monomer onto O2 plasma-treated polypropylene films. The surface modification of the polypropylene films was confirmed using surface measurements, including X-ray photoelectron spectroscopy, atomic force microscopy, and water contact angle goniometry. Significant inhibition of biofilm formation was achieved for both Gram-negative and Gram-positive bacteria.

  14. Curing and toughening of epoxy resins with phosphorus containing monomers and polymers

    Energy Technology Data Exchange (ETDEWEB)

    Park, Y.R.; Park, I.Y.; Yoon, T.H. [Kwangji Inst. of Science and Technology, Kwangju (Korea, Republic of)] [and others

    1996-12-31

    Epoxy resins have been utilized in many areas, from house holds to airplanes, for the past several decades due to some exceptional properties such as low cost, good mechanical properties and excellent adhesive properties. However, low fracture toughness and flame resistance of epoxy resins have limited their applicability. Therefore, enhancing those properties have been of great interest to many researchers and scientists. As introduced by McGrath and co-workers in 1980s, the reactive thermoplastic polymers have proven to be an excellent toughener for improving not only fracture toughness but also adhesive properties without sacrificing thermo-mechanical properties and chemical resistance. Flame retardency could be improved by adding flame retardent additives which are divided into two groups; additives and reactives. However, among the additives, halogen compounds are known to be toxic gas generator and ozone depleter. Moreover, additives could be potentially leached out of the material, while reactives are inferior to additives. Recently, a reactive type phosphine oxide containing flame retardants have been introduced by McGrath and co-workers and proven to be an excellent flame retardant. In this paper, phospine oxide containing monomers were prepared and utilized as curing agents for expoxy resins, and starting materials for the polymers.

  15. Trends in water monomer adsorption and dissociation on flat insulating surfaces.

    Science.gov (United States)

    Hu, Xiao Liang; Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos

    2011-07-21

    The interaction of water with solid surfaces is key to a wide variety of industrial and natural processes. However, the basic principles that dictate how stable and in which state (intact or dissociated) water will be on a given surface are not fully understood. Towards this end, we have used density functional theory to examine water monomer adsorption on the (001) surfaces of a broad range of alkaline earth oxides, alkaline earth sulfides, alkali fluorides, and alkali chlorides. Some interesting general conclusions are arrived at: (i) on all the surfaces considered only a few specific adsorption structures are favoured; (ii) water becomes more stable upon descending the oxide and fluoride series but does not vary much upon going down the chloride and sulfide series; (iii) water is stabilised both by an increase in the lattice constant, which facilitates hydrogen bonding to the substrate, and by the flexibility of the substrate. These are also factors that favour water dissociation. We hope that this study is of some value in better understanding the surface science of water in general, and in assisting in the interpretation and design of future experiments.

  16. Dipentaerythritol penta-acrylate phosphate - an alternative phosphate ester monomer for bonding of methacrylates to zirconia

    Science.gov (United States)

    Chen, Ying; Tay, Franklin R.; Lu, Zhicen; Chen, Chen; Qian, Mengke; Zhang, Huaiqin; Tian, Fucong; Xie, Haifeng

    2016-12-01

    The present work examined the effects of dipentaerythritol penta-acrylate phosphate (PENTA) as an alternative phosphate ester monomer for bonding of methacrylate-based resins to yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) and further investigated the potential bonding mechanism involved. Shear bond strength testing was performed to evaluate the efficacy of experimental PENTA-containing primers (5, 10, 15, 20 or 30 wt% PENTA in acetone) in improving resin-Y-TZP bond strength. Bonding without the use of a PENTA-containing served as the negative control, and a Methacryloyloxidecyl dihydrogenphosphate(MDP)-containing primer was used as the positive control. Inductively coupled plasma-mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) were used to investigate the potential existence of chemical affinity between PENTA and Y-TZP. Shear bond strengths were significant higher in the 15 and 20 wt% PENTA groups. The ICP-MS, XPS and FTIR data indicated that the P content on the Y-TZP surface increased as the concentration of PENTA increased in the experimental primers, via the formation of Zr–O–P bond. Taken together, the results attest that PENTA improves resin bonding of Y-TZP through chemical reaction with Y-TZP. Increasing the concentration of PENTA augments its binding affinity but not its bonding efficacy with zirconia.

  17. Thermometric sensing of nitrofurantoin by noncovalently imprinted polymers containing two complementary functional monomers.

    Science.gov (United States)

    Athikomrattanakul, Umporn; Gajovic-Eichelmann, Nenad; Scheller, Frieder W

    2011-10-15

    Molecularly imprinted polymers (MIPs) for nitrofurantoin (NFT) recognition addressing in parallel of two complementary functional groups were created using a noncovalent imprinting approach. Specific tailor-made functional monomers were synthesized: a diaminopyridine derivative as the receptor for the imide residue and three (thio)urea derivatives for the interaction with the nitro group of NFT. A significantly improved binding of NFT to the new MIPs was revealed from the imprinting factor, efficiency of binding, affinity constants and maximum binding number as compared to previously reported MIPs, which addressed either the imide or the nitro residue. Substances possessing only one functionality (either the imide group or nitro group) showed significantly weaker binding to the new imprinted polymers than NFT. However, the compounds lacking both functionalities binds extremely weak to all imprinted polymers. The new imprinted polymers were applied in a flow-through thermistor in organic solvent for the first time. The MIP-thermistor allows the detection of NFT down to a concentration of 5 μM in acetonitrile + 0.2% dimethyl sulfoxide (DMSO). The imprinting factor of 3.91 at 0.1 mM of NFT as obtained by thermistor measurements is well comparable to the value obtained by batch binding experiments.

  18. A convenient and highly efficient synthesis of one kind of peptide nucleic acid monomer

    Directory of Open Access Journals (Sweden)

    Xuemei Tang

    2012-12-01

    Full Text Available S-Thyminyl-L-cysteine methyl ester hydrochloride (compound 1, a non-classical peptide nucleic acid monomer, was synthesized through the key intermediate, N-tert- butoxycarbonyl-S-thyminyl-L-cysteine (compound 3, which afforded from the reaction of S-thyminyl-L-cysteine hydrochloride (compound 2 with di-tert-butyl dicarbonate (Boc2O. This was followed by the esterification and deprotection of compound 3 at an overall yield of 82%. The mixture of thionyl chloride and methanol was found as an efficient reagent for simultaneous deprotection of tert-butoxycarbonyl (Boc group and esterification of carboxy group of compound 3. This high-yield two-step method was also applied to other analogues of compound 1 successfully. The chemical structures of four new compounds (5a-5d were confirmed by 1H NMR and 13C NMR.DOI: http://dx.doi.org/10.4314/bcse.v26i3.10

  19. Alternate fuels and chemicals from synthesis gas: Vinyl acetate monomer. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Richard D. Colberg; Nick A. Collins; Edwin F. Holcombe; Gerald C. Tustin; Joseph R. Zoeller

    1999-01-01

    There has been a long-standing desire on the part of industry and the U.S. Department of Energy to replace the existing ethylene-based vinyl acetate monomer (VAM) process with an entirely synthesis gas-based process. Although there are a large number of process options for the conversion of synthesis gas to VAM, Eastman Chemical Company undertook an analytical approach, based on known chemical and economic principles, to reduce the potential candidate processes to a select group of eight processes. The critical technologies that would be required for these routes were: (1) the esterification of acetaldehyde (AcH) with ketene to generate VAM, (2) the hydrogenation of ketene to acetaldehyde, (3) the hydrogenation of acetic acid to acetaldehyde, and (4) the reductive carbonylation of methanol to acetaldehyde. This report describes the selection process for the candidate processes, the successful development of the key technologies, and the economic assessments for the preferred routes. In addition, improvements in the conversion of acetic anhydride and acetaldehyde to VAM are discussed. The conclusion from this study is that, with the technology developed in this study, VAM may be produced from synthesis gas, but the cost of production is about 15% higher than the conventional oxidative acetoxylation of ethylene, primarily due to higher capital associated with the synthesis gas-based processes.

  20. Photodeposition of amorphous polydiacetylene films from monomer solutions onto transparent substrates

    Science.gov (United States)

    Paley, M. S.; Frazier, D. O.; Abdeldeyem, H.; Armstrong, S.; McManus, S. P.

    1995-01-01

    Polydiacetylenes are a very promising class of polymers for both photonic and electronic applications because of their highly conjugated structures. For these applications, high-quality thin polydiacetylene films are required. We have discovered a novel technique for obtaining such films of a polydiacetylene derivative of 2-methyl-4-nitroaniline using photodeposition from monomer solutions onto UV transparent substrates. This heretofore unreported process yields amorphous polydiacetylene films with thicknesses on the order of I micron that have optical quality superior to that of films grown by standard crystal growth techniques. Furthermore, these films exhibit good third-order nonlinear optical susceptibilities; degenerate four-wave mixing experiments give x(3) values on the order of 10(exp -8) - 10(exp -7) esu. We have conducted masking experiments which demonstrate that photodeposition occurs only where the substrate is directly irradiated, clearly indicating that the reaction occurs at the surface. Additionally, we have also been able to carry out photodeposition using lasers to form thin polymer circuits. In this work, we discuss the photodeposition of polydiacetylene thin films from solution, perform chemical characterization of these films, investigate the role of the substrate, speculate on the mechanism of the reaction, and make a preliminary determination of the third-order optical nonlinearity of the films. This simple, straightforward technique may ultimately make feasible the production of polydiacetylene thin films for technological applications.